TWI758276B - Sheet for forming protective film, method for producing sheet for forming protective film and method for producing semiconductor device - Google Patents

Sheet for forming protective film, method for producing sheet for forming protective film and method for producing semiconductor device Download PDF

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TWI758276B
TWI758276B TW106105584A TW106105584A TWI758276B TW I758276 B TWI758276 B TW I758276B TW 106105584 A TW106105584 A TW 106105584A TW 106105584 A TW106105584 A TW 106105584A TW I758276 B TWI758276 B TW I758276B
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protective film
sheet
forming
meth
layer
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TW201801160A (en
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山本大輔
米山裕之
小橋力也
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日商琳得科股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/185—Joining of semiconductor bodies for junction formation
    • 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
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dicing (AREA)
  • Adhesive Tapes (AREA)
  • Container, Conveyance, Adherence, Positioning, Of Wafer (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

A sheet for forming protective film, including a protective-film forming layer provided on a supporting sheet and a release film provide on the protective-film forming layer, wherein the surface roughness of a surface opposite to a surface of the supporting sheet on which the protective-film forming layer is provided is 0.5 μm or less, and the static friction force measured according to JIS K 7125 between the surface of the supporting sheet and a surface opposite to a surface of the release film on which the protective-film forming layer is provided is 29 N or less.

Description

保護膜形成用片、保護膜形成用片的製造方法及半導體裝置的製造方法 Sheet for forming a protective film, method for producing a sheet for forming a protective film, and method for producing a semiconductor device

本發明係關於一種保護膜形成用片、保護膜形成用片的製造方法及半導體裝置的製造方法。 The present invention relates to a sheet for forming a protective film, a method for producing the sheet for forming a protective film, and a method for producing a semiconductor device.

本申請案主張基於2016年2月22日在日本提出申請之日本特願2016-031343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. 2016-031343 for which it applied to Japan on February 22, 2016, and the content of this application is incorporated herein by reference.

近年來，業界使用稱為所謂的倒裝(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等電極之半導體晶片，將前述電極與基板接合。因此，有時晶片中的與電路面為相反側的背面裸露。 In recent years, the industry has used a mounting method called a so-called face down method to manufacture semiconductor devices. In the flip-chip method, a semiconductor wafer having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to a substrate. Therefore, the back surface of the wafer on the opposite side to the circuit surface may be exposed.

有時於該裸露之晶片背面形成有由有機材料構成之樹脂膜作為保護膜，以附有保護膜之半導體晶片之形式組入至半導體裝置中。保護膜係用以防止在切割步驟或封裝 (packaging)之後晶片產生龜裂。 In some cases, a resin film made of an organic material is formed on the backside of the exposed wafer as a protective film, and is incorporated into a semiconductor device in the form of a semiconductor wafer with a protective film. Protective film is used to prevent the dicing step or encapsulation After packaging, the wafer was cracked.

形成此種保護膜時，使用於支持片上具備有保護膜形成層之保護膜形成用片。作為前述支持片，例如使用樹脂製基材、或基材及黏著劑層等之積層結構體，有時亦對前述基材之保護膜形成層或黏著劑層等之積層面進行表面處理。前述保護膜形成用片中，保護膜形成層具有形成保護膜之功能，並且支持片能夠發揮作為切割片(dicing sheet)之功能，可謂為保護膜形成層與切割片形成為一體之保護膜形成用片。 When forming such a protective film, the sheet for protective film formation provided with the protective film forming layer on a support sheet is used. As the support sheet, for example, a resin base material or a laminated structure of a base material and an adhesive layer is used, and the laminated layer of the protective film-forming layer or the adhesive layer of the base material may also be surface-treated. In the aforementioned protective film forming sheet, the protective film forming layer has a function of forming a protective film, and the support sheet can function as a dicing sheet, which can be described as a protective film forming layer in which the protective film forming layer and the dicing sheet are integrated. Use slices.

通常，用於支持片之加工前的前述基材的單面或雙面具有凹凸形狀。原因在於，若不具有此種凹凸形狀，則將基材捲取成輥而進行保存時，基材彼此的接觸面黏附而產生黏連(blocking)，使用時無法將基材自輥捲出。若基材彼此的接觸面中至少一者具有凹凸形狀，則接觸面的面積變小，藉此可抑制黏連，從而可將基材良好地捲出。 Usually, the aforementioned base material before processing of the support sheet has a concavo-convex shape on one side or both sides. The reason is that if the base material does not have such a concave-convex shape, when the base material is wound into a roll and stored, the contact surfaces of the base materials adhere to each other to cause blocking, and the base material cannot be rolled out from the roll during use. When at least one of the contact surfaces of the base materials has a concavo-convex shape, the area of the contact surface is reduced, whereby blocking can be suppressed, and the base materials can be satisfactorily rolled out.

典型而言，使用此種具有凹凸面之基材之以往之保護膜形成用片具有如圖10所示之構成。圖10係以示意方式表示以往之保護膜形成用片的一例之剖視圖。再者，以下之說明所使用之圖式中，例如為了易於理解保護膜形成用片的特徵，方便起見，有時將成為主要部分之部分放大表示，各構成要素的尺寸比率等不一定與實際相同。 Typically, a conventional sheet for forming a protective film using such a substrate having an uneven surface has a structure as shown in FIG. 10 . FIG. 10 is a cross-sectional view schematically showing an example of a conventional protective film forming sheet. In addition, in the drawings used in the following description, for example, in order to facilitate the understanding of the characteristics of the sheet for forming a protective film, for the sake of convenience, the part that is the main part may be enlarged and shown, and the dimensional ratio of each component is not necessarily the same as the one. actually the same.

圖10所示之以往之保護膜形成用片9於支持片90上具備有保護膜形成層13，支持片90由基材91及黏著劑層12之積層結構體構成，於黏著劑層12上具備有保護膜形成層13。保護膜形成層13藉由硬化而成為保護膜。保護膜形成用片9進一步於保護膜形成層13上具備有剝離膜15，於使用保護膜形成用片9時將剝離膜15移除。保護膜形成用片9中，支持片90中的與具備有保護膜形成層13之面(表面)90a為相反側的面(背面)90b，亦即基材91中的與具備有黏著劑層12之面(表面)91a為相反側的面(背面)91b成為凹凸面。保護膜形成用片9藉由如此般使基材91的背面91b成為凹凸面，在捲取成輥時，基材91的背面91b與剝離膜15的露出面(剝離膜的表面15a)之黏附亦即黏連得到抑制。 The conventional protective film forming sheet 9 shown in FIG. 10 is provided with the protective film forming layer 13 on the support sheet 90, and the support sheet 90 is constituted by the laminated structure of the base material 91 and the adhesive layer 12, on the adhesive layer 12 The protective film forming layer 13 is provided. The protective film forming layer 13 becomes a protective film by curing. The sheet 9 for forming a protective film is further provided with a release film 15 on the protective film forming layer 13, and the release film 15 is removed when the sheet 9 for forming a protective film is used. In the sheet 9 for forming a protective film, the surface (back surface) 90b on the opposite side to the surface (surface) 90a provided with the protective film forming layer 13 in the support sheet 90, that is, the surface (back surface) 90b on the opposite side to the surface (surface) 90a provided with the protective film forming layer 13, that is, the base material 91 is provided with an adhesive layer. The surface (front surface) 91a of 12 is on the opposite side and the surface (back surface) 91b is a concavo-convex surface. In the sheet 9 for forming a protective film, by forming the back surface 91b of the base material 91 as a concavo-convex surface in this way, the back surface 91b of the base material 91 and the exposed surface of the release film 15 (the surface 15a of the release film) adhere to each other when the sheet 9 is wound into a roll. That is, adhesion is inhibited.

另一方面，將保護膜形成用片，藉由保護膜形成層貼附於半導體晶圓中的與電路面為相反側的背面，繼而，使保護膜形成層硬化，藉此於半導體晶圓的背面形成保護膜。針對此種依序積層有支持片、保護膜及半導體晶圓之積層體，進一步藉由切割而單片化為依序積層有支持片、保護膜及半導體晶片之積層體。進一步切割後，針對具備有保護膜等之狀態之半導體晶片，檢測有無破裂或缺損等破損。由於此種檢測通常係使用紅外線相機自半導體晶片的背面側經由支持片及保護膜而進行，故而對於支持片及保護膜要求具有紅外線透過性。此時，於使用保護膜形成用 片9之情形時，雖然自基材91的背面91b側對半導體晶片照射紅外線，但存在如下問題：由於基材91的背面91b為凹凸面，故而紅外線於該凹凸面發生散射，從而無法對半導體晶片進行檢測。 On the other hand, the sheet for forming a protective film is attached to the back surface of the semiconductor wafer on the opposite side to the circuit surface through the protective film forming layer, and then, the protective film forming layer is cured, whereby the surface of the semiconductor wafer is cured. A protective film is formed on the back. Such a laminate in which a support sheet, a protective film, and a semiconductor wafer are sequentially laminated is further singulated by dicing into a laminate in which a support sheet, a protective film, and a semiconductor wafer are sequentially laminated. After further dicing, the semiconductor wafer in a state with a protective film or the like is inspected for damage such as cracking or chipping. Since such detection is usually performed from the back side of the semiconductor wafer through the support sheet and the protective film using an infrared camera, the support sheet and the protective film are required to have infrared transmittance. At this time, in the use of protective film formation In the case of the sheet 9, although the semiconductor wafer is irradiated with infrared rays from the back surface 91b side of the base material 91, there is a problem that since the back surface 91b of the base material 91 is a concave and convex surface, the infrared rays are scattered on the concave and convex surface, so that the semiconductor wafer cannot be irradiated. wafers are inspected.

作為可防止此種紅外線之散射之保護膜形成用片，已知有具有如圖11所示之構成的保護膜形成用片8(例如參照專利文獻1)。圖11係以示意方式表示以往之保護膜形成用片的另一例之剖視圖。 As a sheet for forming a protective film which can prevent such scattering of infrared rays, there is known a sheet 8 for forming a protective film having a structure as shown in FIG. 11 (for example, refer to Patent Document 1). FIG. 11 is a cross-sectional view schematically showing another example of a conventional protective film forming sheet.

與保護膜形成用片9同樣地，圖11所示之以往之保護膜形成用片8係於支持片80上具備有保護膜形成層13，支持片80由基材81及黏著劑層12之積層結構體構成，於黏著劑層12上具備有保護膜形成層13。但是，支持片80中，基材81中的凹凸面之配置與支持片90中的基材91相反。亦即，保護膜形成用片8中，基材81中的具備有黏著劑層12之面(表面)81a成為凹凸面，基材81中的與表面81a為相反側的面(背面)81b成為平滑面。支持片80中的基材81、保護膜形成層13及剝離膜15分別與支持片90中的基材91、保護膜形成層13及剝離膜15相同。 Like the sheet 9 for forming a protective film, the conventional sheet 8 for forming a protective film shown in FIG. The laminated structure is constituted, and the protective film forming layer 13 is provided on the adhesive layer 12 . However, in the support sheet 80 , the arrangement of the concavo-convex surfaces in the base material 81 is opposite to that of the base material 91 in the support sheet 90 . That is, in the sheet 8 for forming a protective film, the surface (surface) 81a of the base material 81 having the adhesive layer 12 becomes the uneven surface, and the surface (back surface) 81b of the base material 81 on the opposite side to the surface 81a becomes smooth surface. The base material 81 , the protective film-forming layer 13 , and the release film 15 in the support sheet 80 are the same as the base material 91 , the protective film-forming layer 13 , and the release film 15 in the support sheet 90 , respectively.

但是，於保護膜形成用片8之情形時，基材81的背面81b成為平滑面，亦即支持片80中的與具備有黏著劑層12之面(表面)80a為相反側的面(背面)80b成為平滑面，將保 護膜形成用片8捲取成輥時，無法抑制基材81的背面81b與剝離膜15的露出面(剝離膜的表面15a)之黏附亦即黏連。因此，存在如下問題：使用時無法將保護膜形成用片8自輥捲出，或者即便捲出剝離膜15亦會自保護膜形成層13剝離。 However, in the case of the sheet 8 for forming a protective film, the back surface 81b of the base material 81 is a smooth surface, that is, the surface (back surface) on the opposite side to the surface (surface) 80a provided with the adhesive layer 12 in the support sheet 80 )80b becomes a smooth surface, which will keep the When the protective film forming sheet 8 is wound into a roll, the back surface 81b of the base material 81 and the exposed surface of the release film 15 (the surface 15a of the release film) cannot be prevented from adhering, that is, blocking. Therefore, there exists a problem that the sheet 8 for protective film formation cannot be unrolled from a roll at the time of use, or even if the peeling film 15 is unwound, it peels from the protective film forming layer 13.

[先前技術文獻] [Prior Art Literature]

[專利文獻] [Patent Literature]

專利文獻1：日本特許第5432853號公報。 Patent Document 1: Japanese Patent No. 5432853.

如此，實際情況係以往並無能夠無障礙地進行自輥的捲出及半導體晶片的紅外線檢測之保護膜形成用片。 In this way, the actual situation is that there has not been a sheet for forming a protective film that can perform unwinding from a roll and infrared detection of a semiconductor wafer without any problems.

本發明係鑒於上述情況而完成，課題在於提供一種保護膜形成用片，用以於半導體晶片的背面形成保護膜，並且該保護膜形成用片可良好地進行自輥之捲出及半導體晶片之紅外線檢測。 The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a sheet for forming a protective film for forming a protective film on the back surface of a semiconductor wafer, and which can satisfactorily perform unwinding from a roll and separation of semiconductor wafers. Infrared detection.

為了解決上述課題，本發明提供一種保護膜形成用片，係於支持片上具備有保護膜形成層，並於前述保護膜形成層上具備有剝離膜，且前述支持片中的與具備有前述保護膜形成層之側為相反側的表面的表面粗糙度為0.5μm 以下；前述支持片的前述表面以及前述剝離膜中的與具備有前述保護膜形成層之側為相反側的表面之間，依據JIS K7125所測定之靜摩擦力為29N以下。 In order to solve the above-mentioned problems, the present invention provides a sheet for forming a protective film, which includes a protective film-forming layer on a support sheet, a release film on the protective film-forming layer, and the support sheet and the protective film are provided with the protective film. The surface roughness of the surface on the opposite side of the film-forming layer is 0.5 μm Hereinafter, the static friction force measured according to JIS K7125 between the surface of the support sheet and the release film and the surface on the opposite side to the side provided with the protective film forming layer is 29N or less.

本發明之保護膜形成用片中，較佳為前述支持片具備有基材，且前述基材的表面經實施利用噴砂處理之凹凸化處理。 In the sheet for forming a protective film of the present invention, it is preferable that the support sheet includes a base material, and the surface of the base material is subjected to unevenness treatment by sandblasting.

本發明之保護膜形成用片中，較佳為前述支持片為於基材上積層黏著劑層而成。 In the sheet for forming a protective film of the present invention, it is preferable that the support sheet is formed by laminating an adhesive layer on a base material.

本發明之保護膜形成用片中，較佳為前述黏著劑層的厚度為1μm至100μm。 In the sheet for protective film formation of this invention, it is preferable that the thickness of the said adhesive bond layer is 1 micrometer - 100 micrometers.

另外，本發明提供一種保護膜形成用片的製造方法，係製造前述保護膜形成用片，且包含有以下步驟：以前述支持片中的與具備有前述保護膜形成層之側為相反側的表面的表面粗糙度成為0.5μm以下之方式，形成前述支持片與前述保護膜形成層之積層結構之步驟；以及以前述支持片中的與具備有前述保護膜形成層之側為相反側的表面以及前述剝離膜中的與具備有前述保護膜形成層之側為相反側的表面之間，以依據JIS K7125所測定之靜摩擦力成為29N以下之方式，形成前述保護膜形成層與前述剝離膜之積層結構之步驟。 In addition, the present invention provides a method for producing a sheet for forming a protective film, which comprises the step of producing the sheet for forming a protective film, and comprising the step of setting the support sheet on the opposite side to the side on which the protective film forming layer is provided. The step of forming the layered structure of the aforementioned support sheet and the aforementioned protective film-forming layer in such a manner that the surface roughness of the surface becomes 0.5 μm or less; And between the surface on the opposite side to the side provided with the protective film forming layer in the peeling film, the static friction force measured according to JIS K7125 is 29N or less, and the protective film forming layer and the peeling film are formed. The steps of the layered structure.

另外，本發明提供一種使用了前述保護膜形成用片的半導體裝置的製造方法，係包含有以下步驟：自前述保護膜形成用片移除前述剝離膜後，將前述保護膜形成層貼附 於半導體晶圓中的與設置有電路之面為相反側的背面之步驟；使貼附於前述半導體晶圓後的前述保護膜形成層硬化而形成保護膜之步驟；對前述半導體晶圓進行切割而形成半導體晶片之步驟；自前述保護膜形成用片的前述支持片側對前述半導體晶片照射紅外線，而對前述半導體晶片進行檢測之步驟；自前述支持片將前述半導體晶片與貼附於該半導體晶片的背面之保護膜一起剝離，藉此獲得附保護膜之半導體晶片之步驟；以及將前述附保護膜之半導體晶片的半導體晶片以倒裝晶片之方式連接於基板的電路面之步驟。 Further, the present invention provides a method of manufacturing a semiconductor device using the sheet for forming a protective film, comprising the step of attaching the protective film-forming layer after removing the release film from the sheet for forming a protective film. The step of forming a protective film by hardening the protective film-forming layer attached to the semiconductor wafer to form a protective film on the backside of the semiconductor wafer on the opposite side to the surface on which the circuit is arranged; dicing the semiconductor wafer The step of forming a semiconductor wafer; the step of irradiating the semiconductor wafer with infrared rays from the support sheet side of the protective film forming sheet to detect the semiconductor wafer; the step of attaching the semiconductor wafer from the support sheet to the semiconductor wafer The steps of peeling off the protective film on the back side together to obtain a semiconductor chip with protective film; and the step of flip-chip connecting the semiconductor chip of the semiconductor chip with protective film to the circuit surface of the substrate.

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

[1]一種保護膜形成用片，係於支持片上具備有保護膜形成層，並於前述保護膜形成層上具備有剝離膜；前述支持片中的與具備有前述保護膜形成層之側為相反側的表面的表面粗糙度為0.5μm以下；前述支持片的前述表面以及前述剝離膜中的與具備有前述保護膜形成層之側為相反側的表面之間，依據JIS K7125所測定之靜摩擦力為29N以下。 [1] A sheet for forming a protective film, comprising a protective film-forming layer on a support sheet, and a release film on the above-mentioned protective film-forming layer; and the side provided with the above-mentioned protective film-forming layer in the above-mentioned supporting sheet is The surface roughness of the surface on the opposite side is 0.5 μm or less; the static friction measured according to JIS K7125 between the surface of the support sheet and the release film and the surface on the opposite side to the side provided with the protective film forming layer The force is below 29N.

[2]如[1]所記載之保護膜形成用片，其中前述支持片具備有基材，且前述基材的表面經實施利用噴砂處理之凹凸化處理。 [2] The sheet for forming a protective film according to [1], wherein the support sheet includes a base material, and the surface of the base material is subjected to unevenness treatment by sandblasting.

[3]如[1]所記載之保護膜形成用片，其中前述支持片為於基材上積層黏著劑層而成。 [3] The sheet for forming a protective film according to [1], wherein the support sheet is formed by laminating an adhesive layer on a base material.

[4]如[2]所記載之保護膜形成用片，其中前述支持片為於前述基材上積層黏著劑層而成之片。 [4] The sheet for forming a protective film according to [2], wherein the support sheet is a sheet in which an adhesive layer is laminated on the base material.

[5]如[3]或[4]所記載之保護膜形成用片，其中前述黏著劑層的厚度為1μm至100μm。 [5] The sheet for forming a protective film according to [3] or [4], wherein the adhesive layer has a thickness of 1 μm to 100 μm.

[6]一種保護膜形成用片的製造方法，前述保護膜形成用片為如[1]至[5]中任一項所記載之保護膜形成用片，該保護膜形成用片的製造方法係包含有以下步驟：以前述支持片中的與具備有前述保護膜形成層之側為相反側的表面的表面粗糙度成為0.5μm以下之方式，形成前述支持片與前述保護膜形成層之積層結構之步驟；以及以前述支持片中的與具備有前述保護膜形成層之側為相反側的表面以及前述剝離膜中的與具備有前述保護膜形成層之側為相反側的表面之間，以依據JIS K7125所測定之靜摩擦力成為29N以下之方式，形成前述保護膜形成層與前述剝離膜之積層結構之步驟。 [6] A method for producing a sheet for forming a protective film, wherein the sheet for forming a protective film is the sheet for forming a protective film according to any one of [1] to [5], and a method for producing the sheet for forming a protective film The system comprises the following steps: in the above-mentioned support sheet, the surface roughness of the surface on the opposite side with the side provided with the aforementioned protective film forming layer becomes the mode below 0.5 μm, forming the above-mentioned supporting sheet and the above-mentioned protective film forming layer. The step of the structure; And between the surface on the opposite side with the side with the aforementioned protective film forming layer in the aforementioned support sheet and the surface on the opposite side with the side with the aforementioned protective film forming layer in the aforementioned peeling film, The step of forming the laminate structure of the protective film forming layer and the peeling film so that the static friction force measured according to JIS K7125 becomes 29N or less.

[7]一種半導體裝置的製造方法，係包含有以下步驟：自如[1]至[5]中任一項所記載之保護膜形成用片移除前述剝離膜後，將前述保護膜形成層貼附於半導體晶圓中的與設置有電路之面為相反側的背面之步驟；使貼附於前述半導體晶圓後的前述保護膜形成層硬化而形成保護膜之步驟；對形成有前述保護膜之半導體晶圓進行切割而形成半導體晶片之步驟；自前述保護膜形成用片的前述支持片側對前述半導體晶片照射紅外線，而對前述半導體晶片進行檢測之步驟；自前述支持片將前述半導體晶片與貼附於 該半導體晶片的背面之保護膜一起剝離，藉此獲得附保護膜之半導體晶片之步驟；以及將前述附保護膜之半導體晶片的半導體晶片以倒裝晶片之方式連接於基板的電路面之步驟。 [7] A method of manufacturing a semiconductor device, comprising the steps of: after removing the peeling film from the protective film forming sheet according to any one of [1] to [5], and then attaching the protective film forming layer The step of attaching the back surface of the semiconductor wafer on the opposite side to the surface provided with the circuit; the step of hardening the protective film forming layer attached to the semiconductor wafer to form a protective film; the step of forming the protective film The step of dicing the semiconductor wafer to form a semiconductor chip; the step of irradiating the semiconductor chip with infrared rays from the support sheet side of the protective film forming sheet to detect the semiconductor chip; attached to The protective film on the backside of the semiconductor chip is peeled off together to obtain a semiconductor chip with protective film; and the semiconductor chip of the semiconductor chip with protective film is flip-chip connected to the circuit surface of the substrate.

根據本發明，提供一種保護膜形成用片，用以於半導體晶片的背面形成保護膜，並且該保護膜形成用片可良好地進行自輥之捲出及半導體晶片之紅外線檢測。 According to the present invention, there is provided a sheet for forming a protective film for forming a protective film on the back surface of a semiconductor wafer, and which can satisfactorily perform unwinding from a roll and infrared detection of a semiconductor wafer.

1A、1B、1C、1D、1E、1F、1G、1H、8、9:保護膜形成用片 1A, 1B, 1C, 1D, 1E, 1F, 1G, 1H, 8, 9: Sheets for forming protective films

10、80、90:支持片 10, 80, 90: Support sheet

10a、80a、90a:支持片的表面 10a, 80a, 90a: the surface of the support sheet

10b、80b、90b:支持片的背面(露出面) 10b, 80b, 90b: the back side of the support sheet (exposed side)

11、81、91:基材 11, 81, 91: Substrate

11a、81a、91a:基材的表面 11a, 81a, 91a: the surface of the substrate

11b、81b、91b:基材的背面 11b, 81b, 91b: backside of substrate

12:黏著劑層 12: Adhesive layer

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

13、23:保護膜形成層 13, 23: Protective film forming layer

13a、23a:保護膜形成層的表面 13a, 23a: Surface of protective film forming layer

14:塗層 14: Coating

14a:塗層的表面 14a: Surface of coating

14b:塗層的背面 14b: The backside of the coating

15:剝離膜 15: Peel off film

15a:剝離膜的表面 15a: Surface of release film

15b:剝離處理面 15b: Peel off the treated surface

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 adhesive layer for jig

圖1係以示意方式表示本發明之保護膜形成用片的一實施形態之剖視圖。 FIG. 1 is a cross-sectional view schematically showing an embodiment of the sheet for forming a protective film of the present invention.

圖2係以示意方式表示本發明之保護膜形成用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 sheet for forming a protective film of the present invention.

圖3係以示意方式表示本發明之保護膜形成用片的又一實施形態之剖視圖。 3 is a cross-sectional view schematically showing still another embodiment of the sheet for forming a protective film of the present invention.

圖4係以示意方式表示本發明之保護膜形成用片的又一實施形態之剖視圖。 4 is a cross-sectional view schematically showing still another embodiment of the sheet for forming a protective film of the present invention.

圖5係以示意方式表示本發明之保護膜形成用片的又一實施形態之剖視圖。 5 is a cross-sectional view schematically showing still another embodiment of the sheet for forming a protective film of the present invention.

圖6係以示意方式表示本發明之保護膜形成用片的又一實施形態之剖視圖。 6 is a cross-sectional view schematically showing still another embodiment of the sheet for forming a protective film of the present invention.

圖7係以示意方式表示本發明之保護膜形成用片的又 一實施形態之剖視圖。 FIG. 7 is another schematic diagram showing the sheet for forming a protective film of the present invention. A cross-sectional view of an embodiment.

圖8係以示意方式表示本發明之保護膜形成用片的又一實施形態之剖視圖。 FIG. 8 is a cross-sectional view schematically showing still another embodiment of the sheet for forming a protective film of the present invention.

圖9係用以說明圖2所示之保護膜形成用片的製造方法的一例之剖視圖。 FIG. 9 is a cross-sectional view for explaining an example of a method of manufacturing the protective film-forming sheet shown in FIG. 2 .

圖10係以示意方式表示以往之保護膜形成用片的一例之剖視圖。 FIG. 10 is a cross-sectional view schematically showing an example of a conventional protective film forming sheet.

圖11係以示意方式表示以往之保護膜形成用片的另一例之剖視圖。 FIG. 11 is a cross-sectional view schematically showing another example of a conventional protective film forming sheet.

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

本發明之保護膜形成用片係於支持片上具備有保護膜形成層，並於前述保護膜形成層上具備有剝離膜；前述支持片中的與具備有前述保護膜形成層之側為相反側的表面的表面粗糙度為0.5μm以下；前述支持片的前述表面以及前述剝離膜中的與具備有前述保護膜形成層之側為相反側的表面之間，依據JIS K7125所測定之靜摩擦力為29N以下。 The sheet for forming a protective film of the present invention includes a protective film-forming layer on a support sheet, and a release film on the protective film-forming layer; the support sheet is on the opposite side to the side on which the protective film-forming layer is provided The surface roughness of the surface is 0.5 μm or less; the static friction force measured according to JIS K7125 is Below 29N.

針對本發明之保護膜形成用片，移除前述剝離膜後，藉由前述保護膜形成層，貼附於半導體晶圓中的與設置有電路之面為相反側的表面(背面)。然後，於任一階段藉由使前述保護膜形成層硬化而形成保護膜。然後，針對依序積層有支持片、保護膜或保護膜形成層、及半導體晶圓之 積層體，進一步藉由切割而單片化為依序積層有支持片、保護膜或保護膜形成層、及半導體晶片之積層體。將半導體晶片，最終以於該半導體晶片的背面具備有保護膜之狀態，自支持片拾取。如此，本發明之保護膜形成用片用以於半導體晶片的背面形成保護膜。 The sheet for forming a protective film of the present invention is attached to the surface (back surface) opposite to the surface on which the circuit is provided in the semiconductor wafer through the protective film forming layer after removing the peeling film. Then, a protective film is formed by hardening the said protective film forming layer at any stage. Then, for the sequential lamination of the support sheet, the protective film or the protective film forming layer, and the semiconductor wafer The laminated body is further divided into pieces by dicing into a laminated body in which a support sheet, a protective film or a protective film forming layer, and a semiconductor wafer are laminated in this order. The semiconductor wafer is finally picked up from the support sheet in a state where a protective film is provided on the back surface of the semiconductor wafer. Thus, the sheet for protective film formation of this invention is used for forming a protective film on the back surface of a semiconductor wafer.

另一方面，針對支持片、保護膜或保護膜形成層、及半導體晶片依序積層而成之積層體，保持該狀態不變而檢測半導體晶片中有無破裂或缺損等破損。此種檢測通常以下述方式進行：自支持片中的與具備有保護膜或保護膜形成層之側為相反側(背面側)(換言之，自保護膜形成用片的支持片側)照射紅外線，並使用紅外線相機自半導體晶片的背面側經由支持片及保護膜或保護膜形成層而進行。此時，於使用本發明之保護膜形成用片之情形時，前述支持片中的與具備有前述保護膜形成層之側為相反側的表面(背面)的表面粗糙度為0.5μm以下，前述表面(背面)為平滑面，或者成為凹凸度低的面。因此，可抑制紅外線於支持片的前述表面(背面)發生散射，故而可良好地進行上述紅外線檢測。 On the other hand, with respect to a laminate in which a support sheet, a protective film or a protective film-forming layer, and a semiconductor wafer are sequentially laminated, the semiconductor wafer is inspected for damage such as cracking or chipping while maintaining this state. This kind of detection is usually carried out in the following manner: from the side with the protective film or the protective film forming layer in the supporting sheet is the opposite side (back side) (in other words, from the supporting sheet side of the protective film forming sheet) irradiating infrared rays, and It is performed from the back surface side of a semiconductor wafer via a support sheet and a protective film or a protective film forming layer using an infrared camera. At this time, when the sheet for forming a protective film of the present invention is used, the surface roughness of the surface (back surface) on the opposite side to the side provided with the protective film forming layer in the supporting sheet is 0.5 μm or less, and the above The front surface (back surface) is a smooth surface or a surface with low unevenness. Therefore, since the scattering of infrared rays on the surface (back surface) of the support sheet can be suppressed, the above-mentioned infrared detection can be performed favorably.

再者，本發明中，所謂「表面粗糙度」，只要無特別說明，則意指JIS B0601：2001中所規定之所謂算術平均粗糙度(Ra)。 In addition, in this invention, the "surface roughness" means the so-called arithmetic mean roughness (Ra) prescribed|regulated by JIS B0601:2001 unless otherwise specified.

另外，本發明之保護膜形成用片中，前述支持片的前 述表面(背面)以及前述剝離膜中的與具備有前述保護膜形成層之側為相反側的表面之間的靜摩擦力為29N以下，藉此在捲取成輥時，黏連得到抑制。因此，對於本發明之保護膜形成用片，在自輥捲出時，未確認到剝離膜剝離等異常，而可良好地捲出。前述靜摩擦力依存於前述支持片的前述表面以及前述剝離膜中的與具備有前述保護膜形成層之側為相反側的表面之間所決定之靜摩擦係數。 In addition, in the sheet for forming a protective film of the present invention, the front side of the support sheet is The static friction force between the surface (back surface) and the surface opposite to the side provided with the protective film forming layer of the release film is 29 N or less, whereby blocking is suppressed when wound into a roll. Therefore, when the sheet for protective film formation of this invention was unrolled from a roll, abnormality, such as peeling of a peeling film, was not confirmed, but it can roll out favorably. The static friction force depends on the static friction coefficient determined between the surface of the support sheet and the surface of the release film and the surface opposite to the side provided with the protective film forming layer.

再者，本發明中，所謂「靜摩擦力」只要無特別說明，則意指依據JIS K7125所測定之靜摩擦力。 In addition, in this invention, the "static frictional force" means the static frictional force measured based on JISK7125 unless otherwise specified.

本說明書中，對於前述保護膜形成用片中，藉由加熱或照射能量線使保護膜形成層硬化成保護膜之保護膜形成用片，亦只要維持前述支持片及保護膜之積層結構，則稱為保護膜形成用片。另外，對於前述保護膜形成用片中，例如於前述支持片具備有黏著劑層之情形時，該黏著劑層經硬化之保護膜形成用片，亦只要維持黏著劑層的硬化物、及保護膜形成層或保護膜等之積層結構，則稱為保護膜形成用片。 In this specification, among the above-mentioned sheet for forming a protective film, the sheet for forming a protective film in which the protective film-forming layer is cured into a protective film by heating or irradiating energy rays, as long as the laminated structure of the above-mentioned supporting sheet and protective film is maintained, It is called the sheet for protective film formation. In addition, in the aforementioned sheet for forming a protective film, for example, when the aforementioned support sheet is provided with an adhesive layer, the sheet for forming a protective film in which the adhesive layer is cured only needs to maintain the cured product of the adhesive layer and the protection The laminated structure of the film forming layer or the protective film is called a protective film forming sheet.

作為前述支持片，例如可列舉具備有基材之支持片，作為此種支持片，例如可列舉：僅由基材構成之片；以及於基材上積層黏著劑層、中間層、塗層等其他層而成之片。前述其他層可僅為一層(單層)，亦可為兩層以上之複數層；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。 As the aforementioned support sheet, for example, a support sheet provided with a base material is exemplified, and as such a support sheet, for example, a sheet composed of only a base material, and an adhesive layer, an intermediate layer, a coating layer, etc., are laminated on the base material. Pieces of other layers. The aforementioned other layers 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. Also, the combination of these plural layers is not particularly limited.

再者，本說明書中，並不限於前述其他層之情形，所謂「複數層相互可相同亦可不同」意指「可全部層相同，亦可全部層皆不相同，還可僅一部分層相同」，進一步所謂「複數層相互不同」意指「各層的材質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 other layers described above, and the phrase "a plurality of layers may be the same or different from each other" means "all layers may be the same, all layers may be different, or only a part of the layers may be the same." , and further, "a plurality of layers are different from each other" means "at least one of the material and thickness of each layer is different from each other".

如此，本發明中，可使用各種形態之片作為前述支持片。本發明之保護膜形成用片中，所謂表面粗糙度為0.5μm以下之「支持片中的與具備有保護膜形成層之側為相反側的表面」意指支持片中，上述紅外線檢測時被直接照射紅外線之最外層所露出之表面。 In this way, in the present invention, sheets of various forms can be used as the aforementioned support sheet. In the sheet for forming a protective film of the present invention, "the surface on the opposite side of the support sheet to the side provided with the protective film forming layer" having a surface roughness of 0.5 μm or less means that the support sheet is Directly irradiate the exposed surface of the outermost layer of infrared rays.

另一方面，本發明之保護膜形成用片中，所謂與支持片中具有此種表面粗糙度(0.5μm以下)之表面之間的靜摩擦力為29N以下之「剝離膜中的與具備有保護膜形成層之側為相反側的表面」意指如上所述般將保護膜形成用片捲取成輥時以及鄰接之支持片的前述最外層直接接觸之剝離膜所露出之表面。通常，該露出之表面為未經剝離處理之面。 On the other hand, in the sheet for forming a protective film of the present invention, the static friction force with the surface having such a surface roughness (0.5 μm or less) in the support sheet is 29 N or less, which refers to “a release film with a protective "The surface on the opposite side of the film-forming layer" means the surface exposed by the peeling film that is in direct contact with the outermost layer of the adjacent support sheet when the protective film-forming sheet is wound up into a roll as described above. Typically, the exposed surface is the surface that has not been stripped.

以下，按照支持片的每個種類，對本發明之保護膜形成用片進行說明。 Hereinafter, the sheet for forming a protective film of the present invention will be described for each type of the support sheet.

圖1係以示意方式表示本發明之保護膜形成用片的一 實施形態之剖視圖。 FIG. 1 schematically shows a part of the sheet for forming a protective film of the present invention. Cross-sectional view of the embodiment.

再者，以下之說明所使用之圖中，為了易於理解本發明的特徵，方便起見，有時將成為主要部分之部分放大表示，各構成要素的尺寸比率等不一定與實際相同。 In addition, in the drawings used in the following description, in order to facilitate the understanding of the characteristics of the present invention, the main parts may be shown enlarged for convenience, and the dimensional ratios and the like of the respective components are not necessarily the same as the actual ones.

圖1所示之保護膜形成用片1A於基材11上具備有黏著劑層12，於黏著劑層12上具備有保護膜形成層13。支持片10為基材11及黏著劑層12之積層體；保護膜形成用片1A具有於支持片10的一表面10a上積層有保護膜形成層13之構成。另外，保護膜形成用片1A進一步於保護膜形成層13上具備有剝離膜15。 The sheet 1A for protective film formation shown in FIG. 1 is provided with the adhesive bond layer 12 on the base material 11, and is provided with the protective film formation layer 13 on the adhesive bond layer 12. The support sheet 10 is a laminate of a base material 11 and an adhesive layer 12 ; the protective film forming sheet 1A has a structure in which a protective film forming layer 13 is laminated on one surface 10 a of the support sheet 10 . Moreover, the sheet 1A for protective film formation is equipped with the release film 15 on the protective film formation layer 13 further.

保護膜形成用片1A中，於基材11的一表面11a積層有黏著劑層12，於黏著劑層12的表面12a(黏著劑層12中的與和基材11接觸之面為相反側的面)的整個表面積層有保護膜形成層13，於保護膜形成層13的表面13a(保護膜形成層13中的與和黏著劑層12接觸之面為相反側的面)的一部分積層有治具用接著劑層16，於保護膜形成層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層13接觸之面為相反側的面以及側面)積層有剝離膜15。 In the protective film forming sheet 1A, the adhesive layer 12 is laminated on one surface 11a of the substrate 11, and the surface 12a of the adhesive layer 12 (the surface of the adhesive layer 12 in contact with the substrate 11 is the opposite side). The protective film-forming layer 13 is layered over the entire surface area of the protective film-forming layer 13, and a part of the surface 13a of the protective film-forming layer 13 (the surface on the opposite side of the protective film forming layer 13 that is in contact with the adhesive layer 12) is laminated with a protective film forming layer. The adhesive layer 16 for the jig is not laminated on the surface 13a of the protective film forming layer 13, and the surface 16a (the upper surface of the adhesive layer 16 for the jig, that is, the adhesive layer for the jig) is not laminated. The release film 15 is laminated on the surface of the agent layer 16 that is in contact with the protective film forming layer 13 (the surface on the opposite side and the side surface).

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

保護膜形成用片1A中，支持片10中的與具備有保護膜形成層13之側的表面(支持片的表面10a)為相反側的表面(以下，有時稱為支持片的背面)10b換言之基材11中的與具備有黏著劑層12之側的表面11a為相反側的表面(以下，有時稱為基材的背面)11b的表面粗糙度為0.5μm以下。 In the protective film forming sheet 1A, the surface (hereinafter, sometimes referred to as the back surface of the supporting sheet) 10b opposite to the surface on the side having the protective film forming layer 13 (the surface 10a of the supporting sheet) in the supporting sheet 10 In other words, the surface roughness of the surface 11b on the opposite side to the surface 11a on the side including the adhesive layer 12 in the base material 11 (hereinafter sometimes referred to as the back surface of the base material) is 0.5 μm or less.

另外，保護膜形成用片1A中，支持片10的前述背面10b以及剝離膜15中的與具備有保護膜形成層13之側的表面(以下，有時稱為剝離膜的背面)為相反側的表面(剝離膜的表面15a)之間的靜摩擦力為29N以下。 In addition, in the sheet 1A for forming a protective film, the back surface 10b of the support sheet 10 and the surface on the side including the protective film forming layer 13 (hereinafter, sometimes referred to as the back surface of the release film) of the support sheet 10 and the release film 15 are on the opposite side The static frictional force between the surfaces (surface 15a of the release film) is 29N or less.

圖1所示之保護膜形成用片1A係以下述方式使用：在移除剝離膜15之狀態下，於保護膜形成層13的表面13a貼附半導體晶圓(省略圖示)的背面，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 sheet 1A for forming a protective film shown in FIG. 1 is used by attaching the back surface of a semiconductor wafer (not shown) to the surface 13a of the protective film forming layer 13 with the release film 15 removed, and further The upper surface of the surface 16a of the adhesive layer 16 for a jig is attached to a jig such as a ring frame.

圖2係以示意方式表示本發明之保護膜形成用片的另一實施形態之剖視圖。再者，圖2中，對與圖1所示相同的構成要素，標附與圖1之情形相同的符號，並省略該符號的詳細說明。於圖3以後的圖中亦相同。 FIG. 2 is a cross-sectional view schematically showing another embodiment of the sheet for forming a protective film of the present invention. In addition, in FIG. 2, the same code|symbol as in the case of FIG. 1 is attached|subjected to the same component as shown in FIG.1, and the detailed description of the code|symbol is abbreviate|omitted. The same applies to the figures after FIG. 3 .

關於圖2所示之保護膜形成用片1B，除不具備有治具 用接著劑層16之方面以外，與圖1所示之保護膜形成用片1A相同。亦即，保護膜形成用片1B中，於基材11的一表面11a積層有黏著劑層12，於黏著劑層12的表面12a(黏著劑層12中的與和基材11接觸之面為相反側的面)的整個表面積層有保護膜形成層13，於保護膜形成層13的表面13a(保護膜形成層13中的與和黏著劑層12接觸之面為相反側的面)的整個表面積層有剝離膜15。 Regarding the sheet 1B for forming a protective film shown in FIG. 2, except that it does not have a jig Except for the point of using the adhesive layer 16, it is the same as the sheet 1A for forming a protective film shown in FIG. 1 . That is, in the sheet 1B for forming a protective film, the adhesive layer 12 is laminated on one surface 11a of the substrate 11, and the surface 12a of the adhesive layer 12 (the surface of the adhesive layer 12 that is in contact with the substrate 11 is The entire surface area layer of the protective film forming layer 13 is provided on the entire surface area layer of the opposite side), and the entire surface 13a of the protective film forming layer 13 (the surface of the protective film forming layer 13 that is in contact with the adhesive layer 12 is the surface on the opposite side) The surface layer has a release film 15 .

保護膜形成用片1B中，支持片10的前述背面10b(支持片10中的與和保護膜形成層13接觸之面為相反側的面)換言之基材11的前述背面11b(基材11中的與和黏著劑層12接觸之面為相反側的面)的表面粗糙度為0.5μm以下。 In the sheet 1B for forming a protective film, the back surface 10b of the support sheet 10 (the surface of the support sheet 10 that is in contact with the protective film forming layer 13 is the surface on the opposite side), in other words, the back surface 11b of the base material 11 (in the base material 11 ). The surface roughness of the surface that is in contact with the adhesive layer 12 is the surface on the opposite side) is 0.5 μm or less.

另外，保護膜形成用片1B中，支持片10的前述背面10b與剝離膜15的前述表面15a之間的靜摩擦力為29N以下。 Moreover, in the sheet 1B for protective film formation, the static frictional force between the said back surface 10b of the support sheet 10 and the said surface 15a of the peeling film 15 is 29 N or less.

圖2所示之保護膜形成用片1B係以下述方式使用：在移除剝離膜15之狀態下，於保護膜形成層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，進一步將保護膜形成層13中的包圍半導體晶圓之周緣部附近的區域貼附於環狀框等治具。 The sheet 1B for forming a protective film shown in FIG. 2 is used in a state where the release film 15 is removed, and a semiconductor wafer (omitted) is attached to a partial area on the center side of the surface 13a of the protective film forming layer 13 On the back surface of the figure), the region surrounding the periphery of the semiconductor wafer in the protective film forming layer 13 is further attached to a jig such as a ring frame.

圖3係以示意方式表示本發明之保護膜形成用片的又一實施形態之剖視圖。 3 is a cross-sectional view schematically showing still another embodiment of the sheet for forming a protective film of the present invention.

關於圖3所示之保護膜形成用片1C，除不具備有黏著 劑層12之方面以外，與圖1所示之保護膜形成用片1A相同。亦即，保護膜形成用片1C中，支持片10僅由基材11構成。並且，於基材11的一表面11a積層有保護膜形成層13，於保護膜形成層13的表面13a(保護膜形成層13中的與和基材接觸之面為相反側的面)的一部分積層有治具用接著劑層16，於保護膜形成層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層13接觸之面為相反側的面以及側面)積層有剝離膜15。 Regarding the protective film forming sheet 1C shown in FIG. 3 , except that it does not have adhesive Except the point of the agent layer 12, it is the same as the sheet 1A for protective film formation shown in FIG. That is, in the sheet 1C for forming a protective film, the support sheet 10 is constituted only by the base material 11 . In addition, the protective film forming layer 13 is laminated on one surface 11a of the base material 11, and a part of the surface 13a of the protective film forming layer 13 (the surface on the opposite side of the protective film forming layer 13 that is in contact with the base material) The adhesive layer 16 for a jig is laminated, the surface 13a of the protective film forming layer 13 on which the adhesive layer 16 for a jig is not laminated, and the surface 16a of the adhesive layer 16 for a jig (the upper surface, that is, the surface of the adhesive layer 16) The release film 15 is laminated on the surface and the side surface of the adhesive layer 16 which are in contact with the protective film forming layer 13 (the surface and the side surface on the opposite side).

保護膜形成用片1C中，支持片10的前述背面10b(支持片10中的與和保護膜形成層13接觸之面為相反側的面)換言之基材11的前述背面11b(基材11中的與和保護膜形成層13接觸之面為相反側的面)的表面粗糙度為0.5μm以下。 In the protective film-forming sheet 1C, the back surface 10b of the support sheet 10 (the surface of the support sheet 10 that is in contact with the protective film-forming layer 13 is the surface on the opposite side), in other words, the back surface 11b of the base material 11 (in the base material 11 ). The surface roughness of the surface which is in contact with the protective film forming layer 13 is the surface on the opposite side) is 0.5 μm or less.

另外，保護膜形成用片1C中，支持片10的前述背面10b與剝離膜15的前述表面15a之間的靜摩擦力為29N以下。 Moreover, in the sheet 1C for protective film formation, the static frictional force between the said back surface 10b of the support sheet 10, and the said surface 15a of the peeling film 15 is 29 N or less.

圖3所示之保護膜形成用片1C係以下述方式使用：與圖1所示之保護膜形成用片1A同樣地，在移除剝離膜15之狀態下，於保護膜形成層13的表面13a貼附半導體晶圓(省略圖示)的背面，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 sheet 1C shown in FIG. 3 is used in the same manner as the protective film forming sheet 1A shown in FIG. 13a is attached to the back surface of the semiconductor wafer (not shown), and the upper surface of the front surface 16a of the adhesive layer 16 for a jig is attached to a jig such as a ring frame.

圖4係以示意方式表示本發明之保護膜形成用片的又一實施形態之剖視圖。 4 is a cross-sectional view schematically showing still another embodiment of the sheet for forming a protective film of the present invention.

關於圖4所示之保護膜形成用片1D，除不具備有治具用接著劑層16之方面以外，與圖3所示之保護膜形成用片1C相同。亦即，保護膜形成用片1D中，於基材11的一表面11a積層有保護膜形成層13，於保護膜形成層13的表面13a(保護膜形成層13中的與和基材接觸之面為相反側的面)的整個表面積層有剝離膜15。 The sheet 1D for forming a protective film shown in FIG. 4 is the same as the sheet 1C for forming a protective film shown in FIG. 3 except that the adhesive layer 16 for a jig is not provided. That is, in the sheet 1D for forming a protective film, the protective film forming layer 13 is laminated on the one surface 11a of the base material 11, and the surface 13a of the protective film forming layer 13 (the part of the protective film forming layer 13 that is in contact with the base material) A release film 15 is provided on the entire surface area layer of the surface on the opposite side.

保護膜形成用片1D中，支持片10的前述背面10b(支持片10中的與和保護膜形成層13接觸之面為相反側的面)換言之基材11的前述背面11b(基材11中的與和保護膜形成層13接觸之面為相反側的面)的表面粗糙度為0.5μm以下。 In the protective film-forming sheet 1D, the back surface 10b of the support sheet 10 (the surface of the support sheet 10 that is in contact with the protective film-forming layer 13 is the surface on the opposite side), in other words, the back surface 11b of the base material 11 (in the base material 11 ). The surface roughness of the surface which is in contact with the protective film forming layer 13 is the surface on the opposite side) is 0.5 μm or less.

另外，保護膜形成用片1D中，支持片10的前述背面10b與剝離膜15的前述表面15a之間的靜摩擦力為29N以下。 Moreover, in the sheet 1D for protective film formation, the static frictional force between the said back surface 10b of the support sheet 10 and the said surface 15a of the peeling film 15 is 29N or less.

圖4所示之保護膜形成用片1D係以下述方式使用：與圖2所示之保護膜形成用片1B同樣地，在移除剝離膜15之狀態下，於保護膜形成層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，進一步將保護膜形成層13中的包圍半導體晶圓之周緣部附近的區域貼附於環狀框等治具。 The protective film forming sheet 1D shown in FIG. 4 is used in the same manner as the protective film forming sheet 1B shown in FIG. The back surface of the semiconductor wafer (not shown) is attached to a part of the central region of 13a, and the region surrounding the periphery of the semiconductor wafer in the protective film forming layer 13 is attached to a jig such as a ring frame.

圖5係以示意方式表示本發明之保護膜形成用片的又一實施形態之剖視圖。 5 is a cross-sectional view schematically showing still another embodiment of the sheet for forming a protective film of the present invention.

關於圖5所示之保護膜形成用片1E，除於基材11中的與具備有黏著劑層12之側為相反側的表面(以下，有時稱為基材的背面)11b上具備有塗層14之方面以外，與圖1所示之保護膜形成用片1A相同。 The sheet 1E for forming a protective film shown in FIG. 5 is provided with a surface (hereinafter, sometimes referred to as the back surface of the base material) 11 b on the opposite side to the side provided with the adhesive layer 12 in the base material 11 . Except for the coating layer 14, it is the same as the sheet 1A for forming a protective film shown in FIG. 1 .

亦即，保護膜形成用片1E中，支持片10為塗層14、基材11及黏著劑層12依序積層而成之積層體；保護膜形成用片1E具有於支持片10的一表面10a上積層有保護膜形成層13之構成。並且，於基材11的一表面11a積層有黏著劑層12，於黏著劑層12的表面12a(黏著劑層12中的與和基材11接觸之面為相反側的面)的整個表面積層有保護膜形成層13，於保護膜形成層13的表面13a(保護膜形成層13中的與和黏著劑層12接觸之面為相反側的面)的一部分積層有治具用接著劑層16，於保護膜形成層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層13接觸之面為相反側的面以及側面)積層有剝離膜15。 That is, in the sheet 1E for forming a protective film, the support sheet 10 is a laminate in which the coating layer 14, the base material 11 and the adhesive layer 12 are sequentially laminated; A protective film forming layer 13 is laminated on 10a. In addition, an adhesive layer 12 is laminated on one surface 11a of the substrate 11, and the entire surface area of the surface 12a of the adhesive layer 12 (the surface of the adhesive layer 12 that is in contact with the substrate 11 is the opposite side) is layered. The protective film forming layer 13 is provided, and the adhesive layer 16 for a jig is laminated on a part of the surface 13a of the protective film forming layer 13 (the surface on the opposite side of the protective film forming layer 13 that is in contact with the adhesive layer 12 ). , on the surface 13a of the protective film forming layer 13, the surface on which the adhesive layer 16 for jig is not laminated, and the surface 16a of the adhesive layer 16 for jig (the upper surface, that is, the surface of the adhesive layer 16 for jig and the surface 16a of the adhesive layer 16 for jig). A release film 15 is laminated on the surface in contact with the protective film forming layer 13 (the surface on the opposite side and the side surface).

另外，基材11中的與具備有黏著劑層12之面(以下，有時稱為基材的表面)11a為相反側的面(以下，有時稱為基材的背面)11b成為凹凸面。並且，塗層14係被覆該凹凸面而設置，塗層14中的與和基材11接觸之面(以下，有時稱為塗層的表面)14a為相反側的面(以下，有時稱為塗層的背 面)14b相較於基材11的前述背面11b而言，表面粗糙度Ra變小。並且，塗層14的前述背面14b換言之支持片10中的前述背面10b(支持片10中的與和保護膜形成層13接觸之面為相反側的面)的表面粗糙度為0.5μm以下。此處，塗層14發揮作為提高支持片10的背面(亦即露出面)的平滑度之層之功能。 In addition, the surface (hereinafter, sometimes referred to as the back surface of the substrate) 11b on the opposite side to the surface provided with the adhesive layer 12 (hereinafter, sometimes referred to as the surface of the substrate) 11a of the substrate 11 becomes the uneven surface . In addition, the coating layer 14 is provided to cover the uneven surface, and the surface of the coating layer 14 in contact with the substrate 11 (hereinafter, sometimes referred to as the surface of the coating layer) 14a is the opposite side (hereinafter, sometimes referred to as the surface of the coating layer). for the coated back The surface roughness Ra of the surface) 14b is smaller than that of the back surface 11b of the base material 11. The surface roughness of the back surface 14b of the coating layer 14, in other words, the back surface 10b of the support sheet 10 (the surface on the opposite side of the support sheet 10 in contact with the protective film forming layer 13) is 0.5 μm or less. Here, the coating layer 14 functions as a layer for improving the smoothness of the back surface (ie, the exposed surface) of the support sheet 10 .

另外，保護膜形成用片1E中，支持片10的前述背面10b與剝離膜15的前述表面15a(剝離膜15中的與和保護膜形成層13接觸之面為相反側的面)之間的靜摩擦力為29N以下。 In addition, in the sheet 1E for forming a protective film, between the back surface 10b of the support sheet 10 and the front surface 15a of the release film 15 (the surface of the release film 15 that contacts the protective film forming layer 13 is the surface on the opposite side). Static friction is 29N or less.

圖5所示之保護膜形成用片1E係以下述方式使用：與圖1所示之保護膜形成用片1A同樣地，在移除剝離膜15之狀態下，於保護膜形成層13的表面13a貼附半導體晶圓(省略圖示)的背面，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 sheet 1E shown in FIG. 5 is used in the same manner as the protective film forming sheet 1A shown in FIG. 13a is attached to the back surface of the semiconductor wafer (not shown), and the upper surface of the front surface 16a of the adhesive layer 16 for a jig is attached to a jig such as a ring frame.

圖6係以示意方式表示本發明之保護膜形成用片的又一實施形態之剖視圖。 6 is a cross-sectional view schematically showing still another embodiment of the sheet for forming a protective film of the present invention.

關於此處所示之保護膜形成用片1F，除不具備有治具用接著劑層16之方面以外，與圖5所示之保護膜形成用片1E相同。亦即，保護膜形成用片1F中，於基材11的一表面11a積層有黏著劑層12，於黏著劑層12的表面12a(黏著劑層12中的與和基材11接觸之面為相反側的面)的整個表面積 層有保護膜形成層13，於保護膜形成層13的表面13a(保護膜形成層中的與和黏著劑層12接觸之面為相反側的面)的整個表面積層有剝離膜15。另外，基材11的前述背面11b(基材11中的與和黏著劑層12接觸之面為相反側的面)與圖5所示之保護膜形成用片1E之情形相同，積層有塗層14。 The sheet 1F for forming a protective film shown here is the same as the sheet 1E for forming a protective film shown in FIG. 5 except that the adhesive layer 16 for a jig is not provided. That is, in the sheet 1F for forming a protective film, the adhesive layer 12 is laminated on one surface 11a of the substrate 11, and the surface 12a of the adhesive layer 12 (the surface of the adhesive layer 12 that is in contact with the substrate 11 is the entire surface area of the opposite side) A protective film forming layer 13 is provided, and a release film 15 is provided on the entire surface area of the surface 13a of the protective film forming layer 13 (the surface on the opposite side of the protective film forming layer that is in contact with the adhesive layer 12). In addition, the back surface 11b of the base material 11 (the surface on the opposite side of the base material 11 that is in contact with the adhesive layer 12) is the same as the case of the protective film forming sheet 1E shown in FIG. 5, and a coating layer is laminated. 14.

並且，塗層14的前述背面14b(塗層中的與和基材11接觸之面為相反側的面)換言之支持片10的前述背面10b(支持片中的與和保護膜形成層13接觸之面為相反側的面)的表面粗糙度為0.5μm以下。 In addition, the aforementioned back surface 14b of the coating layer 14 (the surface of the coating layer that is in contact with the base material 11 is the surface on the opposite side), in other words, the aforementioned back surface 10b of the support sheet 10 (the one of the support sheet that is in contact with the protective film-forming layer 13) The surface roughness of the surface on the opposite side) is 0.5 μm or less.

另外，保護膜形成用片1F中，支持片10的前述背面10b與剝離膜15的前述表面15a(剝離膜15中的與和保護膜形成層13接觸之面為相反側的面)之間的靜摩擦力為29N以下。 In addition, in the sheet 1F for forming a protective film, between the back surface 10b of the support sheet 10 and the front surface 15a of the release film 15 (the surface of the release film 15 that contacts the protective film forming layer 13 is the surface on the opposite side). Static friction is 29N or less.

圖6所示之保護膜形成用片1F係以下述方式使用：與圖2所示之保護膜形成用片1B同樣地，在移除剝離膜15之狀態下，於保護膜形成層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，進一步將保護膜形成層13中的包圍半導體晶圓之周緣部附近的區域貼附於環狀框等治具。 The protective film forming sheet 1F shown in FIG. 6 is used in the same manner as the protective film forming sheet 1B shown in FIG. The back surface of the semiconductor wafer (not shown) is attached to a part of the central region of 13a, and the region surrounding the periphery of the semiconductor wafer in the protective film forming layer 13 is attached to a jig such as a ring frame.

圖7係以示意方式表示本發明之保護膜形成用片的又一實施形態之剖視圖。 FIG. 7 is a cross-sectional view schematically showing still another embodiment of the sheet for forming a protective film of the present invention.

關於此處所示之保護膜形成用片1G，除保護膜形成 層的形狀不同之方面以外，與圖1所示之保護膜形成用片1A相同。亦即，保護膜形成用片1G於基材11上具備有黏著劑層12，於黏著劑層12上具備有保護膜形成層23。支持片10為基材11及黏著劑層12之積層體，保護膜形成用片1G具有於支持片10的一表面10a上積層有保護膜形成層23之構成。另外，保護膜形成用片1G進一步於保護膜形成層23上具備有剝離膜15。關於保護膜形成層23，除形狀不同之方面以外以及保護膜形成層13相同。 Regarding the protective film forming sheet 1G shown here, except for the protective film formation It is the same as the sheet 1A for protective film formation shown in FIG. 1 except that the shape of a layer is different. That is, the sheet 1G for forming a protective film includes the adhesive layer 12 on the base material 11 , and includes the protective film forming layer 23 on the adhesive layer 12 . The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12 , and the protective film forming sheet 1G has a structure in which the protective film forming layer 23 is laminated on one surface 10 a of the support sheet 10 . Moreover, the sheet 1G for protective film formation is equipped with the release film 15 on the protective film formation layer 23 further. The protective film forming layer 23 is the same as the protective film forming layer 13 except that the shape is different.

自上方往下看而俯視保護膜形成用片1G時，保護膜形成層23相較於黏著劑層12而言，表面積較小，例如具有圓形狀等形狀。 When the sheet 1G for protective film formation is planarly viewed from above, the protective film formation layer 23 has a smaller surface area than the adhesive layer 12 and has a shape such as a circular shape, for example.

保護膜形成用片1G中，於基材11的一表面11a積層有黏著劑層12，於黏著劑層12的表面12a(黏著劑層12中的與和基材11接觸之面為相反側的面)的一部分積層有保護膜形成層23。並且，於黏著劑層12的表面12a中未積層保護膜形成層23之面、及保護膜形成層23的表面23a(上表面，亦即保護膜形成層23中的與和黏著劑層12接觸之面為相反側的面以及側面)上積層有剝離膜15。 In the sheet 1G for forming a protective film, the adhesive layer 12 is laminated on one surface 11a of the substrate 11, and the surface 12a of the adhesive layer 12 (the surface of the adhesive layer 12 that is in contact with the substrate 11 is the opposite side). The protective film forming layer 23 is laminated on a part of the surface). In addition, the surface 12a of the adhesive layer 12 on which the protective film forming layer 23 is not laminated, and the surface 23a of the protective film forming layer 23 (the upper surface, that is, the surface of the protective film forming layer 23 that is in contact with the adhesive layer 12) A release film 15 is laminated on the opposite side and the side surface).

保護膜形成用片1G中，支持片10的前述背面10b(支持片10中的與保護膜形成層23所接觸之面為相反側的面)換言之基材11的前述背面11b(基材11中的與黏著劑層12所 接觸之面為相反側的面)的表面粗糙度為0.5μm以下。 In the protective film forming sheet 1G, the back surface 10b of the support sheet 10 (the surface of the support sheet 10 in contact with the protective film forming layer 23 is the surface on the opposite side), in other words, the back surface 11b of the base material 11 (in the base material 11 ). of 12 layers with adhesive The surface roughness of the contact surface is the surface on the opposite side) of 0.5 μm or less.

另外，保護膜形成用片1G中，支持片10的前述背面10b與剝離膜15的前述表面15a(剝離膜15中的與和保護膜形成層23及黏著劑層12接觸之面為相反側的面)之間的靜摩擦力為29N以下。 In addition, in the sheet 1G for forming a protective film, the back surface 10b of the support sheet 10 and the front surface 15a of the release film 15 (the surface of the release film 15 that is in contact with the protective film forming layer 23 and the adhesive layer 12 are on the opposite side) The static friction force between the surfaces) is 29N or less.

圖7所示之保護膜形成用片1G係以下述方式使用：在移除剝離膜15之狀態下，於保護膜形成層23的表面23a貼附半導體晶圓(省略圖示)的背面，進一步將黏著劑層12的表面12a中未積層保護膜形成層23之面貼附於環狀框等治具。 The protective film forming sheet 1G shown in FIG. 7 is used in the following manner: in the state where the release film 15 is removed, the back surface of a semiconductor wafer (not shown) is attached to the surface 23a of the protective film forming layer 23, and further The surface 12a of the adhesive layer 12 on which the protective film forming layer 23 is not laminated is attached to a jig such as a ring frame.

圖8係以示意方式表示本發明之保護膜形成用片的又一實施形態之剖視圖。 FIG. 8 is a cross-sectional view schematically showing still another embodiment of the sheet for forming a protective film of the present invention.

關於此處所示之保護膜形成用片1H，除不具備有黏著劑層12之方面以外，與圖7所示之保護膜形成用片1G。亦即，保護膜形成用片1H中，支持片僅由基材11構成。另外，於基材11的一表面11a的一部分積層有保護膜形成層23，於基材11的表面11a中未積層保護膜形成層23之面、及保護膜形成層23的表面23a(上表面，亦即保護膜形成層23中的與和基材11接觸之面為相反側的面以及側面)上積層有剝離膜15。 The sheet 1H for forming a protective film shown here is the same as the sheet 1G for forming a protective film shown in FIG. 7 , except that the adhesive layer 12 is not provided. That is, in the sheet 1H for protective film formation, the support sheet consists only of the base material 11 . In addition, the protective film forming layer 23 is laminated on a part of one surface 11 a of the base material 11 , the surface 11 a of the base material 11 on which the protective film forming layer 23 is not laminated, and the surface 23 a (the upper surface of the protective film forming layer 23 ) , that is, the peeling film 15 is laminated on the surface and the side surface of the protective film forming layer 23 on the opposite side to the surface in contact with the base material 11 .

保護膜形成用片1H中，支持片10的前述背面10b(支持 片10中的與和保護膜形成層23及剝離膜11接觸之面為相反側的面)換言之基材11的前述背面11b(基材11中的與和保護膜形成層23及剝離膜11接觸之面為相反側的面)的表面粗糙度為0.5μm以下。 In the sheet 1H for forming a protective film, the back surface 10b of the support sheet 10 (supporting In the sheet 10, the surface in contact with the protective film-forming layer 23 and the release film 11 is the surface on the opposite side) In other words, the back surface 11b of the base material 11 (the surface of the base material 11 in contact with the protective film-forming layer 23 and the release film 11) The surface roughness is 0.5 μm or less.

另外，保護膜形成用片1H中，支持片10的前述背面10b與剝離膜15的前述表面15a(剝離膜15中的與保護膜形成層23和基材11接觸之面為相反側的面)之間的靜摩擦力為29N以下。 In addition, in the sheet 1H for forming a protective film, the back surface 10b of the support sheet 10 and the front surface 15a of the release film 15 (the surface of the release film 15 in contact with the protective film forming layer 23 and the base material 11 is the surface on the opposite side) The static friction force between them is 29N or less.

圖8所示之保護膜形成用片1H係以下述方式使用：在移除剝離膜15之狀態下，於保護膜形成層23的表面23a貼附半導體晶圓(省略圖示)的背面，進一步將基材11的表面11a中未積層保護膜形成層23之面藉由治具用接著劑層(省略圖示)貼附於環狀框等治具。此處，作為治具用接著劑層，可使用與圖1等所示之治具用接著劑層16相同的治具用接著劑層。 The sheet 1H for forming a protective film shown in FIG. 8 is used by attaching the back surface of a semiconductor wafer (not shown) to the surface 23a of the protective film forming layer 23 with the release film 15 removed, and further The surface 11a of the base material 11 on which the protective film forming layer 23 is not laminated is attached to a jig such as a ring frame through an adhesive layer (not shown) for a jig. Here, as the adhesive layer for a jig, the same adhesive layer for a jig as the adhesive layer for a jig 16 shown in FIG. 1 and the like can be used.

再者，無論支持片為何種構成，均可使用治具用接著劑層將保護膜形成用片貼附於環狀框等治具。 In addition, regardless of the structure of the support sheet, the sheet for forming a protective film can be attached to a jig such as an annular frame using an adhesive layer for a jig.

本發明之保護膜形成用片並不限定於圖1至圖8所示之保護膜形成用片，在無損本發明的功效之範圍內，亦可將圖1至圖8所示之保護膜形成用片的一部分構成變更或刪除，或者對上文說明之保護膜形成用片進一步追加其他構成。 The sheet for forming a protective film of the present invention is not limited to the sheet for forming a protective film shown in FIGS. 1 to 8 , and the protective film shown in FIGS. A part of the configuration of the sheet is changed or deleted, or another configuration is further added to the sheet for forming a protective film described above.

例如，圖5及圖6中，對以下保護膜形成用片進行了說明，該保護膜形成用片中，支持片具有塗層及基材之積層結構，基材的背面(與塗層之接觸面)為凹凸面，塗層的背面(不與基材接觸之面)相較於基材的背面而言表面粗糙度Ra變小。但是，本發明之保護膜形成用片中，例如塗層及基材之積層結構中，基材的背面(與塗層之接觸面)亦可為平滑面而並非凹凸面。亦即，塗層亦可具有提高支持片10的背面(露出面)的平滑度之功能以外的功能。 For example, in FIGS. 5 and 6, the following protective film forming sheet is described, in which the supporting sheet has a laminated structure of a coating layer and a base material, and the back surface of the base material (contact with the coating layer) is described. surface) is an uneven surface, and the surface roughness Ra of the back surface of the coating layer (the surface not in contact with the substrate) is smaller than that of the back surface of the substrate. However, in the sheet for forming a protective film of the present invention, for example, in the layered structure of the coating layer and the substrate, the back surface of the substrate (contact surface with the coating layer) may be a smooth surface instead of an uneven surface. That is, the coating layer may have a function other than the function of improving the smoothness of the back surface (exposed surface) of the support sheet 10 .

另外，圖1至圖8中，對以下保護膜形成用片進行了說明，該保護膜形成用片中，支持片的前述背面亦即於支持片僅由基材構成或者支持片為基材及黏著劑層之積層體之情形時基材的前述背面，於支持片具有塗層之情形時塗層的背面分別為平滑面。但是，本發明之保護膜形成用片中，支持片的前述背面亦可為表面粗糙度為0.5μm以下之凹凸面。 In addition, in FIGS. 1 to 8 , the following protective film forming sheet is described, in which the above-mentioned back surface of the supporting sheet, that is, the supporting sheet is composed of only the base material or the supporting sheet is the base material and In the case of the laminate of the adhesive layer, the back surface of the base material is the back surface of the substrate, and when the support sheet has a coating layer, the back surface of the coating layer is a smooth surface, respectively. However, in the sheet for protective film formation of this invention, the said back surface of a support sheet may be the uneven surface whose surface roughness is 0.5 micrometer or less.

另外，圖1至圖8中，對支持片的前述背面均一之保護膜形成用片進行了說明，但本發明之保護膜形成用片中，支持片的前述背面亦可具有例如為平滑面之區域及為凹凸面之區域等平滑度(凹凸度)不同之兩個以上之區域。 In addition, in FIGS. 1 to 8 , the back surface of the support sheet is described as a sheet for forming a protective film that is uniform, but in the sheet for forming a protective film of the present invention, the back surface of the support sheet may have, for example, a smooth surface. Two or more regions with different smoothness (unevenness), such as a region and a region that is a concave-convex surface.

另外，圖1、圖2、圖5、圖6及圖7中，對在基材上直 接接觸設置有黏著劑層之保護膜形成用片進行了說明，但本發明之保護膜形成用片亦可於基材與黏著劑層之間設置有中間層。亦即，本發明之保護膜形成用片中，支持片亦可具有基材、中間層及黏著劑層依序積層而成之積層結構。 In addition, in FIGS. 1, 2, 5, 6 and 7, the alignment on the substrate is The sheet for forming a protective film provided in contact with the adhesive layer was described, but the sheet for forming a protective film of the present invention may have an intermediate layer provided between the base material and the adhesive layer. That is, in the sheet for forming a protective film of the present invention, the support sheet may have a laminated structure in which a base material, an intermediate layer, and an adhesive layer are sequentially laminated.

並且，圖3、圖4及圖8中，對在基材上直接接觸設置有保護膜形成層之保護膜形成用片進行了說明，但本發明之保護膜形成用片亦可於基材與保護膜形成層之間設置有中間層。 3, 4 and 8, the sheet for forming a protective film in which the protective film forming layer is provided in direct contact with the base material has been described, but the sheet for forming a protective film of the present invention may also be used on the base material and the base material. An intermediate layer is provided between the protective film forming layers.

此處，作為中間層，可根據目的選擇任意的中間層；作為較佳的中間層，例如可列舉可使鄰接兩層的密接性提高之中間層。 Here, as an intermediate layer, an arbitrary intermediate layer can be selected according to the purpose; as a preferable intermediate layer, for example, an intermediate layer which can improve the adhesiveness of two adjacent layers is mentioned.

另外，本發明之保護膜形成用片亦可於任意部位設置前述中間層以外的層。 Moreover, the sheet for protective film formation of this invention may provide the layer other than the said intermediate|middle layer in arbitrary places.

以下，對本發明之保護膜形成用片的各構成進行更詳細的說明。 Hereinafter, each structure of the sheet for protective film formation of this invention is demonstrated in detail.

○支持片 ○ Support sheet

前述支持片只要能夠設置前述保護膜形成層，且一併滿足上述表面粗糙度的條件(0.5μm以下)與靜摩擦力的條件(29N以下)，則並無特別限定。作為較佳的支持片，例如可列舉如上文所說明之以下支持片：半導體晶圓之加 工用片之領域中通常所使用之僅由基材構成之支持片；由基材及黏著劑層積層而成之支持片；由塗層及基材積層而成之支持片；以及由塗層、基材及黏著劑層依序積層而成之支持片等。另外，作為較佳的支持片，例如亦可列舉由基材、中間層及黏著劑層積層而成之支持片等上述例示之積層結構中於鄰接之兩層間設置有中間層之支持片。 The support sheet is not particularly limited as long as the protective film-forming layer can be provided and the conditions of the surface roughness (0.5 μm or less) and the conditions of static friction (29 N or less) are satisfied together. As a preferred support sheet, for example, the following support sheets as described above can be listed: In the field of work sheets, a support sheet consisting only of a base material; a support sheet formed by laminating a base material and an adhesive; a support sheet formed by laminating a coating and a base material; , A support sheet formed by sequentially laminating substrates and adhesive layers. In addition, as a preferable support sheet, for example, a support sheet in which an intermediate layer is provided between two adjacent layers in the above-exemplified laminated structure, such as a support sheet formed by laminating a substrate, an intermediate layer, and an adhesive, can also be mentioned.

支持片可由一層(單層)構成，亦可由兩層以上之複數層構成。於支持片由複數層構成之情形時，這些複數層相互可相同亦可不同，這些複數層之組合並無特別限定。 The support sheet may be constituted by one layer (single layer), or may be constituted by plural layers of two or more layers. When the support sheet is composed of plural layers, these plural layers may be the same or different from each other, and the combination of these plural layers is not particularly limited.

支持片的厚度根據目的適宜選擇即可，就可對前述保護膜形成用片賦予充分的可撓性，對半導體晶圓之貼附性良好之方面而言，較佳為10μm至500μm，更佳為20μm至350μm，尤佳為30μm至200μm。 The thickness of the support sheet may be appropriately selected according to the purpose, and is preferably 10 μm to 500 μm, more preferably 10 μm to 500 μm, in terms of imparting sufficient flexibility to the above-mentioned sheet for forming a protective film and good adhesion to a semiconductor wafer. It is 20 μm to 350 μm, particularly preferably 30 μm to 200 μm.

此處，所謂「支持片的厚度」意指構成支持片之各層的合計厚度，例如於由基材及黏著劑層積層而成之支持片之情形時意指基材的厚度及黏著劑層的厚度的合計值。 Here, the so-called "thickness of the support sheet" means the total thickness of each layer constituting the support sheet, for example, in the case of a support sheet formed by laminating a base material and an adhesive, it means the thickness of the base material and the thickness of the adhesive layer. The total value of thickness.

再者，於支持片的至少一面為凹凸面之情形時，關於此種支持片的厚度，於支持片的該凹凸面中包含凸部之部位中，將該凸部的頂端作為一起點而算出即可。 Furthermore, when at least one side of the support sheet is a concave-convex surface, the thickness of the support sheet is calculated by taking the top end of the convex portion as a common point in the position of the convex portion in the concave-convex surface of the supporting sheet. That's it.

另外，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且以平均表示之值。 In addition, in this specification, "thickness" means the value which measures the thickness by the contact thickness meter at arbitrary 5 places, and shows it as an average value.

支持片中的與具備有保護膜形成層之側為相反側的表面(以下，有時稱為露出面)的表面粗糙度如上所述為0.5μm以下，較佳為0.45μm以下，更佳為0.4μm以下，尤佳為0.35μm以下。藉由支持片的前述表面粗糙度為前述上限值以下，可對半導體晶片更良好地進行上述紅外線檢測。支持片的前述表面粗糙度的下限值並無特別限定，例如可為0μm、0.01μm等。 The surface roughness of the surface on the opposite side to the side provided with the protective film forming layer (hereinafter, sometimes referred to as the exposed surface) in the support sheet is 0.5 μm or less as described above, preferably 0.45 μm or less, and more preferably 0.4 μm or less, particularly preferably 0.35 μm or less. When the said surface roughness of a support sheet is below the said upper limit, the said infrared detection can be performed more favorably with respect to a semiconductor wafer. The lower limit value of the surface roughness of the support sheet is not particularly limited, and may be, for example, 0 μm, 0.01 μm, or the like.

亦即，支持片的表面粗糙度為0μm至0.5μm，較佳為0μm至0.45μm，更佳為0.01μm至0.4μm，進一步更佳為0.01μm至0.35μm，尤佳為0.03μm至0.3μm。 That is, the surface roughness of the support sheet is 0 μm to 0.5 μm, preferably 0 μm to 0.45 μm, more preferably 0.01 μm to 0.4 μm, still more preferably 0.01 μm to 0.35 μm, particularly preferably 0.03 μm to 0.3 μm .

支持片的前述表面粗糙度例如可藉由滿足該表面粗糙度的條件之層的形成條件或表面處理條件等進行調節。 The aforementioned surface roughness of the support sheet can be adjusted, for example, by the formation conditions of the layer satisfying the conditions of the surface roughness, the surface treatment conditions, and the like.

‧基材 ‧Substrate

前述基材的材質較佳為各種樹脂，作為該樹脂的具體例，可列舉：聚乙烯(低密度聚乙烯(有時簡稱為LDPE)、直鏈低密度聚乙烯(有時簡稱為LLDPE)、高密度聚乙烯(有時簡稱為HDPE等))、聚丙烯、乙烯-丙烯共聚物、聚丁烯、聚丁二烯、聚甲基戊烯、聚氯乙烯、氯乙烯共聚物、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、聚胺基甲酸酯、聚丙烯酸胺基甲酸酯、聚醯亞胺、乙烯-乙酸乙烯酯共聚物、離子聚合物樹脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物、聚苯乙烯、聚碳酸酯、氟樹脂、這些任一樹脂之氫化物、改性物、交聯 物或共聚物等。 The material of the aforementioned base material is preferably various resins, and specific examples of the resins include polyethylene (low density polyethylene (sometimes abbreviated as LDPE), linear low density polyethylene (sometimes abbreviated as LLDPE), High-density polyethylene (sometimes abbreviated as HDPE, etc.), polypropylene, ethylene-propylene copolymer, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, vinyl chloride copolymer, polyparaphenylene Ethylene Dicarboxylate, Polyethylene Naphthalate, Polybutylene Terephthalate, Polyurethane, Polyurethane Acrylate, Polyimide, Ethylene Vinyl Acetate Copolymer , ionic polymer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, polystyrene, polycarbonate, fluororesin, hydrogenated products, modified products of any of these resins, cross-linked compounds or copolymers, etc.

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，例如，「(甲基)丙烯酸酯」的概念係包含有「丙烯酸酯」及「甲基丙烯酸酯」兩者，「(甲基)丙烯醯基」的概念係包含有「丙烯醯基」及「甲基丙烯醯基」兩者。 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. For example, the concept of "(meth)acrylate" includes both "acrylate" and "methacrylate", and "(meth)acryloyl The concept of "" includes both "acryloyl" and "methacryloyl".

基材的厚度可根據目的適宜選擇。 The thickness of the base material can be appropriately selected according to the purpose.

於支持片由基材與黏著劑層等其他層積層而成之情形時，基材的厚度較佳為15μm至300μm，更佳為20μm至200μm。藉由基材的厚度為此種範圍，保護膜形成用片的可撓性、及對半導體晶圓或半導體晶片之貼附性進一步提高。 When the support sheet is formed by laminating the base material and other layers such as an adhesive layer, the thickness of the base material is preferably 15 μm to 300 μm, more preferably 20 μm to 200 μm. When the thickness of a base material is such a range, the flexibility of the sheet for protective film formation and the adhesiveness to a semiconductor wafer or a semiconductor chip are further improved.

基材可由一層(單層)構成，亦可由兩層以上之複數層構成。於基材由複數層構成之情形時，這些複數層相互可相同亦可不同，這些複數層之組合並無特別限定。 The base material may be constituted by one layer (single layer), or may be constituted by plural layers of two or more layers. When the base material is composed of plural layers, these plural layers may be the same or different from each other, and the combination of these plural layers is not particularly limited.

再者，於基材由複數層構成之情形時，較佳為各層的合計厚度為上述較佳的基材厚度。 Furthermore, when the base material is composed of a plurality of layers, it is preferable that the total thickness of each layer is the above-mentioned preferable base material thickness.

基材的表面亦可經實施以下處理以提高與設置於基材上之黏著劑層、保護膜形成層、塗層等其他層之密接性 ：利用噴砂處理、溶劑處理、壓紋加工處理等之凹凸化處理(消光處理)；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。另外，基材的表面亦可經實施底塗處理。 The surface of the substrate can also be subjected to the following treatments to improve the adhesion with other layers such as the adhesive layer, the protective film forming layer, and the coating layer provided on the substrate : Concavity and convexity treatment (matte treatment) by sandblasting, solvent treatment, embossing treatment, etc.; or corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, Oxidation treatment such as hot air treatment, etc. In addition, the surface of the base material may be subjected to primer treatment.

‧黏著劑層 ‧Adhesive layer

前述黏著劑層可適宜使用公知的黏著劑層。 As the above-mentioned adhesive layer, a known adhesive layer can be suitably used.

黏著劑層可由黏著劑組成物而形成，該黏著劑組成物用以構成該黏著劑層，且含有黏著劑等各種成分。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 from an adhesive composition, and the adhesive composition is used to constitute the adhesive layer and contains various components such as an adhesive. The content ratio of components that do not vaporize at room temperature in the adhesive composition is usually the same as the content ratio of the above-mentioned components in the adhesive layer. In addition, in this specification, "normal temperature" means the temperature which is not particularly cold or particularly hot, that is, a normal temperature, for example, a temperature of 15°C to 25°C, and the like.

黏著劑層的厚度可根據目的適宜選擇，較佳為1μm至100μm，更佳為2μm至80μm，尤佳為3μm至50μm。 The thickness of the adhesive layer can be appropriately selected according to the purpose, and is preferably 1 μm to 100 μm, more preferably 2 μm to 80 μm, and particularly preferably 3 μm to 50 μm.

黏著劑層可由一層(單層)構成，亦可由兩層以上之複數層構成。於黏著劑層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 constituted by one layer (single layer), or may be constituted by plural layers of two or more layers. When the adhesive layer is composed of plural layers, these plural layers may be the same or different from each other, and the combination of these plural layers is not particularly limited.

於黏著劑層由複數層構成之情形時，各層的合計厚度可為上述較佳的黏著劑層的厚度。 When the adhesive layer is composed of a plurality of layers, the total thickness of each layer may be the thickness of the above-mentioned preferred adhesive layer.

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、乙烯醚系樹脂等黏著性樹脂，於著眼於該樹脂之功能之情形時，例如可列舉能量線硬化性樹脂等。 Examples of the above-mentioned adhesives include adhesive resins such as acrylic resins, urethane resins, rubber-based resins, polysiloxane-based resins, and vinyl ether-based resins. When focusing on the function of the resins For example, energy ray curable resin etc. are mentioned.

再者，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；作為該能量線的示例，可列舉紫外線、電子束等。紫外線例如可藉由使用高壓水銀燈、融合(fusion)H型燈或氙氣燈等作為紫外線源而進行照射。電子束可照射藉由電子束加速器等產生之電子束。 In addition, in this specification, an "energy ray" means an electromagnetic wave or a charged particle beam which has an energy quantum, and an ultraviolet-ray, an electron beam, etc. are mentioned as an example of this energy ray. The ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H-type lamp, a xenon lamp, or the like as an ultraviolet source. The electron beam may be irradiated with an electron beam generated by an electron beam accelerator or the like.

作為前述能量線硬化性樹脂，例如可列舉具有(甲基)丙烯醯基、乙烯基等聚合性基之樹脂。 As said energy ray curable resin, resin which has a polymerizable group, such as a (meth)acryloyl group and a vinyl group, is mentioned, for example.

前述黏著性樹脂較佳為丙烯酸系樹脂，更佳為包含源自(甲基)丙烯酸酯之結構單元之(甲基)丙烯酸酯共聚物。 The aforementioned adhesive resin is preferably an acrylic resin, more preferably a (meth)acrylate copolymer containing a structural unit derived from a (meth)acrylate.

此處，所謂「源自」意指因進行聚合而化學結構發生變化。 Here, "derived from" means that the chemical structure changes due to polymerization.

關於前述黏著劑層，於含有能量線硬化性樹脂等藉由照射能量線而聚合之成分之情形時，成為能量線硬化性，藉由照射能量線使該黏著劑層之黏著性降低，而容易拾取後述附有保護膜之半導體晶片。此種黏著劑層例如可由各種黏著劑組成物形成，該黏著劑組成物含有藉由照射能量線而聚合之成分。 The above-mentioned adhesive layer becomes energy ray curable when it contains a component polymerized by energy ray irradiation, such as an energy ray curable resin, and the adhesiveness of the adhesive layer is reduced by irradiating energy rays, and it is easy to The semiconductor wafer with a protective film mentioned later is picked up. Such an adhesive layer may be formed of, for example, various adhesive compositions containing components polymerized by irradiation with energy rays.

<<黏著劑組成物>> <<Adhesive composition>>

作為較佳的前述黏著劑組成物，可列舉含有藉由照射能量線而聚合之成分之黏著劑組成物；作為此種黏著劑組成物，例如可列舉：含有丙烯酸系樹脂及能量線聚合性化合物之黏著劑組成物(以下，有時簡稱為「黏著劑組成物(i)」)；含有丙烯酸系樹脂及異氰酸酯系交聯劑之黏著劑組成物(以下，有時簡稱為「黏著劑組成物(ii)」)，前述丙烯酸系樹脂係具有羥基且於側鏈具有聚合性基之丙烯酸系樹脂(例如，具有羥基且經由胺基甲酸酯鍵而於側鏈具有聚合性基之丙烯酸系樹脂)等。 Preferable examples of the adhesive composition include those containing components polymerized by irradiation with energy rays; examples of such adhesive compositions include those containing an acrylic resin and an energy ray polymerizable compound. The adhesive composition (hereinafter, sometimes referred to as "adhesive composition (i)"); the adhesive composition containing acrylic resin and isocyanate crosslinking agent (hereinafter, sometimes referred to as "adhesive composition (i)"); (ii)"), the aforementioned acrylic resin is an acrylic resin having a hydroxyl group and a polymerizable group in the side chain (for example, an acrylic resin having a hydroxyl group and a polymerizable group in the side chain via a urethane bond) )Wait.

[黏著劑組成物(i)] [Adhesive composition (i)]

黏著劑組成物(i)含有前述丙烯酸系樹脂及能量線聚合性化合物作為必需成分。 The adhesive composition (i) contains the aforementioned acrylic resin and the energy ray polymerizable compound as essential components.

以下，對各成分進行說明。 Hereinafter, each component will be described.

(丙烯酸系樹脂) (acrylic resin)

作為黏著劑組成物(i)中較佳的前述丙烯酸系樹脂，例如可列舉：使(甲基)丙烯酸酯與視需要使用之除(甲基)丙烯酸酯以外的單體作為單體進行聚合而獲得之(甲基)丙烯酸酯共聚物。 As the aforementioned acrylic resin preferable in the adhesive composition (i), for example, a monomer obtained by polymerizing a (meth)acrylate and a monomer other than the (meth)acrylate used as a monomer as a monomer can be mentioned. The obtained (meth)acrylate copolymer.

作為前述(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯 酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(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((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)丙烯酸異十八烷基酯(亦稱為(甲基)丙烯酸異硬脂酯)等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；(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；(甲基)丙烯醯亞胺；(甲基)丙烯酸縮水甘油酯等含縮水甘油基之(甲基)丙烯酸酯；(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-羥基丁酯等含羥基之(甲基)丙烯酸酯等。 As said (meth)acrylate, (meth)propylene is mentioned, for example Methyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate ester, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, Decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, Myristyl (meth)acrylate (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (also known as ((meth)acrylate) palmityl meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (also known as stearyl (meth)acrylate), isotenyl (meth)acrylate Octaalkyl ester (also known as isostearyl (meth)acrylate) and the like, the alkyl group constituting the alkyl ester is an alkyl (meth)acrylate having a chain structure with a carbon number of 1 to 18; (methyl) ) Cycloalkyl (meth)acrylates such as isobornyl acrylate and dicyclopentyl (meth)acrylate; (meth) aralkyl acrylates such as benzyl (meth)acrylate; (meth)acrylate Cycloalkenyl (meth)acrylic acid esters such as cyclopentenyl ester; (meth)acrylic acid cycloalkenyloxyalkyl esters such as dicyclopentenyloxyethyl (meth)acrylate; (meth)acrylimide ; Glycidyl (meth)acrylate and other glycidyl-containing (meth)acrylates; (meth)acrylate hydroxymethyl, (meth)acrylate 2-hydroxyethyl, (meth)acrylate 2-hydroxyl Propyl, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. (Meth)acrylate, etc.

上述之中，較佳為甲基丙烯酸甲酯、丙烯酸2-乙基己 酯、丙烯酸2-羥基乙酯等。 Among the above, preferably methyl methacrylate, 2-ethylhexyl acrylate ester, 2-hydroxyethyl acrylate, etc.

作為前述(甲基)丙烯酸酯以外的單體，例如可列舉：(甲基)丙烯酸、衣康酸、乙酸乙烯酯、丙烯腈、苯乙烯、N-羥甲基丙烯醯胺等。 As a monomer other than the said (meth)acrylate, (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylol acrylamide etc. are mentioned, for example.

構成丙烯酸系樹脂之前述(甲基)丙烯酸酯、除前述(甲基)丙烯酸酯以外的單體等各種單體均可僅為1種，亦可為2種以上。 Various monomers, such as the said (meth)acrylate and monomers other than the said (meth)acrylate which comprise an acrylic resin, may be only 1 type, and may be 2 or more types.

黏著劑組成物(i)所含有之丙烯酸系樹脂可僅為1種，亦可為2種以上。 The acrylic resin contained in the adhesive composition (i) may be only one type or two or more types.

關於黏著劑組成物(i)中的丙烯酸系樹脂的含量，相對於黏著劑組成物(i)中的溶劑以外的全部含有成分的總質量，較佳為40質量%至99質量%，更佳為50質量%至91質量%。 The content of the acrylic resin in the adhesive composition (i) is preferably 40% by mass to 99% by mass, more preferably 40% by mass to 99% by mass relative to the total mass of all components other than the solvent in the adhesive composition (i) It is 50 mass % to 91 mass %.

(能量線聚合性化合物) (Energy ray polymerizable compound)

前述能量線聚合性化合物係藉由照射能量線進行聚合而硬化之化合物；作為該化合物的示例，可列舉於分子內具有能量線硬化性雙鍵等能量線聚合性基之化合物。 The aforementioned energy ray polymerizable compound is a compound that is polymerized and cured by irradiation with energy rays; examples of the compound include compounds having an energy ray polymerizable group such as an energy ray-curable double bond in the molecule.

作為前述能量線聚合性化合物，例如可列舉具有能量 線聚合性基之低分子量化合物(單官能或多官能之單體及低聚物)，更具體而言，可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇單羥基五(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-己二醇二(甲基)丙烯酸酯等(甲基)丙烯酸酯；二環戊二烯二甲氧基二(甲基)丙烯酸酯等含環狀脂肪族骨架之(甲基)丙烯酸酯；聚乙二醇二(甲基)丙烯酸酯、寡酯(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯低聚物、環氧改性(甲基)丙烯酸酯、聚醚(甲基)丙烯酸酯、衣康酸低聚物等(甲基)丙烯酸酯系化合物等。 Examples of the energy ray polymerizable compound include those having energy Linear polymerizable group low molecular weight compounds (monofunctional or polyfunctional monomers and oligomers), more specifically, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate Acrylates, 1,6-hexanediol di(meth)acrylate and other (meth)acrylates; dicyclopentadiene dimethoxydi(meth)acrylate and other (meth)acrylates containing cyclic aliphatic skeleton Meth)acrylate; polyethylene glycol di(meth)acrylate, oligoester (meth)acrylate, (meth)acrylate urethane oligomer, epoxy modified (meth)acrylic acid (meth)acrylate-based compounds such as esters, polyether (meth)acrylates, itaconic acid oligomers, and the like.

前述能量線聚合性化合物的分子量較佳為100至30000，更佳為300至10000。 The molecular weight of the energy ray polymerizable compound is preferably from 100 to 30,000, more preferably from 300 to 10,000.

黏著劑組成物(i)所含有之能量線聚合性化合物可僅為1種，亦可為2種以上。 The energy ray polymerizable compound contained in the adhesive composition (i) may be only one type or two or more types.

黏著劑組成物(i)中的能量線聚合性化合物的含量相對於前述丙烯酸系樹脂的含量100質量份，較佳為1質量份至125質量份，更佳為10質量份至125質量份。 The content of the energy ray polymerizable compound in the adhesive composition (i) is preferably 1 to 125 parts by mass, more preferably 10 to 125 parts by mass relative to 100 parts by mass of the content of the acrylic resin.

(光聚合起始劑) (photopolymerization initiator)

黏著劑組成物(i)除前述丙烯酸系樹脂及能量線聚合 性化合物以外，亦可含有光聚合起始劑。 Adhesive composition (i) in addition to the aforementioned acrylic resin and energy ray polymerization In addition to the natural compound, a photopolymerization initiator may be contained.

前述光聚合起始劑可為公知的光聚合起始劑，具體而言，例如可列舉：4-(2-羥基乙氧基)苯基-2-(羥基-2-丙基)酮、α-羥基-α,α'-二甲基苯乙酮、2-甲基-2-羥基苯丙酮、1-羥基環己基苯基酮、2-羥基-1-{4-[4-(2-羥基-2-甲基-丙醯基)-苄基]苯基}-2-甲基-丙烷-1-酮等α-酮醇系化合物；苯乙酮、二甲胺基苯乙酮、甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-羥基環己基苯基酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎福林(morpholine)基丙烷-1-酮、2-苄基-2-二甲胺基-1-(4-嗎福林基苯基)-丁酮-1等苯乙酮系化合物；安息香、安息香甲醚、安息香***、安息香異丙醚、安息香正丁醚、安息香異丁醚、大茴香偶姻甲醚等安息香醚系化合物；苯偶醯二甲基縮酮、苯乙酮二甲基縮酮等縮酮系化合物；2-萘磺醯氯等芳香族磺醯氯系化合物；1-苯酮-1,1-丙二酮-2-(鄰乙氧基羰基)肟、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)等光活性肟系化合物；二苯甲酮、對苯基二苯甲酮、苯甲醯苯甲酸、二氯二苯甲酮、4,4'-二乙基胺基二苯甲酮、3,3'-二甲基-4-甲氧基二苯甲酮等二苯甲酮系化合物；2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、2-胺基蒽醌等蒽醌系化合物；噻噸酮(thioxanthone)、2-氯噻噸酮、2-甲基噻噸酮、2-乙基噻噸酮、異丙基噻 噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮、2,4-二異丙基噻噸酮等噻噸酮系化合物；對二甲胺基苯甲酸酯；樟腦醌；鹵代酮；二苯基(2,4,6-三甲基苯甲醯基)氧化膦等醯基氧化膦；醯基膦酸鹽/酯、寡聚[2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮]等。 The photopolymerization initiator may be a known photopolymerization initiator, and specific examples thereof include 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, α- -Hydroxy-α,α'-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-1-{4-[4-(2- Hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one and other α-keto alcohol compounds; acetophenone, dimethylaminoacetophenone, methyl Oxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2,2-diethoxy-2-phenylacetophenone Ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2 - Acetophenone compounds such as morpholine propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholine phenyl)-butanone-1; Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, anisin methyl ether and other benzoin ether compounds; benzoin dimethyl ketal, acetophenone dimethyl ether Ketal-based compounds such as ketal; ,1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) and other photoactive oxime compounds; Benzophenone, p-phenylbenzophenone, benzoic acid, dichlorobenzophenone, 4,4'-diethylaminobenzophenone, 3,3'-dimethyl- Benzophenone-based compounds such as 4-methoxybenzophenone; anthraquinone-based compounds such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 2-aminoanthraquinone Compounds; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, isopropylthioxanthone Xanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diisopropylthioxanthone and other thioxanthone series compounds; p-dimethylaminobenzoate; camphorquinone; halogenated ketones; salt/ester, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone], etc.

黏著劑組成物(i)所含有之光聚合起始劑可僅為1種，亦可為2種以上。 The photopolymerization initiator contained in the adhesive composition (i) may be only one type or two or more types.

於使用光聚合起始劑之情形時，黏著劑組成物(i)中的光聚合起始劑的含量相對於前述能量線聚合性化合物的含量100質量份，較佳為0.1質量份至10質量份，更佳為1質量份至5質量份。藉由光聚合起始劑的前述含量為前述下限值以上，可獲得充分的由使用光聚合起始劑所帶來之功效。另外，藉由光聚合起始劑的前述含量為前述上限值以下，可抑制由過量的光聚合起始劑產生副生成分，從而使黏著劑層更良好地進行硬化。 In the case of using a photopolymerization initiator, the content of the photopolymerization initiator in the adhesive composition (i) is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the energy ray polymerizable compound content parts, more preferably 1 to 5 parts by mass. When the said content of a photopolymerization initiator is more than the said lower limit, sufficient effect by using a photopolymerization initiator can be obtained. Moreover, since the said content of a photoinitiator is below the said upper limit, generation|occurrence|production of a by-product from an excess photoinitiator can be suppressed, and hardening of an adhesive bond layer can be performed more favorably.

(交聯劑) (crosslinking agent)

黏著劑組成物(i)中，除前述丙烯酸系樹脂及能量線聚合性化合物以外，亦可進一步含有交聯劑。 The adhesive composition (i) may further contain a crosslinking agent in addition to the aforementioned acrylic resin and the energy ray polymerizable compound.

作為前述交聯劑，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等。 As said crosslinking agent, an organic polyvalent isocyanate compound, an organic polyvalent imine compound, etc. are mentioned, for example.

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、脂環族多元異氰酸酯化合物及這些化合物的三聚物、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、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以及乙二醇、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化合物之反應物。 Examples of the organic polyvalent isocyanate compound include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, and trimers, isocyanurates, and adducts of these compounds; An aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, or an alicyclic polyvalent isocyanate compound and a polyol compound are reacted with a terminal isocyanate urethane prepolymer, and the like. The aforementioned adduct means the aforementioned aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound or alicyclic polyvalent isocyanate compound, as well as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil containing low molecular activity. Reactants of hydrogen compounds.

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及六亞甲基二異氰酸酯的任一者或兩者而成之化合物；離胺酸二異氰酸酯等。 As said organic polyvalent isocyanate compound, more specifically, 2, 4- toluene diisocyanate; 2, 6- toluene diisocyanate; 1, 3- xylylene diisocyanate; 1, 4- xylene diisocyanate are mentioned, for example Isocyanates; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone Diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; All or part of the hydroxyl groups of polyols such as p-trimethylolpropane, added with toluene diisocyanate and Compounds of either or both of hexamethylene diisocyanate; lysine diisocyanate, etc.

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

於使用異氰酸酯化合物作為交聯劑之情形時，作為丙烯酸系樹脂，較佳為使用含羥基之聚合物。於交聯劑具有異氰酸酯基且丙烯酸系樹脂具有羥基之情形時，可藉由這些異氰酸酯基與羥基之反應，而將交聯結構簡便地導入至黏著劑層中。 When an isocyanate compound is used as a crosslinking agent, it is preferable to use a hydroxyl-containing polymer as an acrylic resin. When the crosslinking agent has an isocyanate group and the acrylic resin has a hydroxyl group, the crosslinked structure can be easily introduced into the adhesive layer by the reaction between these isocyanate groups and the hydroxyl group.

黏著劑組成物(i)所含有之交聯劑可僅為1種，亦可為2種以上。 The crosslinking agent contained in the adhesive composition (i) may be only one type or two or more types.

於使用交聯劑之情形時，黏著劑組成物(i)中的交聯劑的含量相對於前述丙烯酸系樹脂的含量100質量份，較佳為0.01質量份至20質量份，更佳為0.1質量份至16質量份。 In the case of using a crosslinking agent, the content of the crosslinking agent in the adhesive composition (i) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the content of the aforementioned acrylic resin, more preferably 0.1 parts by mass to 16 parts by mass.

(溶劑) (solvent)

黏著劑組成物(i)較佳為除前述丙烯酸系樹脂及能量線聚合性化合物以外，進一步含有溶劑。 The adhesive composition (i) preferably further contains a solvent in addition to the aforementioned acrylic resin and the energy ray polymerizable compound.

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

黏著劑組成物(i)所含有之溶劑可僅為1種，亦可為2種以上。 The solvent contained in the adhesive composition (i) may be only one type or two or more types.

黏著劑組成物(i)含有溶劑之情形時，溶劑的含量相對於黏著劑組成物的總質量，較佳為40質量%至90質量%，更佳為50質量%至80質量%。 When the adhesive composition (i) contains a solvent, the content of the solvent is preferably 40 to 90 mass %, more preferably 50 to 80 mass % with respect to the total mass of the adhesive composition.

(其他成分) (other ingredients)

黏著劑組成物(i)中，除前述丙烯酸系樹脂及能量線聚合性化合物以外，亦可在無損本發明的功效之範圍內，進一步含有不屬於前述光聚合起始劑、交聯劑及溶劑之其他成分。 In the adhesive composition (i), in addition to the aforementioned acrylic resin and the energy ray polymerizable compound, it is also possible to further contain a photopolymerization initiator, a crosslinking agent and a solvent that do not belong to the aforementioned photopolymerization initiators, within the scope of impairing the effect of the present invention. other ingredients.

前述其他成分可為公知的成分，可根據目的任意選擇，並無特別限定，作為較佳的前述其他成分，例如可列舉：著色劑(染料、顏料)、抗劣化劑、抗靜電劑、阻燃劑、聚矽氧化合物、鏈轉移劑等各種添加劑。 The above-mentioned other components may be known components, and can be arbitrarily selected according to the purpose without particular limitation. Preferred examples of the above-mentioned other components include colorants (dyes, pigments), anti-deterioration agents, antistatic agents, flame retardants Agents, polysiloxanes, chain transfer agents and other additives.

黏著劑組成物(i)所含有之前述其他成分可僅為1種，亦可為2種以上。 The said other component contained in an adhesive composition (i) may be only 1 type, and may be 2 or more types.

[黏著劑組成物(ii)] [Adhesive composition (ii)]

黏著劑組成物(ii)含有丙烯酸系樹脂及異氰酸酯系交聯劑作為必需成分，前述丙烯酸系樹脂係具有羥基且於側 鏈具有聚合性基之丙烯酸系樹脂(例如，具有羥基且經由胺基甲酸酯鍵而於側鏈具有聚合性基之丙烯酸系樹脂)。 The adhesive composition (ii) contains, as essential components, an acrylic resin and an isocyanate-based crosslinking agent, wherein the acrylic resin has a hydroxyl group on the side An acrylic resin having a polymerizable group in the chain (eg, an acrylic resin having a hydroxyl group and having a polymerizable group in a side chain via a urethane bond).

於使用黏著劑組成物(ii)之情形時，藉由丙烯酸系樹脂於側鏈具有聚合性基，相較於如黏著劑組成物(i)之情形般使用能量線聚合性化合物並藉由照射能量線進行聚合反應之情形而言，因聚合反應(硬化)後的黏著劑層的黏著性降低而自被黏著體之剝離性提高，附有保護膜之半導體晶片之拾取性提高。 In the case of using the adhesive composition (ii), since the acrylic resin has a polymerizable group in the side chain, as compared with the case of the adhesive composition (i), the energy ray polymerizable compound is used and irradiated. When the energy ray undergoes the polymerization reaction, the adhesiveness of the adhesive layer after the polymerization reaction (curing) is reduced, and the peelability from the adherend is improved, and the pick-up property of the semiconductor wafer with the protective film is improved.

再者，本說明書中，關於黏著劑組成物(ii)中的「丙烯酸系樹脂」之記載，只要無特別說明，則意指「於側鏈具有聚合性基之丙烯酸系樹脂」。 In addition, in this specification, the description of "acrylic resin" in the adhesive composition (ii) means "acrylic resin having a polymerizable group in a side chain" unless otherwise specified.

(丙烯酸系樹脂) (acrylic resin)

作為上述之於側鏈具有聚合性基之丙烯酸系樹脂，例如可列舉以下述方式獲得之丙烯酸系樹脂：使作為單體之不具有羥基之不含羥基之(甲基)丙烯酸酯以及具有羥基之含羥基之(甲基)丙烯酸酯等含羥基之化合物進行共聚合，而獲得含羥基之共聚物，使所獲得之含羥基之共聚物的羥基以及具有異氰酸酯基及聚合性基之化合物的異氰酸酯基反應，而形成胺基甲酸酯鍵，從而獲得丙烯酸系樹脂。 Examples of the above-mentioned acrylic resin having a polymerizable group in the side chain include acrylic resins obtained by mixing a (meth)acrylate having no hydroxyl group as a monomer and a hydroxyl group-free (meth)acrylate having a hydroxyl group as a monomer. A hydroxyl-containing compound such as a hydroxyl-containing (meth)acrylate is copolymerized to obtain a hydroxyl-containing copolymer, and the hydroxyl group of the obtained hydroxyl-containing copolymer and the isocyanate group of the compound having an isocyanate group and a polymerizable group are A urethane bond is formed by reaction, and an acrylic resin is obtained.

作為前述不含羥基之(甲基)丙烯酸酯，例如可列舉：黏著劑組成物(i)中的(甲基)丙烯酸酯中除含羥基之(甲基) 丙烯酸酯以外的(甲基)丙烯酸酯。 As the aforementioned hydroxyl-free (meth)acrylate, for example, in the (meth)acrylate in the adhesive composition (i), a hydroxyl-containing (meth)acrylate can be exemplified. (Meth)acrylates other than acrylates.

另外，作為前述含羥基之化合物，可列舉：與黏著劑組成物(i)中的含羥基之(甲基)丙烯酸酯相同之化合物。 Moreover, as said hydroxyl-containing compound, the compound similar to the hydroxyl-containing (meth)acrylate in an adhesive composition (i) is mentioned.

構成前述丙烯酸系樹脂之不含羥基之(甲基)丙烯酸酯及含羥基之化合物可分別僅為1種，亦可為2種以上。 The hydroxyl group-free (meth)acrylate and the hydroxyl group-containing compound constituting the above-mentioned acrylic resin may be only one type, respectively, or two or more types may be used.

作為前述具有異氰酸酯基及聚合性基之化合物，例如可列舉：異氰酸2-甲基丙烯醯氧基乙酯等含異氰酸酯基之(甲基)丙烯酸酯等。 As a compound which has the said isocyanate group and a polymerizable group, isocyanate group-containing (meth)acrylates, such as 2-methacryloyloxyethyl isocyanate, are mentioned, for example.

構成前述丙烯酸系樹脂之前述具有異氰酸酯基及聚合性基之化合物可僅為1種，亦可為2種以上。 The compound which has the said isocyanate group and a polymerizable group which comprises the said acrylic resin may be only 1 type, and may be 2 or more types.

黏著劑組成物(ii)所含有之丙烯酸系樹脂可僅為1種，亦可為2種以上。 The acrylic resin contained in the adhesive composition (ii) may be only one type or two or more types.

關於黏著劑組成物(ii)中的丙烯酸系樹脂的含量，相對於黏著劑組成物(ii)中的溶劑以外的全部含有成分的總質量，較佳為80質量%至99質量%，更佳為90質量%至97質量%。 The content of the acrylic resin in the adhesive composition (ii) is preferably 80% by mass to 99% by mass relative to the total mass of all components other than the solvent in the adhesive composition (ii), more preferably It is 90 mass % to 97 mass %.

(異氰酸酯系交聯劑) (Isocyanate based crosslinking agent)

作為前述異氰酸酯系交聯劑，例如可列舉：與黏著劑組成物(i)中的作為交聯劑之前述有機多元異氰酸酯化合物相同之化合物。 As said isocyanate type crosslinking agent, the same compound as the said organic polyvalent isocyanate compound which is a crosslinking agent in an adhesive composition (i) is mentioned, for example.

黏著劑組成物(ii)所含有之異氰酸酯系交聯劑可僅為1種，亦可為2種以上。 Only one type of isocyanate-based crosslinking agent contained in the adhesive composition (ii) may be used, or two or more types may be used.

黏著劑組成物(ii)中的異氰酸酯系交聯劑所具有之異氰酸酯基的莫耳數相對於黏著劑組成物(ii)中的丙烯酸系樹脂所具有之羥基的莫耳數，較佳為0.2倍至3倍。藉由異氰酸酯基的前述莫耳數為前述下限值以上，因硬化後的黏著劑層的黏著性降低而自被黏著體之剝離性提高，附有保護膜之半導體晶片之拾取性提高。另外，藉由異氰酸酯基的前述莫耳數為前述上限值以下，可進一步抑制因異氰酸酯系交聯劑彼此之反應而產生副產物。 The molar number of isocyanate groups in the isocyanate-based crosslinking agent in the adhesive composition (ii) is preferably 0.2 relative to the molar number of hydroxyl groups in the acrylic resin in the adhesive composition (ii) times to 3 times. Since the said molar number of an isocyanate group is more than the said lower limit, the adhesiveness of the adhesive layer after hardening falls, the peelability from a to-be-adhered body improves, and the pick-up property of the semiconductor wafer with a protective film improves. Moreover, by the said molar number of an isocyanate group being below the said upper limit, generation|occurrence|production of a by-product by the reaction of isocyanate type crosslinking agents can be suppressed further.

黏著劑組成物(ii)中的異氰酸酯系交聯劑的含量以使異氰酸酯基的莫耳數成為如上述之範圍之方式適宜調節即可，但較佳為滿足此種條件，並且相對於丙烯酸系樹脂的含量100質量份為0.01質量份至20質量份，更佳為0.1質量份至15質量份，尤佳為0.3質量份至12質量份。 The content of the isocyanate-based crosslinking agent in the adhesive composition (ii) may be appropriately adjusted so that the number of moles of isocyanate groups falls within the above-mentioned range. The content of the resin is 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and particularly preferably 0.3 to 12 parts by mass, per 100 parts by mass of the resin.

(光聚合起始劑) (photopolymerization initiator)

黏著劑組成物(ii)中，除前述丙烯酸系樹脂及異氰酸酯系交聯劑以外，亦可含有光聚合起始劑。 The adhesive composition (ii) may contain a photopolymerization initiator in addition to the aforementioned acrylic resin and isocyanate-based crosslinking agent.

作為前述光聚合起始劑，例如可列舉與黏著劑組成物(i)之情形相同之光聚合起始劑。 As said photoinitiator, the photoinitiator similar to the case of an adhesive composition (i) is mentioned, for example.

黏著劑組成物(ii)所含有之光聚合起始劑可僅為1種，亦可為2種以上。 The photopolymerization initiator contained in the adhesive composition (ii) may be only one type or two or more types.

於使用光聚合起始劑之情形時，黏著劑組成物(ii)中的光聚合起始劑的含量相對於丙烯酸系樹脂的含量100質量份，較佳為0.05質量份至20質量份。 In the case of using a photopolymerization initiator, the content of the photopolymerization initiator in the adhesive composition (ii) is preferably 0.05 to 20 parts by mass relative to 100 parts by mass of the content of the acrylic resin.

藉由光聚合起始劑的前述含量為前述下限值以上，可獲得充分的由使用光聚合起始劑所帶來之功效。另外，藉由光聚合起始劑的前述含量為前述上限值以下，可抑制由過量的光聚合起始劑產生副生成分，從而使黏著劑層更良好地進行硬化。 When the said content of a photopolymerization initiator is more than the said lower limit, sufficient effect by using a photopolymerization initiator can be obtained. Moreover, since the said content of a photoinitiator is below the said upper limit, generation|occurrence|production of a by-product from an excess photoinitiator can be suppressed, and hardening of an adhesive bond layer can be performed more favorably.

(溶劑) (solvent)

黏著劑組成物(ii)較佳為除前述丙烯酸系樹脂及異氰酸酯系交聯劑以外，進一步含有溶劑。 The adhesive composition (ii) preferably further contains a solvent in addition to the aforementioned acrylic resin and isocyanate-based crosslinking agent.

作為前述溶劑，例如可列舉與黏著劑組成物(i)之情形相同之溶劑。 As said solvent, the thing similar to the case of an adhesive composition (i) is mentioned, for example.

黏著劑組成物(ii)所含有之溶劑可僅為1種，亦可為2種以上。 The solvent contained in the adhesive composition (ii) may be only one type or two or more types.

黏著劑組成物(ii)含有溶劑之情形時，溶劑的含量相對於黏著劑組成物(ii)的總質量，較佳為40質量%至90質量%，更佳為50質量%至80質量%。 When the adhesive composition (ii) contains a solvent, the content of the solvent is preferably 40 to 90 mass %, more preferably 50 to 80 mass % relative to the total mass of the adhesive composition (ii). .

(其他成分) (other ingredients)

黏著劑組成物(ii)中，除前述丙烯酸系樹脂及異氰酸酯系交聯劑以外，亦可在無損本發明的功效之範圍內，含有不符合前述光聚合起始劑及溶劑之其他成分。 In addition to the aforementioned acrylic resin and isocyanate-based crosslinking agent, the adhesive composition (ii) may also contain other components that do not conform to the aforementioned photopolymerization initiator and solvent within the scope of impairing the efficacy of the present invention.

作為前述其他成分，例如可列舉與黏著劑組成物(i)之情形相同之成分。 As said other component, the thing similar to the case of an adhesive composition (i) is mentioned, for example.

黏著劑組成物(ii)所含有之前述其他成分可僅為1種，亦可為2種以上。 The said other component contained in an adhesive composition (ii) may be only 1 type, and may be 2 or more types.

至此，對含有藉由照射能量線而聚合之成分之黏著劑組成物進行了說明，但形成黏著劑層時，亦可使用不含藉由照射能量線而聚合之成分之黏著劑組成物。亦即，黏著劑層亦可為不具有能量線硬化性之非能量線硬化性。 Heretofore, the adhesive composition containing the component polymerized by irradiation with energy ray has been described, but when forming the adhesive layer, an adhesive composition containing no component polymerized by irradiation with energy ray can also be used. That is, the adhesive layer may be non-energy ray sclerosing which does not have energy ray sclerosis.

作為較佳的此種非能量線硬化性黏著劑組成物，例如可列舉含有丙烯酸系樹脂及交聯劑之黏著劑組成物(以下，有時簡稱為「黏著劑組成物(iii)」)等，亦可含有溶劑、不屬於溶劑之其他成分等任意成分。 As such a preferable non-energy ray-curable adhesive composition, for example, an adhesive composition containing an acrylic resin and a crosslinking agent (hereinafter, may be simply referred to as "adhesive composition (iii)"), etc. , and may contain optional components such as solvents and other components that are not solvents.

[黏著劑組成物(iii)] [Adhesive composition (iii)]

黏著劑組成物(iii)所含有之前述丙烯酸系樹脂、交聯劑、溶劑及其他成分均與黏著劑組成物(i)中的這些成分相同。 The aforementioned acrylic resin, crosslinking agent, solvent and other components contained in the adhesive composition (iii) are the same as those in the adhesive composition (i).

關於黏著劑組成物(iii)中的丙烯酸系樹脂的含量，相 對於黏著劑組成物(iii)中的溶劑以外的全部含有成分的總質量，較佳為40質量%至99質量%，更佳為50質量%至97質量%。 Regarding the content of the acrylic resin in the adhesive composition (iii), phase The total mass of all components other than the solvent in the adhesive composition (iii) is preferably 40 to 99 mass %, more preferably 50 to 97 mass %.

關於黏著劑組成物(iii)中的交聯劑的含量，相對於丙烯酸系樹脂的含量100質量份，較佳為2質量份至30質量份，更佳為4質量份至25質量份。 The content of the crosslinking agent in the adhesive composition (iii) is preferably 2 to 30 parts by mass, more preferably 4 to 25 parts by mass, relative to 100 parts by mass of the acrylic resin.

黏著劑組成物(iii)除上述方面以外與黏著劑組成物(i)相同。 The adhesive composition (iii) is the same as the adhesive composition (i) except for the above points.

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

黏著劑組成物(i)至黏著劑組成物(iii)等前述黏著劑組成物可藉由下述方式而獲得：將前述黏著劑、及視需要之除前述黏著劑以外的成分等用以構成黏著劑組成物之各成分加以調配。 The above-mentioned adhesive compositions such as the adhesive composition (i) to the adhesive composition (iii) can be obtained by the following means: the above-mentioned adhesive and, if necessary, components other than the above-mentioned adhesive are used to constitute The components of the adhesive composition are formulated.

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

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。 The method of mixing the components during the preparation is not particularly limited, and may be appropriately selected from the following well-known methods: a method of mixing by rotating a stirring bar or a stirring blade, a method of mixing using a mixer, and a method of applying ultrasonic waves for mixing method etc.

關於添加及混合各成分時的溫度及時間，只要不會使各調配成分劣化，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 they do not deteriorate the components, and can be adjusted as appropriate. It is preferably 15°C to 30°C.

‧塗層 ‧coating

關於前述塗層，例如較佳為前述塗層中的與和基材接觸之側為相反側的表面的表面粗糙度Ra小於基材中的具備有塗層之側的表面的表面粗糙度Ra。 Regarding the coating layer, for example, it is preferable that the surface roughness Ra of the surface of the coating layer on the side opposite to the side in contact with the substrate is smaller than the surface roughness Ra of the surface having the coating layer in the substrate.

作為塗層，例如較佳為含有藉由照射能量線進行硬化而獲得之硬化物之塗層，較佳為使含有藉由照射能量線進行聚合之能量線聚合性化合物之塗佈組成物硬化而獲得之塗層。並且，前述能量線聚合性化合物較佳為(甲基)丙烯酸或其衍生物。 As the coating layer, for example, a coating layer containing a cured product obtained by curing by irradiating energy rays is preferable, and a coating composition containing an energy ray polymerizable compound polymerizing by irradiating energy rays is preferably cured. obtained coating. Further, the energy ray polymerizable compound is preferably (meth)acrylic acid or a derivative thereof.

再者，本說明書中，所謂「衍生物」意指原本之化合物的至少1個氫原子被氫原子以外的基(取代基)取代而成之化合物。 In addition, in this specification, the "derivative" means a compound in which at least one hydrogen atom of the original compound is substituted by a group (substituent) other than a hydrogen atom.

前述保護膜形成用片不僅具有形成用以保護切割所得之半導體晶片的背面之保護膜之功能，例如亦可兼具作為切割半導體晶圓時之切割片之功能。並且，切割半導體晶圓時，有時將貼附有保護膜形成用片之半導體晶圓延伸，該情形時，要求保護膜形成用片具有適度的柔軟性。為了對保護膜形成用片賦予適度的柔軟性，例如有時選擇聚丙烯等柔軟的樹脂作為構成前述支持片之材質。另一方面，此種柔軟的樹脂等有時因加熱而變形或產生褶皺。因此，塗層可謂較理想為可使成為原料之組成物藉由照射能量 線進行硬化，並非進行熱硬化而形成。 The sheet for forming a protective film not only has a function of forming a protective film for protecting the back surface of a semiconductor wafer obtained by dicing, but also functions as a dicing sheet when dicing a semiconductor wafer, for example. In addition, when a semiconductor wafer is diced, the semiconductor wafer to which the sheet for forming a protective film is attached may be stretched, and in this case, the sheet for forming a protective film is required to have moderate flexibility. In order to impart moderate flexibility to the sheet for forming a protective film, for example, a flexible resin such as polypropylene may be selected as a material constituting the support sheet. On the other hand, such a soft resin or the like may be deformed or wrinkled by heating. Therefore, the coating can be described ideally as a composition that can become a raw material by irradiating energy The wire is hardened, not formed by thermal hardening.

前述塗層的厚度並無特別限定，較佳為0.1μm至20μm，更佳為0.4μm至15μm，尤佳為0.8μm至10μm。藉由塗層的厚度為前述下限值以上，塗層中的與和基材接觸之側為相反側的表面的表面粗糙度Ra變得更容易降低，進一步抑制前述保護膜形成用片之黏連之功效變得更高。另外，藉由塗層的厚度為前述上限值以下，經由前述片藉由紅外線相機等檢測貼附前述保護膜形成用片後的半導體晶片的狀態時，可獲取更清晰的檢測圖像，進一步可更容易地伴隨延伸切割半導體晶圓。 The thickness of the aforementioned coating layer is not particularly limited, but is preferably 0.1 μm to 20 μm, more preferably 0.4 μm to 15 μm, and particularly preferably 0.8 μm to 10 μm. When the thickness of the coating layer is equal to or more than the aforementioned lower limit value, the surface roughness Ra of the surface of the coating layer on the opposite side to the side in contact with the substrate becomes more easily reduced, and the sticking of the sheet for forming a protective film is further suppressed. Link's efficacy has become higher. In addition, when the thickness of the coating layer is equal to or less than the upper limit value, when the state of the semiconductor wafer to which the sheet for forming a protective film is attached is detected by an infrared camera or the like through the sheet, a clearer inspection image can be obtained, and further The semiconductor wafer can be more easily diced with the extension.

再者，由於塗層如上所述般被覆基材的凹凸面，故而與基材之接觸面可成為凹凸面，然而關於塗層的厚度，只要於塗層的該凹凸面中包含凸部之部位中將該凸部的頂端作為一起點而算出即可。 Furthermore, since the coating coats the uneven surface of the substrate as described above, the contact surface with the substrate can be the uneven surface. However, regarding the thickness of the coating, as long as the uneven surface of the coating includes the convex portion. It is sufficient to calculate the top end of the convex portion as a common point.

保護膜形成用片中，於前述塗層成為與前述剝離膜側為相反側的最外層之情形時，前述塗層中的與和基材接觸之側為相反側的表面(亦即露出面)的表面粗糙度Ra為0μm以上0.5μm以下。 In the sheet for forming a protective film, when the coating layer is the outermost layer on the opposite side to the release film side, the side of the coating layer that is in contact with the substrate is the surface on the opposite side (that is, the exposed surface). The surface roughness Ra is 0 μm or more and 0.5 μm or less.

塗層的前述表面粗糙度Ra例如可藉由基材中的具備有塗層之側的表面的表面粗糙度Ra、塗層的厚度、用以形成塗層之後述塗佈組成物的塗敷方法等進行調節。 The aforementioned surface roughness Ra of the coating layer can be determined, for example, by the surface roughness Ra of the surface on the side having the coating layer in the substrate, the thickness of the coating layer, and the coating method of the coating composition described later for forming the coating layer. etc. to adjust.

<<塗佈組成物>> <<Coating composition>>

前述塗佈組成物較佳為含有二氧化矽溶膠及鍵結有含自由基聚合性不飽和基之有機化合物之二氧化矽微粒子中的任一者或兩者(α)(以下，有時簡稱為「成分(α)」)、以及選自由多官能性丙烯酸酯系單體及丙烯酸酯系預聚物所組成之群組中的至少1種(β)(以下，有時簡稱為「成分(β)」)。 The coating composition is preferably one or both (α) (hereinafter, sometimes abbreviated as abbreviated as SiO 2 sol) and silica fine particles bound with an organic compound containing a radically polymerizable unsaturated group. "component (α)"), and at least one (β) selected from the group consisting of a polyfunctional acrylate-based monomer and an acrylate-based prepolymer (hereinafter, sometimes abbreviated as "component ( β)").

[成分(α)] [Ingredient (α)]

前述成分(α)係使前述塗層的折射率降低，並且使前述保護膜形成用片的硬化收縮性及熱濕收縮性降低，從而抑制因這些收縮而導致保護膜形成用片中產生捲曲。 The said component (α) reduces the refractive index of the said coating layer, and reduces the hardening shrinkage property and the heat-moisture shrinkage property of the said sheet for protective film formation, and suppresses the generation of curl in the sheet for protective film formation due to these shrinkages.

作為成分(α)中的二氧化矽溶膠，例如可列舉膠體二氧化矽，該膠體二氧化矽係二氧化矽微粒子於醇、源自乙二醇之醚(例如溶纖劑)等有機溶劑中以膠體狀態懸浮而成；懸浮之前述二氧化矽微粒子的平均粒徑較佳為0.001μm至1μm，更佳為0.03μm至0.05μm。 Examples of the silica sol in the component (α) include colloidal silica in which fine particles of silica-based silica are contained in organic solvents such as alcohols and ethers derived from ethylene glycol (eg, cellosolve). Suspended in a colloidal state; the average particle size of the suspended silica particles is preferably 0.001 μm to 1 μm, more preferably 0.03 μm to 0.05 μm.

成分(α)中的鍵結有含自由基聚合性不飽和基之有機化合物之二氧化矽微粒子藉由照射能量線而進行交聯及硬化。 The silica fine particles in which the radically polymerizable unsaturated group-containing organic compound is bonded in the component (α) are cross-linked and cured by irradiation with energy rays.

作為前述鍵結有含自由基聚合性不飽和基之有機化合物之二氧化矽微粒子，例如可列舉存在於二氧化矽微粒 子的表面之矽烷醇基與含自由基聚合性不飽和基之有機化合物中的官能基反應而成之粒子，該二氧化矽微粒子的平均粒徑較佳為0.005μm至1μm。含自由基聚合性不飽和基之有機化合物中的前述官能基只要可與二氧化矽微粒子中的前述矽烷醇基反應，則並無特別限定。 Examples of the silica fine particles to which the radically polymerizable unsaturated group-containing organic compound is bound include, for example, those present in the silica fine particles. Silanol groups on the surface of the particles react with functional groups in an organic compound containing a radically polymerizable unsaturated group. The silica particles preferably have an average particle size of 0.005 μm to 1 μm. The functional group in the radically polymerizable unsaturated group-containing organic compound is not particularly limited as long as it can react with the silanol group in the silica fine particle.

作為具有前述官能基之含自由基聚合性不飽和基之有機化合物，例如可列舉下述通式(1)所表示之化合物等。 As a radical polymerizable unsaturated group containing organic compound which has the said functional group, the compound etc. which are represented by following general formula (1) are mentioned, for example.

Figure 106105584-A0305-02-0053-1
Figure 106105584-A0305-02-0053-1

(式中，R1為氫原子或甲基；R2為鹵素原子或下述式(2a)至式(2f)中的任一者所表示之基) (In the formula, R 1 is a hydrogen atom or a methyl group; R 2 is a halogen atom or a group represented by any one of the following formulae (2a) to (2f))

Figure 106105584-A0305-02-0053-2
Figure 106105584-A0305-02-0053-2

作為R2中的前述鹵素原子，例如可列舉：氯原子、溴 原子、碘原子等。 As said halogen atom in R< 2 >, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.

作為較佳的前述含自由基聚合性不飽和基之有機化合物，例如可列舉：(甲基)丙烯酸、(甲基)丙烯醯氯、(甲基)丙烯酸2-異氰酸酯基乙酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸2,3-亞胺基丙酯、(甲基)丙烯酸2-羥基乙酯、(3-(甲基)丙烯醯氧基丙基)三甲氧基矽烷等。 Examples of preferable radical-polymerizable unsaturated group-containing organic compounds include (meth)acrylic acid, (meth)acryloyl chloride, 2-isocyanatoethyl (meth)acrylate, (meth)acrylic acid, and (meth)acrylic acid. ) glycidyl acrylate, 2,3-iminopropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (3-(meth)acryloyloxypropyl)trimethoxysilane Wait.

本發明中，前述含自由基聚合性不飽和基之有機化合物可單獨使用1種，亦可併用2種以上。 In the present invention, the radically polymerizable unsaturated group-containing organic compound may be used alone or in combination of two or more.

成分(α)中，二氧化矽溶膠、及鍵結有含自由基聚合性不飽和基之有機化合物之二氧化矽微粒子可分別僅為1種，亦可為2種以上。 In the component (α), the silica sol and the silica fine particles bound with the radically polymerizable unsaturated group-containing organic compound may each be only one type or two or more types.

作為成分(α)，可僅使用二氧化矽溶膠，亦可僅使用前述鍵結有含自由基聚合性不飽和基之有機化合物之二氧化矽微粒子，還可併用二氧化矽溶膠及前述鍵結有含自由基聚合性不飽和基之有機化合物之二氧化矽微粒子。 As the component (α), only silica sol may be used, only the above-mentioned silica fine particles bound with an organic compound containing a radically polymerizable unsaturated group may be used, or a combination of silica sol and the above-mentioned bonding may be used. Silica microparticles containing organic compounds containing radically polymerizable unsaturated groups.

前述塗佈組成物中的成分(α)的含量較佳為根據前述支持片之塗層以外的層的折射率進行選擇，通常較佳為使前述塗層中的源自成分(α)之二氧化矽的含量相對於塗佈組成物的總質量成為20質量%至60質量%之量。藉由 二氧化矽的前述含量為前述下限值以上，使塗層的折射率降低之功效、及抑制前述保護膜形成用片中產生捲曲之功效變得更高。另外，藉由二氧化矽的前述含量為前述上限值以下，更容易形成塗層，並且抑制塗層硬度降低之功效變得更高。 The content of the component (α) in the aforementioned coating composition is preferably selected according to the refractive index of the layer other than the coating layer of the aforementioned support sheet, and it is usually preferable to make the second of the aforementioned coating layer derived from the component (α) The content of silicon oxide is in an amount of 20% by mass to 60% by mass with respect to the total mass of the coating composition. by When the said content of silicon dioxide is more than the said lower limit, the effect of reducing the refractive index of a coating layer, and the effect of suppressing the generation|occurence|production of curl in the said sheet for protective film formation become high. In addition, by the above-mentioned content of silicon dioxide being equal to or less than the above-mentioned upper limit value, it becomes easier to form a coating layer, and the effect of suppressing a decrease in the hardness of the coating layer becomes higher.

就上述塗層的折射率、形成容易性及硬度、以及抑制保護膜形成用片中產生捲曲之性質變得更良好而言，塗層中的源自成分(α)之二氧化矽的含量更佳為相對於塗佈組成物的總質量為20質量%至45質量%。 The refractive index, ease of formation and hardness of the above-mentioned coating layer, and the property of suppressing the occurrence of curling in the sheet for forming a protective film become better, and the content of silicon dioxide derived from the component (α) in the coating layer is higher. It is preferably 20% by mass to 45% by mass relative to the total mass of the coating composition.

[成分(β)] [Ingredient (β)]

前述成分(β)為形成前述塗層之主要的光硬化性成分。 The said component (β) is the main photocurable component which forms the said coating layer.

前述成分(β)中的多官能性丙烯酸酯系單體只要為於1分子中具有至少2個(甲基)丙烯醯基之(甲基)丙烯酸衍生物，則並無特別限定。 The polyfunctional acrylate-based monomer in the component (β) is not particularly limited as long as it is a (meth)acrylic acid derivative having at least two (meth)acryloyl groups in one molecule.

作為較佳的前述多官能性丙烯酸酯系單體，例如可列舉：1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、羥基特戊酸新戊二醇二(甲基)丙烯酸酯、二(甲基)丙烯酸二環戊酯、己內酯改性二(甲基)丙烯酸二環戊烯酯、環氧乙烷改性磷酸二(甲基)丙烯酸酯、烯丙基化環己基二(甲基)丙烯酸酯、異氰脲酸酯二(甲基)丙烯酸酯、 三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、丙酸改性二季戊四醇三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、環氧丙烷改性三羥甲基丙烷三(甲基)丙烯酸酯、異氰脲酸三(丙烯醯氧基乙基)酯、二季戊四醇五(甲基)丙烯酸酯、丙酸改性二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、己內酯改性二季戊四醇六(甲基)丙烯酸酯等。 As a preferable said polyfunctional acrylate type monomer, for example, 1, 4- butanediol di(meth)acrylate, 1, 6-hexanediol di(meth)acrylate, neopentyl Glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, dicyclopentyl di(meth)acrylate, hexamethylene Lactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate Di(meth)acrylate, Trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide modified Trimethylolpropane tri(meth)acrylate, tris(acrylooxyethyl) isocyanurate, dipentaerythritol penta(meth)acrylate, propionic acid modified dipentaerythritol penta(methyl) Acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, etc.

前述成分(β)中的丙烯酸酯系預聚物只要為利用(甲基)丙烯酸酯而具有光硬化性之聚合物或低聚物，則並無特別限定。 The acrylate-based prepolymer in the aforementioned component (β) is not particularly limited as long as it is a polymer or oligomer having photocurability using (meth)acrylate.

作為較佳的前述丙烯酸酯系預聚物，例如可列舉：聚酯丙烯酸酯系預聚物、環氧丙烯酸酯系預聚物、丙烯酸胺基甲酸酯系預聚物、多元醇丙烯酸酯系預聚物等。 Examples of preferable acrylate-based prepolymers include polyester acrylate-based prepolymers, epoxy acrylate-based prepolymers, acrylic urethane-based prepolymers, and polyol acrylate-based prepolymers. prepolymer, etc.

作為前述聚酯丙烯酸酯系預聚物，例如可列舉藉由下述方式而獲得之預聚物等：藉由多元羧酸與多元醇之縮合反應而獲得於分子的兩末端具有羥基之聚酯低聚物，利用(甲基)丙烯酸將所獲得之聚酯低聚物的羥基酯化；使多元羧酸與環氧烷進行加成反應而獲得低聚物，利用(甲基)丙烯酸將所獲得之低聚物的末端的羥基酯化。 Examples of the polyester acrylate-based prepolymer include a prepolymer obtained by, for example, a polyester having a hydroxyl group at both ends of the molecule by condensation reaction of a polyvalent carboxylic acid and a polyhydric alcohol. Oligomer, the hydroxyl group of the obtained polyester oligomer is esterified with (meth)acrylic acid; the oligomer is obtained by addition reaction of polycarboxylic acid and alkylene oxide, and the obtained oligomer is obtained with (meth)acrylic acid The terminal hydroxyl group of the obtained oligomer is esterified.

作為前述環氧丙烯酸酯系預聚物，例如可列舉藉由下述方式而獲得之預聚物：使相對較低分子量的雙酚型環氧樹脂或酚醛清漆型環氧樹脂的環氧乙烷環(oxirane ring)與 (甲基)丙烯酸反應而進行酯化。 As said epoxy acrylate type prepolymer, the prepolymer obtained by, for example, a relatively low molecular weight bisphenol-type epoxy resin or a novolac-type epoxy resin of ethylene oxide can be mentioned. oxirane ring and (Meth)acrylic acid reacts and is esterified.

作為前述丙烯酸胺基甲酸酯系預聚物，例如可列舉藉由下述方式而獲得之預聚物：藉由聚醚多元醇或聚酯多元醇與多異氰酸酯之反應而獲得聚胺基甲酸酯低聚物，利用(甲基)丙烯酸將所獲得之聚胺基甲酸酯低聚物酯化。 Examples of the aforementioned acrylic urethane-based prepolymer include prepolymers obtained by reacting polyether polyol or polyester polyol with polyisocyanate to obtain polyurethane The obtained polyurethane oligomer was esterified with (meth)acrylic acid.

作為前述多元醇丙烯酸酯系預聚物，例如可列舉藉由下述方式而獲得之預聚物：利用(甲基)丙烯酸將聚醚多元醇的羥基酯化。 As said polyol acrylate type prepolymer, the prepolymer obtained by esterifying the hydroxyl group of a polyether polyol with (meth)acrylic acid is mentioned, for example.

成分(β)中，前述多官能性丙烯酸酯系單體及丙烯酸酯系預聚物可分別僅為1種，亦可為2種以上。 In the component (β), each of the multifunctional acrylate-based monomer and the acrylate-based prepolymer may be only one type, or two or more types may be used.

作為成分(β)，可僅使用前述多官能性丙烯酸酯系單體，亦可僅使用前述丙烯酸酯系預聚物，還可併用前述多官能性丙烯酸酯系單體及丙烯酸酯系預聚物。 As the component (β), only the above-described polyfunctional acrylate-based monomer may be used, only the above-described acrylate-based prepolymer may be used, or the above-described polyfunctional acrylate-based monomer and acrylate-based prepolymer may be used in combination .

前述塗佈組成物較佳為除成分(α)及成分(β)以外進一步含有溶劑。藉由塗佈組成物含有溶劑，如後所述，可更容易地將塗佈組成物塗敷及乾燥，而形成用以形成塗層之塗膜。 In addition to the component (α) and the component (β), the coating composition preferably further contains a solvent. When the coating composition contains a solvent, as will be described later, the coating composition can be more easily applied and dried to form a coating film for forming a coating layer.

前述溶劑可單獨使用1種，亦可併用2種以上。 The said solvent may be used individually by 1 type, and may use 2 or more types together.

作為前述溶劑，例如可列舉：己烷、庚烷、環己烷等脂肪族烴；甲苯、二甲苯等芳香族烴；二氯甲烷、二氯乙 烷等鹵代烴；甲醇、乙醇、丙醇、丁醇、1-甲氧基-2-丙醇等醇；丙酮、甲基乙基酮、2-戊酮、異佛爾酮、環己酮等酮；乙酸乙酯、乙酸丁酯等酯；2-乙氧基乙醇(亦稱為乙基溶纖劑)等溶纖劑等。 Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene; dichloromethane, dichloroethane, and the like. Halogenated hydrocarbons such as alkane; alcohols such as methanol, ethanol, propanol, butanol, 1-methoxy-2-propanol; acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone ketones; ethyl acetate, butyl acetate and other esters; 2-ethoxyethanol (also known as ethyl cellosolve) and other cellosolves.

前述塗佈組成物中，除成分(α)及成分(β)以外，亦可在無損本發明的功效之範圍內，進一步含有單官能性丙烯酸酯系單體、光聚合起始劑、光增感劑、聚合抑制劑、交聯劑、抗氧化劑、紫外線吸收劑、光穩定劑、調平劑、消泡劑等各種任意成分。 In addition to the component (α) and the component (β), the coating composition may further contain a monofunctional acrylate-based monomer, a photopolymerization initiator, a photointensifier, and a Various optional components such as sensitizers, polymerization inhibitors, cross-linking agents, antioxidants, ultraviolet absorbers, light stabilizers, leveling agents, and antifoaming agents.

前述任意成分可單獨使用1種，亦可併用2種以上。 The said arbitrary components may be used individually by 1 type, and may use 2 or more types together.

作為任意成分之前述單官能性丙烯酸酯系單體為光硬化性成分，只要為於1分子中僅具有1個(甲基)丙烯醯基之(甲基)丙烯酸衍生物，則並無特別限定。 The aforementioned monofunctional acrylate-based monomer as an optional component is a photocurable component, and is not particularly limited as long as it is a (meth)acrylic derivative having only one (meth)acryloyl group in one molecule. .

作為較佳的前述單官能性丙烯酸酯系單體，例如可列舉：(甲基)丙烯酸環己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸十二烷基酯(亦稱為(甲基)丙烯酸月桂酯)、(甲基)丙烯酸十八烷基酯(亦稱為(甲基)丙烯酸硬脂酯)、(甲基)丙烯酸異冰片酯等。 As a preferable said monofunctional acrylate type monomer, for example, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate ( Also known as lauryl (meth)acrylate), octadecyl (meth)acrylate (also known as stearyl (meth)acrylate), isobornyl (meth)acrylate, and the like.

作為任意成分之前述光聚合起始劑可列舉：針對自由基聚合以往所使用之公知的光聚合起始劑。 As said photoinitiator of an arbitrary component, the well-known photoinitiator conventionally used for radical polymerization is mentioned.

作為較佳的前述光聚合起始劑，例如可列舉：苯乙酮 系化合物、二苯甲酮系化合物、烷基胺基二苯甲酮系化合物、苯偶醯系化合物、安息香系化合物、安息香醚系化合物、苯偶醯二甲基縮酮系化合物、苯甲醯苯甲酸酯系化合物、α-醯基肟酯系化合物等芳基酮系光聚合起始劑；硫醚系化合物、噻噸酮系化合物等含硫系光聚合起始劑；醯基二芳基氧化膦等醯基氧化膦系化合物；蒽醌系化合物等。 As a preferable aforementioned photopolymerization initiator, for example, acetophenone can be mentioned: series compounds, benzophenone series compounds, alkylaminobenzophenone series compounds, benzoin series compounds, benzoin series compounds, benzoin ether series compounds, benzoin dimethyl ketal series compounds, benzyl alcohol series compounds Aryl ketone-based photopolymerization initiators such as benzoate-based compounds and α-acyl oxime ester-based compounds; sulfur-containing photopolymerization initiators such as thioether-based compounds and thioxanthone-based compounds; acyl diarylide Acrylophosphine oxide-based compounds such as phosphine oxide; anthraquinone-based compounds, etc.

再者，於藉由照射電子束使前述塗佈組成物硬化之情形時，無需光聚合起始劑。 Furthermore, in the case where the coating composition is cured by irradiating an electron beam, a photopolymerization initiator is not required.

前述塗佈組成物中，光聚合起始劑的含量相對於光硬化性成分的總含量100質量份，較佳為0.2質量份至10質量份，更佳為0.5質量份至7質量份。 In the aforementioned coating composition, the content of the photopolymerization initiator is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 7 parts by mass relative to 100 parts by mass of the total content of the photocurable components.

作為前述光增感劑，例如可列舉：三級胺類、對二甲胺基苯甲酸酯、硫醇系增感劑等。 As said photosensitizer, a tertiary amine, p-dimethylaminobenzoate, a thiol-type sensitizer etc. are mentioned, for example.

前述塗佈組成物中，光增感劑的含量相對於光硬化性成分的總含量100質量份，較佳為1質量份至20質量份，更佳為2質量份至10質量份。 In the aforementioned coating composition, the content of the photosensitizer is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass relative to 100 parts by mass of the total content of the photocurable components.

前述抗氧化劑、紫外線吸收劑及光穩定劑可為公知的化合物，但較佳為於分子內具有(甲基)丙烯醯基等之反應型的抗氧化劑、紫外線吸收劑及光穩定劑。這些抗氧化劑、紫外線吸收劑及光穩定劑鍵結於藉由照射能量線而形成 之聚合物鏈上，因此可抑制隨時間經過自硬化層逸散，從而長期發揮這些成分的功能。 The aforementioned antioxidants, ultraviolet absorbers and light stabilizers may be known compounds, but are preferably reactive antioxidants, ultraviolet absorbers, and light stabilizers having a (meth)acryloyl group or the like in the molecule. These antioxidants, ultraviolet absorbers, and light stabilizers are bonded to the On the polymer chain, it can suppress the escape of the self-hardening layer over time, so that the functions of these components can be exerted for a long time.

前述塗佈組成物較佳為含有二氧化矽溶膠作為成分(α)，更佳為含有以膠體狀態懸浮之二氧化矽微粒子的平均粒徑為0.03μm至0.05μm之二氧化矽溶膠。 The coating composition preferably contains silica sol as the component (α), and more preferably contains silica sol having an average particle diameter of 0.03 μm to 0.05 μm suspended in a colloidal state.

藉由前述塗層含有此種二氧化矽溶膠，抑制前述保護膜形成用片之黏連之功效變得更高。並且，前述塗層中，此種二氧化矽溶膠在與基材側為相反側的表面或該表面的附近區域，較其他區域更多地存在而偏集存在，藉此抑制前述保護膜形成用片之黏連之功效變得更高。前述塗層中，為了使二氧化矽溶膠等含有成分偏集存在，調節前述塗佈組成物的塗敷條件即可。 By containing such a silica sol in the coating layer, the effect of suppressing the blocking of the protective film-forming sheet becomes higher. In addition, in the coating layer, such silica sol is more present and segregated than other regions on the surface opposite to the substrate side or in the vicinity of the surface, thereby suppressing the protective film formation. The effect of sheet adhesion has become higher. In the coating layer, the coating conditions of the coating composition may be adjusted in order to allow components such as silica sol to exist in a segregated manner.

<<塗佈組成物的製造方法>> <<Manufacturing method of coating composition>>

塗佈組成物例如可藉由下述方式而獲得：將成分(α)及成分(β)等能量線聚合性化合物、及視需要的這些能量線聚合性化合物以外的成分等用以構成塗佈組成物之各成分加以調配。塗佈組成物例如可利用除調配成分不同之方面以外與上述黏著劑組成物之情形相同之方法獲得。 The coating composition can be obtained, for example, by using energy ray polymerizable compounds such as the component (α) and the component (β), and if necessary components other than these energy ray polymerizable compounds to constitute the coating composition. The components of the composition are adjusted. The coating composition can be obtained, for example, by the same method as in the case of the above-mentioned adhesive composition except that the composition is different.

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

塗佈組成物中的溶劑以外的成分可溶解，亦可不溶解而分散。並且，關於塗佈組成物中的各成分的濃度或黏度，只要使得塗佈組成物能夠塗敷，則並無特別限定。 Components other than the solvent in the coating composition may be dissolved or dispersed without being dissolved. In addition, the concentration and viscosity of each component in the coating composition are not particularly limited as long as the coating composition can be applied.

利用公知的方法塗敷塗佈組成物即可，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(meyer)棒式塗佈機、接觸式塗佈機等。 The coating composition may be applied by a known method, and examples thereof include methods using the following various coaters: air knife coater, knife coater, bar coater, gravure coater, roll coater Cloth machine, roll knife coater, curtain coater, die coater, knife coater, screen coater, meyer bar coater, contact coater, etc. .

○保護膜形成層 ○Protective film forming layer

前述保護膜形成層可為熱硬化性及能量線硬化性之任一種。保護膜形成層經由硬化而最終成為耐衝擊性高的保護膜。該保護膜例如防止切割步驟以後的半導體晶片中產生龜裂。 The above-mentioned protective film forming layer may be any of thermosetting properties and energy ray hardening properties. The protective film forming layer finally becomes a protective film with high impact resistance through curing. This protective film prevents, for example, cracks from occurring in the semiconductor wafer after the dicing step.

保護膜形成層可使用後述之熱硬化性保護膜形成層用組成物或能量線硬化性保護膜形成層用組成物(以下，有時將這些統稱為「保護膜形成層用組成物」)而形成。 The protective film-forming layer can be formed by using a composition for a thermosetting protective film-forming layer or a composition for an energy ray-curable protective film-forming layer (hereinafter, these may be collectively referred to as "the composition for a protective film-forming layer"), which will be described later. form.

保護膜形成層可僅為一層(單層)，亦可為兩層以上之複數層；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 protective film forming layer may be only one layer (single layer), or it may be a plurality of layers of two or more layers; in the case of a plurality of layers, these layers may be the same or different from each other, and the combination of these layers is not particularly limited .

保護膜形成層的厚度並無特別限定，較佳為1μm至100μm，更佳為5μm至75μm，尤佳為5μm至50μm。藉 由保護膜形成層的厚度為前述下限值以上，對保護膜或保護膜形成層照射雷射而進行雷射印字時，防止伴隨雷射之穿透而導致半導體晶圓破損之功效變高。另外，保護膜的保護能力提高。另一方面，藉由保護膜形成層的厚度為前述上限值以下，降低前述膜硬化時的收縮程度，減少附保護膜之半導體晶片的翹曲之功效變高。另外，溫度循環試驗時，抑制因保護膜與半導體晶圓之線膨脹係數之差而產生應力，抑制保護膜自半導體晶圓剝離之功效變高。 The thickness of the protective film forming layer is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 5 μm to 75 μm, and particularly preferably 5 μm to 50 μm. borrow When the thickness of the protective film forming layer is equal to or greater than the aforementioned lower limit value, when laser printing is performed by irradiating the protective film or the protective film forming layer with a laser, the effect of preventing the semiconductor wafer from being damaged due to penetration of the laser increases. In addition, the protective ability of the protective film is improved. On the other hand, when the thickness of a protective film forming layer is below the said upper limit, the shrinkage degree at the time of hardening of the said film is reduced, and the effect of reducing the warpage of the semiconductor wafer with a protective film becomes high. In addition, in the temperature cycle test, the generation of stress due to the difference between the linear expansion coefficients of the protective film and the semiconductor wafer is suppressed, and the effect of suppressing peeling of the protective film from the semiconductor wafer is increased.

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

‧熱硬化性保護膜形成層 ‧Thermosetting protective film forming layer

作為較佳的熱硬化性保護膜形成層，例如可列舉含有聚合物成分(A)及熱硬化性成分(B)之層。聚合物成分(A)係被視為聚合性化合物進行聚合反應而形成之成分。另外，熱硬化性成分(B)係可將熱作為反應之觸發(trigger)而進行硬化(聚合)反應之成分。再者，本發明中，聚合反應中亦包含有縮聚反應。 As a preferable thermosetting protective film forming layer, the layer containing a polymer component (A) and a thermosetting component (B) is mentioned, for example. The polymer component (A) is regarded as a component formed by a polymerization reaction of a polymerizable compound. Moreover, a thermosetting component (B) is a component which can perform a hardening (polymerization) reaction using heat as a trigger of a reaction. Furthermore, in the present invention, the polycondensation reaction is also included in the polymerization reaction.

<<熱硬化性保護膜形成層用組成物>> <<The composition for thermosetting protective film forming layer>>

熱硬化性保護膜形成層可由熱硬化性保護膜形成層用組成物形成，該熱硬化性保護膜形成層用組成物含有該熱硬化性保護膜形成層的構成材料。例如，於熱硬化性保 護膜形成層之形成對象面塗敷熱硬化性保護膜形成層用組成物，視需要使之乾燥，藉此可於目標部位形成熱硬化性保護膜形成層。熱硬化性保護膜形成層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熱硬化性保護膜形成層中的前述成分彼此的含量比率相同。 The thermosetting protective film-forming layer may be formed from a composition for a thermosetting protective film-forming layer containing a constituent material of the thermosetting protective film-forming layer. For example, in thermosetting A thermosetting protective film-forming layer can be formed on a target site by applying the composition for a thermosetting protective film-forming layer to the surface to be formed of the protective film-forming layer, and drying it if necessary. The content ratio of components that do not vaporize at normal temperature in the composition for a thermosetting protective film-forming layer is usually the same as the content ratio of the above-mentioned components in the thermosetting protective film-forming layer.

此處，所謂「常溫」係如上文所說明。 Here, the so-called "normal temperature" is as described above.

利用公知的方法塗敷熱硬化性保護膜形成層用組成物即可，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|coat the composition for thermosetting protective film-forming layers by a well-known method, for example, the method of using the following various coaters: Air knife coater, knife coater, bar coater, gravure coater, Cloth machine, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, wire rod coater, contact coater Cloth machine, etc.

熱硬化性保護膜形成層用組成物的乾燥條件並無特別限定，於熱硬化性保護膜形成層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 thermosetting protective film-forming layers are not particularly limited, and when the composition for thermosetting protective film-forming layers contains a solvent described later, it is preferable to perform heat drying, and in this case, it is preferable to Drying is performed, for example, at 70°C to 130°C for 10 seconds to 5 minutes.

<保護膜形成層用組成物(III-1)> <The composition for protective film forming layer (III-1)>

作為熱硬化性保護膜形成層用組成物，例如可列舉含有聚合物成分(A)及熱硬化性成分(B)之熱硬化性保護膜形成層用組成物(III-1)(本說明書中，有時簡稱為「保護膜形成層用組成物(III-1)」)等。 Examples of the composition for a thermosetting protective film-forming layer include the composition (III-1) for a thermosetting protective film-forming layer (in this specification) containing a polymer component (A) and a thermosetting component (B). , sometimes abbreviated as "the composition for protective film forming layer (III-1)") and the like.

[聚合物成分(A)] [Polymer component (A)]

聚合物成分(A)係用以對熱硬化性保護膜形成層賦予造膜性或可撓性等之聚合物化合物。 The polymer component (A) is a polymer compound for imparting film-forming properties, flexibility, and the like to the thermosetting protective film-forming layer.

保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層所含有之聚合物成分(A)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The composition (III-1) for a protective film-forming layer and the polymer component (A) contained in the thermosetting protective film-forming layer may be only one type or two or more types; in the case of two or more types , the combination and ratio of these can be arbitrarily selected.

作為聚合物成分(A)，例如可列舉：丙烯酸系樹脂(例如，具有(甲基)丙烯醯基之樹脂)、聚酯、胺基甲酸酯系樹脂(例如，具有胺基甲酸酯鍵之樹脂)、丙烯酸胺基甲酸酯樹脂、聚矽氧系樹脂(例如具有矽氧烷鍵之樹脂)、橡膠系樹脂(例如具有橡膠結構之樹脂)、苯氧基樹脂、熱硬化性聚醯亞胺等，較佳為丙烯酸系樹脂。 Examples of the polymer component (A) include acrylic resins (for example, resins having a (meth)acryloyl group), polyesters, and urethane resins (for example, those having urethane bonds) resins), acrylic urethane resins, polysiloxane-based resins (such as resins with siloxane bonds), rubber-based resins (such as resins with rubber structures), phenoxy resins, thermosetting polyamides imines, etc., preferably acrylic resins.

作為聚合物成分(A)中的前述丙烯酸系樹脂，可列舉公知的丙烯酸系聚合物。 As said acrylic resin in a polymer component (A), a well-known acrylic polymer is mentioned.

丙烯酸系樹脂的重量平均分子量(Mw)較佳為10000至2000000，更佳為100000至1500000。藉由丙烯酸系樹脂的重量平均分子量為前述下限值以上，熱硬化性保護膜形成層的形狀穩定性(保管時的經時穩定性)提高。另外，藉由丙烯酸系樹脂的重量平均分子量為前述上限值以下，熱硬化性保護膜形成層變得易於追隨被黏著體的凹凸面，可進一步抑制於被黏著體與熱硬化性保護膜形成層之間產生孔隙(void)等。 The weight average molecular weight (Mw) of the acrylic resin is preferably from 10,000 to 2,000,000, more preferably from 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is equal to or more than the above lower limit value, the shape stability of the thermosetting protective film-forming layer (time stability during storage) is improved. In addition, when the weight average molecular weight of the acrylic resin is equal to or less than the above-mentioned upper limit value, the thermosetting protective film-forming layer can easily follow the uneven surface of the adherend, and the formation of the adherend and the thermosetting protective film can be further suppressed. Voids and the like are generated between the layers.

丙烯酸系樹脂的玻璃轉移溫度(Tg)較佳為-60℃至70℃，更佳為-30℃至50℃。藉由丙烯酸系樹脂的Tg為前述下限值以上，可抑制保護膜與支持片之接著力，支持片之剝離性提高。另外，藉由丙烯酸系樹脂的Tg為前述上限值以下，熱硬化性保護膜形成層及保護膜與被黏著體之接著力提高。 The glass transition temperature (Tg) of the acrylic resin is preferably -60°C to 70°C, more preferably -30°C to 50°C. When Tg of an acrylic resin is more than the said lower limit, the adhesive force of a protective film and a support sheet can be suppressed, and the peelability of a support sheet improves. Moreover, since Tg of an acrylic resin is below the said upper limit, the adhesive force of a thermosetting protective film forming layer, a protective film, and a to-be-adhered body improves.

本說明書中，所謂「玻璃轉移溫度」係使用示差掃描熱量計測定試樣的DSC(Differential Scanning Calorimeter；示差掃描熱分析儀)曲線並以所獲得之DSC曲線的反曲點溫度表示。 In this specification, the "glass transition temperature" refers to a DSC (Differential Scanning Calorimeter) curve of a sample measured using a differential scanning calorimeter, and is represented by the inflection point temperature of the obtained DSC curve.

作為丙烯酸系樹脂，例如可列舉：1種或2種以上之(甲基)丙烯酸酯之聚合物；選自(甲基)丙烯酸、衣康酸、乙酸乙烯酯、丙烯腈、苯乙烯及N-羥甲基丙烯醯胺等中的至少2種單體之共聚物等。 Examples of acrylic resins include polymers of one or more (meth)acrylates; polymers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N- A copolymer of at least two monomers among methylol acrylamide and the like.

作為構成丙烯酸系樹脂之前述(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、 (甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯(亦稱為(甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯(亦稱為(甲基)丙烯酸肉豆蔻酯)、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯(亦稱為(甲基)丙烯酸棕櫚酯)、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯(亦稱為(甲基)丙烯酸硬脂酯)等構成烷基酯之烷基為碳數為1至18之鏈狀結構之(甲基)丙烯酸烷基酯；(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；(甲基)丙烯醯亞胺；(甲基)丙烯酸縮水甘油酯等含縮水甘油基之(甲基)丙烯酸酯；(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-羥基丁酯等含羥基之(甲基)丙烯酸酯；(甲基)丙烯酸N-甲基胺基乙酯等含取代胺基之(甲基)丙烯酸酯等。此處，所謂「取代胺基」意指胺基之1個或2個氫原子被氫原子以外的基取代而成之基。 As said (meth)acrylate which comprises an acrylic resin, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate are mentioned, for example ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate (methyl)hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-octyl (meth)acrylate nonyl ester, Isononyl (meth)acrylate, Decyl (meth)acrylate, Undecyl (meth)acrylate, Lauryl (meth)acrylate (also known as lauryl (meth)acrylate) , tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, (meth)acrylate ) cetyl acrylate (also known as palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (also known as (meth)acrylic acid) Stearyl) etc. The alkyl group constituting the alkyl ester is (meth)acrylic acid alkyl ester with a chain structure of carbon number from 1 to 18; (meth)acrylic acid isobornyl ester, (meth)acrylic acid dicyclopentane (meth)acrylic acid cycloalkyl esters; (meth)acrylic acid benzyl esters and other (meth)acrylic acid aralkyl esters; (meth)acrylic acid dicyclopentenyl esters and other (meth)acrylic acid cycloalkenyl esters ; (meth) acrylic acid cycloalkenyloxy ethyl ester and the like (meth) acrylic acid cycloalkenyloxy ethyl ester; (meth) acryl imide; (meth) acrylic acid glycidyl ester and the like containing glycidyl group The (meth)acrylate; hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylic acid 2-hydroxybutyl acrylate, (meth)acrylic acid 3-hydroxybutyl ester, (meth)acrylic acid 4-hydroxybutyl ester and other hydroxyl-containing (meth)acrylates; (meth)acrylic acid N- Substituted amine group-containing (meth)acrylates, such as methylaminoethyl ester, etc. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom.

上述之中，較佳為丙烯酸正丁酯、丙烯酸甲酯、甲基丙烯酸縮水甘油酯、及丙烯酸2-羥基乙酯等。 Among the above, n-butyl acrylate, methyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, and the like are preferred.

丙烯酸系樹脂例如除前述(甲基)丙烯酸酯以外，亦可 為進一步使選自(甲基)丙烯酸、衣康酸、乙酸乙烯酯、丙烯腈、苯乙烯及N-羥甲基丙烯醯胺等中的1種或2種以上之單體進行共聚合而成之樹脂。 Acrylic resins may be used, for example, in addition to the aforementioned (meth)acrylates. It is obtained by further copolymerizing one or more monomers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylol acrylamide. of resin.

構成丙烯酸系樹脂之單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 Only one kind of monomers constituting the acrylic resin may be used, or two or more kinds thereof may be sufficient; in the case of two or more kinds, the combination and ratio of these may be arbitrarily selected.

丙烯酸系樹脂亦可具有乙烯基、(甲基)丙烯醯基、胺基、羥基、羧基、異氰酸酯基等可與其他化合物鍵結之官能基。丙烯酸系樹脂中的前述官能基可經由後述交聯劑(F)與其他化合物鍵結，亦可不經由交聯劑(F)與其他化合物直接鍵結。藉由使丙烯酸系樹脂經由前述官能基與其他化合物鍵結，有使用保護膜形成用片所獲得之封裝的可靠性提高之傾向。 The acrylic resin may also have functional groups that can bond with other compounds, such as vinyl groups, (meth)acryloyl groups, amine groups, hydroxyl groups, carboxyl groups, and isocyanate groups. The functional group in the acrylic resin may be bonded to other compounds via the crosslinking agent (F) described later, or may be directly bonded to other compounds without the crosslinking agent (F). There exists a tendency for the reliability of the package obtained by using the sheet for protective film formation to improve by making an acrylic resin couple|bond with another compound via the said functional group.

本發明中，作為聚合物成分(A)，亦可將丙烯酸系樹脂以外的熱塑性樹脂(以下，有時僅簡稱為「熱塑性樹脂」)與丙烯酸系樹脂併用。 In the present invention, as the polymer component (A), a thermoplastic resin other than the acrylic resin (hereinafter, only abbreviated as "thermoplastic resin" in some cases) may be used together with the acrylic resin.

藉由使用前述熱塑性樹脂，有時保護膜自支持片之剝離性提高，或熱硬化性保護膜形成層變得易於追隨被黏著體的凹凸面，從而可進一步抑制於被黏著體與熱硬化性保護膜形成層之間產生孔隙等。 By using the aforementioned thermoplastic resin, the peelability of the protective film from the supporting sheet may be improved, or the thermosetting protective film-forming layer may easily follow the uneven surface of the adherend, thereby further suppressing the adherence and thermosetting properties. Pores and the like are generated between the protective film-forming layers.

前述熱塑性樹脂的重量平均分子量較佳為1000至100000，更佳為3000至80000。 The weight average molecular weight of the aforementioned thermoplastic resin is preferably 1,000 to 100,000, more preferably 3,000 to 80,000.

前述熱塑性樹脂的玻璃轉移溫度(Tg)較佳為-30℃至150℃，更佳為-20℃至120℃。 The glass transition temperature (Tg) of the aforementioned thermoplastic resin is preferably -30°C to 150°C, more preferably -20°C to 120°C.

作為前述熱塑性樹脂，例如可列舉：聚酯、聚胺基甲酸酯、苯氧基樹脂、聚丁烯、聚丁二烯、聚苯乙烯等。 As said thermoplastic resin, polyester, a polyurethane, a phenoxy resin, a polybutene, a polybutadiene, a polystyrene etc. are mentioned, for example.

保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層所含有之前述熱塑性樹脂可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The above-mentioned thermoplastic resin contained in the composition (III-1) for a protective film-forming layer and the thermosetting protective film-forming layer may be only one kind or two or more kinds; in the case of two or more kinds, the other Combinations and ratios can be arbitrarily selected.

關於聚合物成分(A)的含量，無論聚合物成分(A)的種類如何，相對於構成保護膜形成層用組成物(III-1)中的溶劑以外的全部成分的總質量(亦即，相對於熱硬化性保護膜形成層的總質量)，較佳為5質量%至50質量%，更佳為10質量%至40質量%，尤佳為15質量%至35質量%。 Regarding the content of the polymer component (A), regardless of the type of the polymer component (A), it is relative to the total mass of all components other than the solvent in the composition (III-1) constituting the protective film-forming layer (that is, It is preferably 5 to 50 mass %, more preferably 10 to 40 mass %, and still more preferably 15 to 35 mass % relative to the total mass of the thermosetting protective film-forming layer).

聚合物成分(A)有時亦符合熱硬化性成分(B)。本發明中，於保護膜形成層用組成物(III-1)含有此種屬於聚合物成分(A)及熱硬化性成分(B)之兩者之成分之情形時，視為保護膜形成層用組成物(III-1)含有聚合物成分(A)及熱硬化性成分(B)。 The polymer component (A) may also correspond to the thermosetting component (B). In the present invention, when the composition (III-1) for a protective film-forming layer contains such a component belonging to both the polymer component (A) and the thermosetting component (B), it is regarded as a protective film-forming layer The composition (III-1) contains a polymer component (A) and a thermosetting component (B).

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

熱硬化性成分(B)係用以使熱硬化性保護膜形成層硬化而形成硬質之保護膜之成分。 The thermosetting component (B) is a component for forming a hard protective film by hardening the thermosetting protective film-forming layer.

保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層所含有之熱硬化性成分(B)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The composition (III-1) for a protective film-forming layer and the thermosetting component (B) contained in the thermosetting protective film-forming layer may be only one type or two or more types; in the case of two or more types , the combination and ratio of these can be arbitrarily selected.

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

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

環氧系熱硬化性樹脂由環氧樹脂(B1)及熱硬化劑(B2)構成。 The epoxy-based thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2).

保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層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，這些之組合及比率可任意選擇。 The composition (III-1) for a protective film-forming layer and the epoxy-based thermosetting resin contained in the thermosetting protective film-forming layer may be only one type or two or more types; in the case of two or more types , the combination and ratio of these can be arbitrarily selected.

‧環氧樹脂(B1) ‧Epoxy resin (B1)

作為環氧樹脂(B1)，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。 As epoxy resin (B1), well-known epoxy resins are mentioned, for example, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl are mentioned. Oil ether and its hydrides, o-cresol novolac epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, extension Difunctional or higher epoxy compounds such as phenyl skeleton type epoxy resins.

上述之中，較佳為雙酚A型環氧樹脂、二環戊二烯型環氧樹脂等。 Among the above, bisphenol A-type epoxy resins, dicyclopentadiene-type epoxy resins, and the like are preferred.

作為環氧樹脂(B1)，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以及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，使用保護膜形成用片所獲得之封裝的可靠性提高。 As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can also be used. Compared with epoxy resins without unsaturated hydrocarbon groups, epoxy resins with unsaturated hydrocarbon groups and acrylic resins have higher compatibility. Therefore, by using the epoxy resin which has an unsaturated hydrocarbon group, the reliability of the package obtained using the sheet for protective film formation improves.

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

另外，作為具有不飽和烴基之環氧樹脂，例如可列舉：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 are directly couple|bonded with the group which has an unsaturated hydrocarbon group are mentioned to the aromatic ring etc. which comprise an epoxy resin, for example.

不飽和烴基為具有聚合性之不飽和基，作為該不飽和烴基之具體例，可列舉：次乙基(乙烯基)、2-丙烯基(烯丙基)、(甲基)丙烯醯基、(甲基)丙烯醯胺基等，較佳為丙烯醯基。 The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples of the unsaturated hydrocarbon group include ethylene (vinyl), 2-propenyl (allyl), (meth)acryloyl, A (meth)acrylamido group or the like is preferably an acrylamide group.

環氧樹脂(B1)的數量平均分子量並無特別限定，就熱硬化性保護膜形成層的硬化性、以及硬化後的保護膜的強度及耐熱性之方面而言，較佳為300至30000，更佳為300至10000，尤佳為300至3000。 The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is preferably 300 to 30,000 in terms of the curability of the thermosetting protective film-forming layer, and the strength and heat resistance of the protective film after curing, More preferably, it is 300 to 10,000, and still more preferably, it is 300 to 3,000.

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；Gel Permeation Chromatography)法所測定之標準聚苯乙烯換算之值所表示之數量平均分子量。環氧樹脂(B1)的環氧當量較佳為100g/eq至1100g/eq，更佳為150g/eq至1000g/eq。 In this specification, the term "number average molecular weight" means the number average molecular weight represented by the value in terms of standard polystyrene measured by gel permeation chromatography (GPC; Gel Permeation Chromatography) unless otherwise specified. . The epoxy equivalent of the epoxy resin (B1) is preferably 100 g/eq to 1100 g/eq, more preferably 150 g/eq to 1000 g/eq.

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

環氧樹脂(B1)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，這些之組合及比率可任意選擇。 An epoxy resin (B1) may be used individually by 1 type, and may use 2 or more types together; When using 2 or more types together, the combination and ratio of these can be selected arbitrarily.

‧熱硬化劑(B2) ‧Thermosetting agent (B2)

熱硬化劑(B2)發揮針對環氧樹脂(B1)之硬化劑的功能。 The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).

作為熱硬化劑(B2)，例如可列舉1分子中具有至少2個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 (B2), the compound which has at least 2 functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an acid group formed by an anhydride, and preferably a phenolic hydroxyl group, an amino group, or an acid group formed by an anhydride. The base formed is more preferably a phenolic hydroxyl group or an amine group.

熱硬化劑(B2)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 (B2), examples of the phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-based phenol resins, and aralkylphenols. resin, etc.

熱硬化劑(B2)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。 In a thermosetting agent (B2), as an amine type hardening agent which has an amine group, dicyandiamine (it may abbreviate "DICY" hereafter) etc. are mentioned, for example.

熱硬化劑(B2)亦可具有不飽和烴基。 The thermal hardener (B2) may have an unsaturated hydrocarbon group.

作為具有不飽和烴基之熱硬化劑(B2)，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 (B2) having an unsaturated hydrocarbon group include a compound in which a part of the hydroxyl groups of a phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a group having an unsaturated hydrocarbon group directly bonded to the aromatic ring of the phenol resin. Compounds, etc.

熱硬化劑(B2)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 (B2) 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(B2)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(B2)較佳為軟化點或玻璃轉移溫度高的酚系硬化劑。 In the case of using a phenol-based hardener as the thermal hardener (B2), the thermal hardener (B2) is preferably a phenol having a high softening point or glass transition temperature from the viewpoint of improving the peelability of the protective film from the support sheet. System hardener.

熱硬化劑(B2)較佳為在常溫下為固體，且對環氧樹脂(B1)不顯示硬化活性，另一方面，藉由加熱而溶解，且對環氧樹脂(B1)顯示硬化活性之熱硬化劑(以下，有時簡稱為「熱活性潛伏性環氧樹脂硬化劑」)。 The thermosetting agent (B2) is preferably solid at room temperature, and has no hardening activity to the epoxy resin (B1), but is dissolved by heating and exhibits hardening activity to the epoxy resin (B1). Thermosetting agent (Hereinafter, it may be abbreviated as "thermally active latent epoxy resin curing agent").

前述熱活性潛伏性環氧樹脂硬化劑在常溫下於熱硬化性保護膜形成層中穩定地分散於環氧樹脂(B1)中，但藉由加熱與環氧樹脂(B1)相容，且與環氧樹脂(B1)反應。藉由使用前述熱活性潛伏性環氧樹脂硬化劑，保護膜形成用片的保存穩定性顯著提高。例如，可抑制該硬化劑自保護膜形成用膜向鄰接之支持片轉移，可有效抑制熱硬化性保護膜形成層的熱硬化性降低。並且，熱硬化性保護膜形成層藉由加熱而熱硬化度變得更高，故而後述之附保護膜之半導體晶片的拾取性進一步提高。 The aforementioned thermally active latent epoxy resin hardener is stably dispersed in the epoxy resin (B1) in the thermosetting protective film-forming layer at room temperature, but is compatible with the epoxy resin (B1) by heating, and is compatible with the epoxy resin (B1). The epoxy resin (B1) reacts. By using the aforementioned thermally active latent epoxy resin hardener, the storage stability of the sheet for forming a protective film is remarkably improved. For example, the transfer of the curing agent from the film for protective film formation to the adjacent support sheet can be suppressed, and the reduction in the thermosetting properties of the thermosetting protective film forming layer can be effectively suppressed. Furthermore, since the thermosetting protective film forming layer has a higher degree of thermosetting by heating, the pick-up property of the semiconductor wafer with a protective film which will be described later is further improved.

作為前述熱活性潛伏性環氧樹脂硬化劑，例如可列舉：鎓鹽、二元酸醯肼、二氰二胺、硬化劑的胺加成物等。 As said thermally active latent epoxy resin hardener, an onium salt, a dibasic acid hydrazide, dicyandiamine, an amine adduct of a hardener, etc. are mentioned, for example.

熱硬化劑(B2)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 (B2), the number average molecular weight of resin components such as polyfunctional phenol resin, novolak-type phenol resin, dicyclopentadiene-based phenol resin, aralkylphenol resin, etc. is preferably 300 to 30,000, more preferably 400 to 10,000, more preferably 500 to 3,000.

熱硬化劑(B2)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 (B2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamine is not particularly limited, but is preferably 60 to 500, for example.

熱硬化劑(B2)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，這些之組合及比率可任意選擇。 A thermosetting agent (B2) may be used individually by 1 type, and may use 2 or more types together; When using 2 or more types together, the combination and ratio of these can be selected arbitrarily.

保護膜形成層用組成物(III-1)及熱硬化性保護膜形成 層中，熱硬化劑(B2)的含量相對於環氧樹脂(B1)的含量100質量份，較佳為0.1質量份至500質量份，更佳為1質量份至200質量份。藉由熱硬化劑(B2)的前述含量為前述下限值以上，熱硬化性保護膜形成層變得更易於進行硬化。另外，藉由熱硬化劑(B2)的前述含量為前述上限值以下，熱硬化性保護膜形成層的吸濕率降低，使用保護膜形成用片所獲得之封裝的可靠性進一步提高。 Composition for protective film forming layer (III-1) and thermosetting protective film formation In the layer, the content of the thermosetting agent (B2) is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass, relative to 100 parts by mass of the content of the epoxy resin (B1). When the said content of a thermosetting agent (B2) is more than the said lower limit, it becomes easy to harden a thermosetting protective film-forming layer. Moreover, when the said content of a thermosetting agent (B2) is below the said upper limit, the moisture absorption rate of a thermosetting protective film forming layer falls, and the reliability of the package obtained using the sheet for protective film forming is further improved.

保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層中，熱硬化性成分(B)的含量(例如，環氧樹脂(B1)及熱硬化劑(B2)的總含量)相對於聚合物成分(A)的含量100質量份，較佳為1質量份至100質量份，更佳為1.5質量份至85質量份，尤佳為2質量份至70質量份。藉由熱硬化性成分(B)的前述含量為此種範圍，保護膜與支持片之接著力得到抑制，支持片之剝離性提高。 In the composition for protective film forming layer (III-1) and the thermosetting protective film forming layer, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2) ) is preferably 1 to 100 parts by mass, more preferably 1.5 to 85 parts by mass, and particularly preferably 2 to 70 parts by mass relative to 100 parts by mass of the content of the polymer component (A). When the said content of a thermosetting component (B) is such a range, the adhesive force of a protective film and a support sheet is suppressed, and the peelability of a support sheet improves.

作為另一態樣，保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層中，熱硬化性成分(B)的含量相對於保護膜形成層用組成物(III-1)中的溶劑以外的全部成分的總質量(亦即，相對於熱硬化性保護膜形成層的總質量)，較佳為1質量%至90質量%，更佳為10質量%至80質量%，進一步更佳為30質量%至70質量%。 As another aspect, in the composition for protective film-forming layers (III-1) and the thermosetting protective film-forming layer, the content of the thermosetting component (B) is relative to the composition for protective film-forming layers (III-1). ), the total mass of all components other than the solvent (that is, with respect to the total mass of the thermosetting protective film-forming layer) is preferably 1 to 90 mass %, more preferably 10 to 80 mass % , more preferably 30% by mass to 70% by mass.

[硬化促進劑(C)] [Hardening accelerator (C)]

保護膜形成層用組成物(III-1)及熱硬化性保護膜形成 層亦可含有硬化促進劑(C)。硬化促進劑(C)係用以調整保護膜形成層用組成物(III-1)的硬化速度之成分。 Composition for protective film forming layer (III-1) and thermosetting protective film formation The layer may also contain a hardening accelerator (C). The hardening accelerator (C) is a component for adjusting the hardening rate of the composition (III-1) for protective film-forming layers.

作為較佳的硬化促進劑(C)，例如可列舉：三乙二胺、苄基二甲胺、三乙醇胺、二甲胺基乙醇、三(二甲胺基甲基)苯酚等三級胺；2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑等咪唑類(至少1個氫原子被氫原子以外的基取代而成之咪唑)；三丁基膦、二苯基膦、三苯基膦等有機膦類(至少1個氫原子被有機基取代而成之膦)；四苯基硼酸四苯基鏻、四苯基硼酸三苯基膦等四苯基硼鹽等。 As preferable hardening accelerator (C), for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, etc. can be mentioned; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethylimidazole (imidazoles in which at least one hydrogen atom is substituted by a group other than a hydrogen atom); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (at least one hydrogen atom) Phosphine substituted by organic groups); tetraphenyl boron salts such as tetraphenyl phosphonium tetraphenyl borate, triphenyl phosphine tetraphenyl borate, etc.

上述之中，較佳為2-苯基-4,5-二羥基甲基咪唑。 Among the above, 2-phenyl-4,5-dihydroxymethylimidazole is preferred.

保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層所含有之硬化促進劑(C)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The composition for protective film-forming layer (III-1) and the curing accelerator (C) contained in the thermosetting protective film-forming layer may be only one type or two or more types; in the case of two or more types , the combination and ratio of these can be arbitrarily selected.

於使用硬化促進劑(C)之情形時，保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層中，硬化促進劑(C)的含量相對於熱硬化性成分(B)的含量100質量份，較佳為0.01質量份至10質量份，更佳為0.1質量份至5質量份。藉由硬化促進劑(C)的前述含量為前述下限值以上，可獲得更顯著的由使用硬化促進劑(C)所帶來之功效。另外，藉由硬化促進劑(C)的含量為前述上限值以下，例如抑制高極性的硬化促進劑(C)於高溫、高濕度條件下在熱硬化性 保護膜形成層中向與被黏著體之接著界面側轉移而偏析之功效變高，從而使用保護膜形成用片所獲得之封裝的可靠性進一步提高。 In the case of using a curing accelerator (C), in the protective film-forming layer composition (III-1) and the thermosetting protective film-forming layer, the content of the curing accelerator (C) is relative to the thermosetting component (B) ) content of 100 parts by mass, preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass. When the said content of a hardening accelerator (C) is more than the said lower limit, the effect by using a hardening accelerator (C) is more remarkable. In addition, when the content of the hardening accelerator (C) is below the above-mentioned upper limit value, for example, the thermosetting property of the high-polarity hardening accelerator (C) under high temperature and high humidity conditions is suppressed. In the protective film forming layer, the effect of transferring to the interface side with the adherend and segregating becomes high, and the reliability of the package obtained by using the protective film forming sheet is further improved.

[填充材料(D)] [filler (D)]

保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層亦可含有填充材料(D)。藉由熱硬化性保護膜形成層含有填充材料(D)，使熱硬化性保護膜形成層硬化而獲得之保護膜變得容易調整熱膨脹係數，藉由使該熱膨脹係數對於保護膜之形成對象物而言最適宜，使用保護膜形成用片所獲得之封裝的可靠性進一步提高。另外，藉由熱硬化性保護膜形成層含有填充材料(D)，亦可降低保護膜的吸濕率，或提高散熱性。 The composition (III-1) for protective film forming layers and the thermosetting protective film forming layer may contain a filler (D). By containing the filler (D) in the thermosetting protective film-forming layer, the protective film obtained by curing the thermosetting protective film-forming layer becomes easy to adjust the thermal expansion coefficient. Most preferably, the reliability of the package obtained by using the sheet for forming a protective film is further improved. Moreover, when a thermosetting protective film forming layer contains a filler (D), the moisture absorption rate of a protective film can also be reduced, or heat dissipation can also be improved.

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

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

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

保護膜形成層用組成物(III-1)及熱硬化性保護膜形成 層所含有之填充材料(D)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 Composition for protective film forming layer (III-1) and thermosetting protective film formation The filler (D) contained in the layer may be only one type or two or more types; in the case of two or more types, the combination and ratio of these may be arbitrarily selected.

於使用填充材料(D)之情形時，保護膜形成層用組成物(III-1)中，填充材料(D)的含量(亦即，熱硬化性保護膜形成層中的填充材料(D)的含量)相對於溶劑以外的全部成分的總含量(總質量)，較佳為5質量%至80質量%，更佳為7質量%至60質量%。藉由填充材料(D)的含量為此種範圍，變得更容易調整上述熱膨脹係數。 In the case of using the filler (D), in the composition (III-1) for a protective film-forming layer, the content of the filler (D) (that is, the filler (D) in the thermosetting protective film-forming layer) content) relative to the total content (total mass) of all components other than the solvent, preferably 5 to 80 mass %, more preferably 7 to 60 mass %. When the content of the filler (D) is in such a range, it becomes easier to adjust the thermal expansion coefficient.

[偶合劑(E)] [Coupling agent (E)]

保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層亦可含有偶合劑(E)。藉由使用可與無機化合物或有機化合物反應之官能基之化合物作為偶合劑(E)，可提高熱硬化性保護膜形成層對被黏著體之接著性及密接性。另外，藉由使用偶合劑(E)，使熱硬化性保護膜形成層硬化而獲得之保護膜不損害耐熱性而耐水性提高。 The composition (III-1) for protective film forming layers and the thermosetting protective film forming layer may contain a coupling agent (E). By using the compound of the functional group which can react with an inorganic compound or an organic compound as a coupling agent (E), the adhesiveness and adhesiveness of a thermosetting protective film-forming layer to a to-be-adhered body can be improved. Moreover, by using the coupling agent (E), the water resistance improves without impairing the heat resistance of the protective film obtained by hardening the thermosetting protective film-forming layer.

偶合劑(E)較佳為具有可與聚合物成分(A)、熱硬化性成分(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 functional groups possessed by the polymer component (A), the thermosetting component (B), and the like, and is more preferably a silane coupling agent.

作為較佳的前述矽烷偶合劑，例如可列舉：3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘 油氧基甲基二乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基甲基二乙氧基矽烷、3-(苯基胺基)丙基三甲氧基矽烷、3-苯胺基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、雙(3-三乙氧基矽烷基丙基)四硫化物、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、咪唑矽烷等。 Examples of preferable silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyl Triethoxysilane, 3-glycidyl Oleyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyl trimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-( Phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl Methyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane Acetyloxysilane, imidazosilane, etc.

保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層所含有之偶合劑(E)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The composition (III-1) for protective film-forming layer and the coupling agent (E) contained in the thermosetting protective film-forming layer may be only one kind or two or more kinds; in the case of two or more kinds, The combination and ratio of these can be arbitrarily selected.

於使用偶合劑(E)之情形時，保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層中，偶合劑(E)的含量相對於聚合物成分(A)及熱硬化性成分(B)的總含量100質量份，較佳為0.03質量份至20質量份，更佳為0.05質量份至10質量份，尤佳為0.1質量份至5質量份。藉由偶合劑(E)的前述含量為前述下限值以上，可獲得更顯著的以下由使用偶合劑(E)所帶來之功效：填充材料(D)於樹脂中之分散性提高，或熱硬化性保護膜形成層與被黏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，可更進一步抑制產生逸氣。 When the coupling agent (E) is used, in the composition for protective film-forming layer (III-1) and the thermosetting protective film-forming layer, the content of the coupling agent (E) is relative to the polymer component (A) and the heat The total content of the curable component (B) is 100 parts by mass, preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass. By the above-mentioned content of the coupling agent (E) being more than the above-mentioned lower limit value, the following effect brought about 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 The adhesion between the thermosetting protective film forming layer and the adherend is improved, etc. Moreover, when the said content of a coupling agent (E) is below the said upper limit, generation|occurrence|production of outgas can be suppressed further.

[交聯劑(F)] [Crosslinker (F)]

於使用具有可與其他化合物鍵結之官能基，例如乙烯基、(甲基)丙烯醯基、胺基、羥基、羧基、異氰酸酯基等之上述丙烯酸系樹脂等作為聚合物成分(A)之情形時，保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層亦可進一步含有交聯劑(F)，該交聯劑(F)用以使前述官能基與其他化合物鍵結而進行交聯。藉由使用交聯劑(F)進行交聯，可調節熱硬化性保護膜形成層的初期接著力及凝聚力。 In the case of using the above-mentioned acrylic resins having functional groups that can bond with other compounds, such as vinyl groups, (meth)acryloyl groups, amine groups, hydroxyl groups, carboxyl groups, isocyanate groups, etc., as the polymer component (A) In this case, the composition (III-1) for a protective film-forming layer and the thermosetting protective film-forming layer may further contain a crosslinking agent (F) for bonding the aforementioned functional groups to other compounds. junction and cross-linking. By crosslinking using the crosslinking agent (F), the initial adhesion force and cohesion force of the thermosetting protective film-forming layer can be adjusted.

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

作為前述有機多元異氰酸酯化合物，例如可列舉：芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物及脂環族多元異氰酸酯化合物(以下，有時將這些化合物統一簡稱為「芳香族多元異氰酸酯化合物等」)；前述芳香族多元異氰酸酯化合物等的三聚物、異氰脲酸酯體及加合物；使前述芳香族多元異氰酸酯化合物等與多元醇化合物反應而獲得之末端異氰酸酯胺基甲酸酯預聚物等。前述「加合物」意指前述芳香族多元異氰酸酯化合物、脂肪族多 元異氰酸酯化合物或脂環族多元異氰酸酯化合物以及乙二醇、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，並且於分子的末端部具有異氰酸酯基之預聚物。 Examples of the organic polyvalent isocyanate compound include: aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyvalent isocyanate compounds, etc."); Trimers, isocyanurate compounds, and adducts of the aforementioned aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers, etc. obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc. with a polyol compound, etc. . The aforementioned "adduct" means the aforementioned aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound A reactant of a basic isocyanate compound or an alicyclic polyvalent isocyanate compound and a low-molecular-weight active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, as examples of the aforementioned adducts, can be For example, a xylylene diisocyanate adduct of trimethylolpropane, which will be described later, and the like are exemplified. In addition, the term "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and having an isocyanate group at a terminal portion of the molecule.

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

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

於使用有機多元異氰酸酯化合物作為交聯劑(F)之情形時，作為聚合物成分(A)，較佳為使用含羥基之聚合物。於交聯劑(F)具有異氰酸酯基，聚合物成分(A)具有羥基之情形時，藉由交聯劑(F)與聚合物成分(A)之反應，可將交聯結構簡便地導入至熱硬化性保護膜形成層中。 When an organic polyvalent isocyanate compound is used as the crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A). When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the crosslinking structure can be easily introduced to the In the thermosetting protective film forming layer.

保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層所含有之交聯劑(F)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The crosslinking agent (F) contained in the composition (III-1) for a protective film-forming layer and the thermosetting protective film-forming layer may be only one type or two or more types; in the case of two or more types , the combination and ratio of these can be arbitrarily selected.

於使用交聯劑(F)之情形時，保護膜形成層用組成物(III-1)中，交聯劑(F)的含量相對於聚合物成分(A)的含量100質量份，較佳為0.01質量份至20質量份，更佳為0.1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，可抑制熱硬化性保護膜形成層與支持片之接著力或熱硬化性保護膜形成層與半導體晶圓或半導體晶片之接著力過度降低。 In the case of using the crosslinking agent (F), in the protective film-forming layer composition (III-1), the content of the crosslinking agent (F) is preferably 100 parts by mass relative to the content of the polymer component (A). It is 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass. When the said content of a crosslinking agent (F) is more than the said lower limit, the effect by using a crosslinking agent (F) is more remarkable. Moreover, since the said content of the crosslinking agent (F) is below the said upper limit, the adhesive force of the thermosetting protective film forming layer and the support sheet, or the thermosetting protective film forming layer and the semiconductor wafer or the semiconductor wafer can be suppressed The adhesion force is excessively reduced.

本發明中，即便不使用交聯劑(F)，亦可充分地獲得本發明的功效。 In the present invention, even if the crosslinking agent (F) is not used, the effect of the present invention can be sufficiently obtained.

[能量線硬化性樹脂(G)] [Energy beam curable resin (G)]

保護膜形成層用組成物(III-1)亦可含有能量線硬化性樹脂(G)。熱硬化性保護膜形成層藉由含有能量線硬化性樹脂(G)，可藉由照射能量線而改變特性。 The composition (III-1) for protective film forming layers may contain an energy ray curable resin (G). Since the thermosetting protective film forming layer contains the energy ray curable resin (G), the properties can be changed by irradiating the energy ray.

能量線硬化性樹脂(G)係使能量線硬化性化合物進行聚合(硬化)而獲得。 The energy ray curable resin (G) is obtained by polymerizing (hardening) an energy ray curable compound.

作為前述能量線硬化性化合物，例如可列舉分子內具有至少1個聚合性雙鍵之化合物，較佳為具有(甲基)丙烯醯基之丙烯酸酯系化合物。 As said energy-beam curable compound, the compound which has at least 1 polymerizable double bond in a molecule|numerator is mentioned, for example, Preferably it is an acrylate type compound which has a (meth)acryloyl group.

作為前述丙烯酸酯系化合物，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇單羥基五(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-己二醇二(甲基)丙烯酸酯等含鏈狀脂肪族骨架之(甲基)丙烯酸酯；二(甲基)丙烯酸二環戊酯等含環狀脂肪族骨架之(甲基)丙烯酸酯；聚乙二醇二(甲基)丙烯酸酯等聚伸烷基二醇(甲基)丙烯酸酯；寡酯(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲酸酯低聚物；環氧改性(甲基)丙烯酸酯；前述聚伸烷基二醇(甲基)丙烯酸酯以外的聚醚(甲基)丙烯酸酯；衣康酸低聚物等。 As said acrylate type compound, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, base) acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate (Meth)acrylates containing chain-like aliphatic skeletons such as (meth)acrylates; (meth)acrylates containing cyclic aliphatic skeletons such as dicyclopentyl di(meth)acrylates; polyethylene glycol Polyalkylene glycol (meth)acrylates such as di(meth)acrylates; oligoester (meth)acrylates; (meth)acrylate urethane oligomers; epoxy modified (meth)acrylates base) acrylates; polyether (meth)acrylates other than the aforementioned polyalkylene glycol (meth)acrylates; itaconic acid oligomers, and the like.

前述能量線硬化性化合物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 energy ray curable compound is preferably 100 to 30,000, more preferably 300 to 10,000.

用於聚合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，這些之組合及比率可任意選擇。 Only one type of the above-mentioned energy ray-curable compound used for polymerization may be used, or two or more types may be sufficient; in the case of two or more types, the combination and ratio of these may be arbitrarily selected.

保護膜形成層用組成物(III-1)所含有的能量線硬化性樹脂(G)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The energy ray-curable resin (G) contained in the composition (III-1) for forming a protective film may be only one type or two or more types; in the case of two or more types, the combination and ratio of these may be used Can be arbitrarily selected.

保護膜形成層用組成物(III-1)中，能量線硬化性樹脂(G)的含量相對於保護膜形成層用組成物(III-1)中的溶劑以外的全部成分的總質量，較佳為1質量%至95質量%，更佳為2質量%至90質量%，尤佳為3質量%至85質量%。 In the composition for protective film-forming layers (III-1), the content of the energy ray-curable resin (G) is higher than the total mass of all components other than the solvent in the composition for protective film-forming layers (III-1). It is preferably 1% by mass to 95% by mass, more preferably 2% by mass to 90% by mass, and still more preferably 3% by mass to 85% by mass.

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

於保護膜形成層用組成物(III-1)含有能量線硬化性樹脂(G)之情形時，為了使能量線硬化性樹脂(G)高效率地進行聚合反應，亦可含有光聚合起始劑(H)。 When the composition (III-1) for a protective film-forming layer contains the energy ray curable resin (G), in order to efficiently carry out the polymerization reaction of the energy ray curable resin (G), a photopolymerization initiator may be contained. Agent (H).

作為保護膜形成層用組成物(III-1)中的光聚合起始劑(H)，可列舉與黏著劑組成物(ii)中的光聚合起始劑相同的化合物。 As the photopolymerization initiator (H) in the composition (III-1) for forming a protective film, the same compounds as those of the photopolymerization initiator in the adhesive composition (ii) can be mentioned.

保護膜形成層用組成物(III-1)所含有之光聚合起始劑(H)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The photopolymerization initiator (H) contained in the composition (III-1) for forming a protective film may be only one type or two or more types; in the case of two or more types, the combination and ratio of these Can be arbitrarily selected.

保護膜形成層用組成物(III-1)中，光聚合起始劑(H)的含量相對於能量線硬化性樹脂(G)的含量100質量份，較佳為0.1質量份至20質量份，更佳為1質量份至10質量份，尤佳為2質量份至5質量份。 In the composition (III-1) for a protective film-forming layer, the content of the photopolymerization initiator (H) is 100 parts by mass, preferably 0.1 parts by mass to 20 parts by mass, relative to the content of the energy ray-curable resin (G) in 100 parts by mass , more preferably 1 to 10 parts by mass, particularly preferably 2 to 5 parts by mass.

[著色劑(I)] [Colorant (I)]

保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層亦可含有著色劑(I)。 The composition (III-1) for protective film forming layers and the thermosetting protective film forming layer may contain a colorant (I).

作為著色劑(I)，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 (I), well-known coloring agents, such as an inorganic type pigment, an organic type pigment, and an organic type 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、偶氮色素、縮合偶氮色素、靛藍系色素、紫環酮(perinone)系色素、苝系色素、二噁烷(dioxane)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)系色等。 Examples of the organic pigments and organic dyes include ammonium-based dyes, cyanine-based dyes, merocyanine-based dyes, croconium-based dyes, squalilium-based dyes, and azulium-based dyes. Pigments, polymethine based pigments, naphthoquinone based pigments, pyrylium based pigments, phthalocyanine based pigments, naphthalocyanine based pigments, naphthalamide based pigments, azo pigments, condensed azo pigments, indigo based pigments , Perinone dyes, perylene dyes, dioxane dyes, quinacridone dyes, isoindolinone dyes, quinophthalone dyes, pyrrole dyes , thioindigo pigments, metal complex pigments (metal salt dyes), gold dithiolate It belongs to complex dyes, indoxyl dyes, triallylmethane dyes, anthraquinone dyes, naphthol dyes, methine azo dyes, benzimidazolone dyes, and picanthrone dyes Pigment and threne color, 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(Indium Tin Oxide；氧化銦錫)系色素、ATO(Antimony Tin Oxide；氧化銻錫)系色素等。 Examples of the inorganic pigments include carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, and ITO. (Indium Tin Oxide; indium tin oxide)-based dye, ATO (Antimony Tin Oxide; antimony tin oxide)-based dye, and the like.

保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層所含有之著色劑(I)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The coloring agent (I) contained in the composition (III-1) for a protective film-forming layer and the thermosetting protective film-forming layer may be only one kind or two or more kinds; in the case of two or more kinds, The combination and ratio of these can be arbitrarily selected.

於使用著色劑(I)之情形時，熱硬化性保護膜形成層中的著色劑(I)的含量根據目的適宜調節即可。例如，有時藉由雷射照射對保護膜實施印字，藉由調節熱硬化性保護膜形成層中的著色劑(I)的含量，調節保護膜的透光性，可調節印字視認性。另外，藉由調節熱硬化性保護膜形成層中的著色劑(I)的含量，亦可提高保護膜的設計性，或者使得半導體晶圓的背面的研削痕跡不易見。若考慮這一方面，則保護膜形成層用組成物(III-1)中，著色劑(I)的含量(亦即，熱硬化性保護膜形成層中的著色劑(I)的含量)相對於溶劑以外的全部成分的總含量(總質量)，較佳為0.1質量%至 10質量%，更佳為0.1質量%至7.5質量%，尤佳為0.1質量%至5質量%。藉由著色劑(I)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(I)所帶來之功效。另外，藉由著色劑(I)的前述含量為前述上限值以下，可抑制熱硬化性保護膜形成層的透光性過度降低。 In the case of using the colorant (I), the content of the colorant (I) in the thermosetting protective film-forming layer may be appropriately adjusted according to the purpose. For example, the protective film may be printed by laser irradiation, and by adjusting the content of the colorant (I) in the thermosetting protective film-forming layer, the light transmittance of the protective film may be adjusted, and the visibility of the printing may be adjusted. In addition, by adjusting the content of the colorant (I) in the thermosetting protective film forming layer, the designability of the protective film can be improved, or the grinding traces on the back surface of the semiconductor wafer can be made less visible. Considering this aspect, in the composition (III-1) for a protective film-forming layer, the content of the coloring agent (I) (that is, the content of the coloring agent (I) in the thermosetting protective film-forming layer) is relatively The total content (total mass) of all components other than the solvent is preferably 0.1% by mass to 10% by mass, more preferably 0.1% by mass to 7.5% by mass, particularly preferably 0.1% by mass to 5% by mass. When the aforementioned content of the colorant (I) is more than the aforementioned lower limit value, a more significant effect by using the colorant (I) can be obtained. Moreover, when the said content of a coloring agent (I) is below the said upper limit, it can suppress that the light transmittance of a thermosetting protective film forming layer falls too much.

[通用添加劑(J)] [General Additives (J)]

保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層中，亦可在無損本發明的功效之範圍內，含有通用添加劑(J)。 The composition (III-1) for a protective film-forming layer and the thermosetting protective film-forming layer may contain a general-purpose additive (J) within a range that does not impair the effect of the present invention.

通用添加劑(J)可為公知的添加劑，可根據目的任意選擇，並無特別限定，作為較佳的通用添加劑(J)，例如可列舉：塑化劑、抗靜電劑、抗氧化劑、吸氣劑(gettering agent)等。 The general-purpose additive (J) may be a known additive, and can be arbitrarily selected according to the purpose without particular limitation. As the preferred general-purpose additive (J), for example, a plasticizer, an antistatic agent, an antioxidant, and a getter can be mentioned. (gettering agent), etc.

保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層所含有之通用添加劑(I)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The composition for protective film forming layer (III-1) and the general additive (I) contained in the thermosetting protective film forming layer may be only one kind or two or more kinds; in the case of two or more kinds, The combination and ratio of these can be arbitrarily selected.

保護膜形成層用組成物(III-1)及熱硬化性保護膜形成層中的通用添加劑(I)的含量並無特別限定，根據目的適宜選擇即可。 The content of the general-purpose additive (I) in the composition (III-1) for a protective film-forming layer and the thermosetting protective film-forming layer is not particularly limited, and may be appropriately selected according to the purpose.

[溶劑] [solvent]

保護膜形成層用組成物(III-1)較佳為進一步含有溶劑 。含有溶劑之保護膜形成層用組成物(III-1)的操作性良好。 It is preferable that the composition (III-1) for protective film-forming layers further contains a solvent . The solvent-containing composition for a protective film-forming layer (III-1) has good handleability.

前述溶劑並無特別限定，作為較佳的前述溶劑，例如可列舉：甲苯、二甲苯等烴；甲醇、乙醇、2-丙醇、異丁醇(2-甲基丙烷-1-醇)、1-丁醇等醇；乙酸乙酯、乙酸丁酯等酯；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 solvent is not particularly limited, and preferable examples of the aforementioned solvent 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 and butyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amine bond compound) and so on.

保護膜形成層用組成物(III-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，這些之組合及比率可任意選擇。 The solvent contained in the composition (III-1) for a protective film-forming layer may be only one type or two or more types, and in the case of two or more types, the combination and ratio of these may be arbitrarily selected.

就可使保護膜形成層用組成物(III-1)中的含有成分更均勻地混合之方面而言，保護膜形成層用組成物(III-1)所含有之溶劑較佳為甲基乙基酮等。 The solvent contained in the composition for a protective film-forming layer (III-1) is preferably methyl ethyl alcohol because the components contained in the composition for a protective film-forming layer (III-1) can be mixed more uniformly. Ketones etc.

關於溶劑的含量，較佳為相對於前述保護膜形成用組成物的總質量，前述保護膜形成用組成物中的固形物成分濃度成為10質量%至80質量%之量，更佳為成為20質量%至70質量%之量，進一步更佳為成為30質量%至65質量%之量。 The content of the solvent is preferably such that the solid content concentration in the composition for forming a protective film is 10 to 80% by mass, more preferably 20% by mass relative to the total mass of the composition for forming a protective film. The amount of mass % to 70 mass % is more preferably 30 mass % to 65 mass %.

<<熱硬化性保護膜形成層用組成物的製造方法>> <<The manufacturing method of the composition for thermosetting protective film forming layers>>

保護膜形成層用組成物(III-1)等熱硬化性保護膜形成層用組成物藉由調配用以構成該組成物之各成分而獲得。 The composition for thermosetting protective film-forming layers, such as the composition for protective film-forming layers (III-1), is obtained by blending the respective components constituting the composition.

調配各成分時之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 the ingredients is not particularly limited, and they may be added at the same time. Add 2 or more ingredients.

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

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

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

‧能量線硬化性保護膜形成層 ‧Energy ray curable protective film forming layer

能量線硬化性保護膜形成層含有能量線硬化性成分(a)。 The energy ray curable protective film forming layer contains the 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。此處，所謂「能量線」及「能量線硬化性」係如上文所說明。 The energy ray curable component (a) is preferably uncured, preferably has adhesiveness, and is more preferably uncured and has adhesiveness. Here, the so-called "energy ray" and "energy ray sclerosis" are as described above.

<<能量線硬化性保護膜形成層用組成物>> <<The composition for energy ray curable protective film forming layer>>

能量線硬化性保護膜形成層可由含有該層的構成材料之能量線硬化性保護膜形成層用組成物形成。例如，於能量線硬化性保護膜形成層之形成對象面塗敷能量線硬 化性保護膜形成層用組成物，視需要使之乾燥，藉此可於目標部位形成能量線硬化性保護膜形成層。能量線硬化性保護膜形成層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能量線硬化性保護膜形成層中的前述成分彼此的含量比率相同。此處，所謂「常溫」係如上文所說明。 The energy-ray-curable protective film-forming layer can be formed from a composition for energy-ray-curable protective film-forming layers containing the constituent materials of the layer. For example, applying energy ray hardening to the surface to be formed of the energy ray curable protective film forming layer The composition for a chemical protective film forming layer can be dried, if necessary, to form an energy ray curable protective film forming layer at a target site. The content ratio of components that do not vaporize at normal temperature in the composition for an energy ray curable protective film-forming layer is usually the same as the content ratio of the aforementioned components in the energy ray-curable protective film-forming layer. Here, the so-called "normal temperature" is as described above.

利用公知的方法塗敷能量線硬化性保護膜形成層用組成物即可，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 energy ray-curable protective film-forming layer by a known method, for example, methods using the following various coaters: air knife coater, blade coater, bar coater, gravure coater, etc. Coaters, Roll Coaters, Roll Knife Coaters, Curtain Coaters, Die Coaters, Knife Coaters, Screen Coaters, Rod Coaters, Contact Coating machine, etc.

能量線硬化性保護膜形成層用組成物的乾燥條件並無特別限定，於能量線硬化性保護膜形成層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 energy ray-curable protective film-forming layers are not particularly limited, and when the composition for energy-ray-curable protective film-forming layers contains a solvent described later, it is preferable to perform heating and drying, and in this case, it is preferable to perform drying by heating. Preferably, drying is performed under the conditions of, for example, 70° C. to 130° C. and 10 seconds to 5 minutes.

<保護膜形成層用組成物(IV-1)> <Composition for protective film-forming layer (IV-1)>

作為能量線硬化性保護膜形成層用組成物，例如可列舉含有前述能量線硬化性成分(a)的能量線硬化性保護膜形成層用組成物(IV-1)(本說明書中，有時僅簡稱為「保護 膜形成層用組成物(IV-1)」)等。 Examples of the composition for energy ray curable protective film-forming layers include composition (IV-1) for energy ray curable protective film-forming layers containing the aforementioned energy ray curable component (a) (in this specification, there may be simply referred to as "protection Film-forming layer composition (IV-1)") and the like.

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

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

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)可該聚合物的至少一部分藉由交聯劑進行交聯，亦可不進行交聯。 Examples of the energy ray curable component (a) include a polymer (a1) having an energy ray curable group and a weight average molecular weight of 80,000 to 2,000,000, and a compound having an energy ray curable group and a molecular weight of 100 to 80,000. (a2). At least a part of the said polymer (a1) may be crosslinked by a crosslinking agent, and may not be crosslinked.

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

作為具有能量線硬化性基且重量平均分子量為80000至2000000之聚合物(a1)，例如可列舉丙烯酸系樹脂(a1-1)，該丙烯酸系樹脂(a1-1)係使丙烯酸系聚合物(a11)與能量線硬化性化合物(a12)進行加成反應而成，該丙烯酸系聚合物(a11)具有可與其他化合物所具有之基反應之官能基，該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 (a1-1). a11) is formed by addition reaction with an energy ray curable compound (a12), the acrylic polymer (a11) has a functional group reactive with a group of other compounds, and the energy ray curable compound (a12) has Energy ray hardening groups such as groups reactive with the aforementioned functional groups and energy ray hardening double bonds.

作為丙烯酸系聚合物(a11)中可與其他化合物所具有之基反應之前述官能基，例如可列舉：羥基、羧基、胺基、 取代胺基(胺基的1個或2個氫原子被氫原子以外的基取代而成之基)、環氧基等。但是，就防止半導體晶圓或半導體晶片等的電路腐蝕之方面而言，前述官能基較佳為羧基以外的基。 Examples of the functional groups that can react with groups contained in other compounds in the acrylic polymer (a11) include hydroxyl groups, carboxyl groups, amino groups, Substituted amino groups (groups in which one or two hydrogen atoms of an amino group are substituted by groups other than hydrogen atoms), epoxy groups, and the like. However, it is preferable that the said functional group is a group other than a carboxyl group from the viewpoint of preventing circuit corrosion of a semiconductor wafer, a semiconductor wafer, or the like.

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

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

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

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

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

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

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

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

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

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((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 acrylic monomer not having the above-mentioned functional group, the alkyl group constituting the alkyl ester is preferably an alkyl (meth)acrylate having a chain structure of 1 to 18 carbon atoms, and the like, for example: (methyl) base) methyl acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-butyl (meth)acrylate, 3rd-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2 (meth)acrylate -Ethyl Hexyl ester, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, (meth)acrylate ) Undecyl acrylate, dodecyl (meth)acrylate (also known as lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate base ester (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (also known as palmityl (meth)acrylate), (meth)acrylate ) heptadecyl acrylate, octadecyl (meth)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。 Moreover, as an acryl-type monomer which does not have the said functional group, (meth)acrylate methoxymethyl, (meth)acrylate methoxyethyl, (meth)acrylate ethoxymethyl can also be mentioned, for example. (meth)acrylates containing alkoxyalkyl groups such as ethoxyethyl (meth)acrylates; aromatic groups containing aryl (meth)acrylates such as phenyl (meth)acrylates (meth)acrylate; non-crosslinkable (meth)acrylamide and its derivatives; (meth)acrylate N,N-dimethylaminoethyl ester, (meth)acrylate N,N- Non-crosslinkable (meth)acrylates having tertiary amine groups, such as dimethylaminopropyl ester, etc.

構成前述丙烯酸系聚合物(a11)之前述不具有官能基之丙烯酸系單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The acryl-based monomer that does not have a functional group constituting the acryl-based polymer (a11) may be only one type or two or more types; in the case of two or more types, the combination and ratio of these may be arbitrarily selected .

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

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

前述丙烯酸系聚合物(a11)中，由具有前述官能基之丙烯酸系單體衍生之結構單元的比例(含量)相對於構成前述丙烯酸系聚合物(a11)之結構單元的總質量，較佳為0.1質量%至50質量%，更佳為1質量%至40質量%，尤佳為3質量%至30質量%。藉由前述比例為此種範圍，可藉由利用前述丙烯酸系聚合物(a11)與前述能量線硬化性化合物(a12)之共聚合所獲得之前述丙烯酸系樹脂(a1-1)中能量線硬化性基的含量，將保護膜的硬化程度容易地調節為較佳的範圍。 In the aforementioned acrylic polymer (a11), the ratio (content) of the structural unit derived from the acrylic monomer having the aforementioned functional group with respect 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, and still more preferably 3% by mass to 30% by mass. Since the aforementioned ratio is in such a range, energy ray curing in the aforementioned acrylic resin (a1-1) obtained by the copolymerization of the aforementioned acrylic polymer (a11) and the aforementioned energy ray curing compound (a12) can be achieved The content of the radicals can easily adjust the degree of hardening of the protective film to a preferred 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，這些之組合及比率可任意選擇。 The said acrylic polymer (a11) which comprises the said acrylic resin (a1-1) may be only 1 type, and may be 2 or more types; In the case of 2 or more types, the combination and ratio of these can be selected arbitrarily.

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

前述能量線硬化性化合物(a12)較佳為具有選自由異氰酸酯基、環氧基及羧基所組成之群組中的1種或2種以上作為可與前述丙烯酸系聚合物(a11)所具有之官能基反應之基，更佳為具有異氰酸酯基作為前述基。於前述能量線硬化性化合物(a12)例如具有異氰酸酯基作為前述基之情 形時，該異氰酸酯基與前述具有羥基作為官能基之丙烯酸系聚合物(a11)的該羥基容易反應。 The aforementioned energy ray-curable compound (a12) preferably has one or more selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group as a compound that the aforementioned acrylic polymer (a11) has. More preferably, the functional group reacts with an isocyanate group as the aforementioned group. In the case where the aforementioned energy ray-curable compound (a12) has, for example, an isocyanate group as the aforementioned group In the form of the isocyanate group, it is easy to react with the hydroxyl group of the aforementioned 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2個。 It is preferable that the said energy ray hardening compound (a12) has 1 to 5 pieces of the said energy ray hardening group in 1 molecule, More preferably, it has 1 piece to 2 pieces.

作為前述能量線硬化性化合物(a12)，例如可列舉：異氰酸2-甲基丙烯醯氧基乙酯、間-異丙烯基-α,α-二甲基苄基異氰酸酯、甲基丙烯醯基異氰酸酯、異氰酸烯丙酯、異氰酸1,1-(雙丙烯醯氧基甲基)乙酯；藉由二異氰酸酯化合物或多異氰酸酯化合物與(甲基)丙烯酸羥基乙酯之反應而獲得之丙烯醯基單異氰酸酯化合物；藉由二異氰酸酯化合物或多異氰酸酯化合物、多元醇化合物及(甲基)丙烯酸羥基乙酯之反應而獲得之丙烯醯基單異氰酸酯化合物等。 Examples of the energy ray curable compound (a12) include 2-methacryloyloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and methacryloyl isocyanate. diisocyanate, allyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate; by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth)acrylate Acryloyl monoisocyanate compound obtained; acryl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound, polyol compound and hydroxyethyl (meth)acrylate, etc.

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

構成前述丙烯酸系樹脂(a1-1)之前述能量線硬化性化合物(a12)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之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 two or more types; in the case of two or more types, the combination and ratio of these may be arbitrarily selected .

丙烯酸系樹脂(a1-1)的含量相對於保護膜形成層用組成物(IV-1)中的溶劑以外的成分的總質量，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 1% by mass with respect to the total mass of the components other than the solvent in the composition for protective film-forming layers (IV-1) It is to 40 mass %, More preferably, it is 2 to 30 mass %, More preferably, it is 3 to 20 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%。藉由前述含量之比例為此種範圍，硬化後的保護膜的接著力進一步變大。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，前述含量之比例的上限值有時超過100莫耳%。 In the acrylic resin (a1-1), the ratio of the content of the energy ray curable group derived from the energy ray curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) It is preferably 20 mol% to 120 mol%, more preferably 35 mol% to 100 mol%, particularly preferably 50 mol% to 100 mol%. When the ratio of the said content is in such a range, the adhesive force of the protective film after hardening becomes further large. Furthermore, in the case where the energy ray-curable compound (a12) is a monofunctional (having one of the aforementioned groups in 1 molecule) compound, the upper limit of the ratio of the aforementioned content is 100 mol%, but in the aforementioned energy When the linear curable compound (a12) is a polyfunctional (having two or more of the aforementioned groups in one molecule) compound, the upper limit of the ratio of the aforementioned content may exceed 100 mol %.

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

此處，所謂「重量平均分子量」係如上文所說明。 Here, the so-called "weight average molecular weight" is as described above.

於前述聚合物(a1)的至少一部分藉由交聯劑進行交聯之情形時，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反應之基之單體進行聚合，在前述與交聯劑反應之基中進行交聯，亦可在源自前述能量線硬化性化合物(a12)之與前述 官能基反應之基中進行交聯。 When at least a part of the above-mentioned polymer (a1) is cross-linked by a cross-linking agent, the above-mentioned polymer (a1) may be any monomer constituting the above-mentioned acrylic polymer (a11) which does not meet the above description and The monomer having a group reactive with the crosslinking agent is polymerized, and the crosslinking is carried out in the group reactive with the crosslinking agent, or the energy ray curable compound (a12) derived from the energy ray curable compound (a12) and the above The crosslinking is carried out in the reactive group of the functional group.

保護膜形成層用組成物(IV-1)及能量線硬化性保護膜形成層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，這些之組合及比率可任意選擇。 The above-mentioned polymer (a1) contained in the composition (IV-1) for a protective film-forming layer and the energy ray-curable protective film-forming layer may be only one type or two or more types; in the case of two or more types , the combination and ratio of these can be arbitrarily selected.

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

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

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

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

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

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之樹脂，但本發明中視作前述化合物(a2)。 Among the above-mentioned compounds (a2), as the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group, for example, those described in paragraph 0043 of "Japanese Unexamined Patent Application Publication No. 2013-194102" can be used. of resin. This resin also corresponds to the resin constituting the thermosetting component 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.

保護膜形成層用組成物(IV-1)及能量線硬化性保護膜形成層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，這些之組合及比率可任意選擇。 The above-mentioned compound (a2) contained in the composition (IV-1) for a protective film-forming layer and the energy ray-curable protective film-forming layer may be only one kind or two or more kinds; in the case of two or more kinds , the combination and ratio of these can be arbitrarily selected.

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

於保護膜形成層用組成物(IV-1)及能量線硬化性保護膜形成層含有前述化合物(a2)作為前述能量線硬化性成分(a)之情形時，較佳為亦進一步含有不具有能量線硬化性基之聚合物(b)。 When the composition (IV-1) for a protective film-forming layer and the energy ray-curable protective film-forming layer contain the compound (a2) as the energy ray-curable component (a), it is preferable to further contain no Energy ray curable base polymer (b).

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

作為不具有能量線硬化性基之聚合物(b)，例如可列舉：丙烯酸系聚合物、苯氧基樹脂、胺基甲酸酯樹脂、聚 酯、橡膠系樹脂、丙烯酸胺基甲酸酯樹脂等。 Examples of the polymer (b) not having an energy ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polymer Ester, rubber-based resin, urethane acrylate resin, etc.

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

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

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

作為前述(甲基)丙烯酸烷基酯，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((甲基)丙烯酸硬脂酯)等。 As the above-mentioned (meth)acrylic acid alkyl ester, the alkyl group constituting the alkyl ester is preferably a (meth)acrylic acid alkyl ester having a chain structure of 1 to 18 carbon atoms, for example, (methyl) ) methyl acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, ( 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-(meth)acrylate Ethylhexyl, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-octyl (meth)acrylate Nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as (meth)acrylic acid) lauryl), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, Cetyl (meth)acrylate (also known as palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate ((meth)acrylic acid) stearyl ester) etc.

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

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

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

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

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

作為至少一部分藉由交聯劑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反應之聚合物。 Examples of the polymer (b) that is at least partially cross-linked by a cross-linking agent and does not have the above-mentioned energy ray-curable group include polymerization in which the reactive functional group in the above-mentioned polymer (b) reacts with a cross-linking agent. thing.

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

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

具有反應性官能基之前述聚合物(b)中，由具有反應性官能基之單體衍生之結構單元的比例(含量)相對於構成前述聚合物(b)之結構單元的總質量，較佳為1質量%至20質量%，更佳為2質量%至10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 units derived from the monomer having a reactive functional group is preferably relative to the total mass of the structural units constituting the aforementioned polymer (b) It is 1 mass % - 20 mass %, More preferably, it is 2 mass % - 10 mass %. Since the said ratio is such a range, in the said polymer (b), the degree of crosslinking becomes a more preferable range.

就保護膜形成層用組成物(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。此處，所謂「重量平均分子量」係如上文所說明。 The weight average molecular weight (Mw) of the polymer (b) not having an energy ray-curable group is preferably from 10,000 to 2,000,000 in terms of better film-forming properties of the composition (IV-1) for forming a protective film. , more preferably 100,000 to 1,500,000. Here, the so-called "weight average molecular weight" is as described above.

保護膜形成層用組成物(IV-1)及能量線硬化性保護膜形成層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，這些之組合及比率可任意選擇。 The composition (IV-1) for a protective film-forming layer and the polymer (b) that does not have an energy ray-curable group contained in the energy-ray-curable protective film-forming layer may be only one kind or two or more kinds; In the case of two or more types, the combination and ratio of these can be arbitrarily selected.

作為保護膜形成層用組成物(IV-1)，可列舉含有前述 聚合物(a1)及前述化合物(a2)之任一者或兩者之組成物。並且，於保護膜形成層用組成物(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，較佳為亦進一步含有前述(a1)。另外，保護膜形成層用組成物(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 a protective film-forming layer include those containing the above-mentioned A composition of either or both of the polymer (a1) and the aforementioned compound (a2). In addition, when the composition (IV-1) for a protective film-forming layer contains the aforementioned compound (a2), it is preferable to further contain a polymer (b) having no energy ray curable group, and in this case, the It is preferable that the above-mentioned (a1) is further contained. Moreover, the composition (IV-1) for protective film forming layers may not contain the said compound (a2), and may also contain the said polymer (a1) and the polymer (b) which does not have an energy ray curable group together.

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

保護膜形成層用組成物(IV-1)中，相對於溶劑以外的成分的總含量(總質量)，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，能量線硬化性保護膜形成層中的前述能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的合計含量)較佳為5質量%至90質量%，更佳為10質量%至80質量%，尤佳為20質量%至70質量%。藉由能量線硬化性成分的含量的前述比例為此種範圍，能量線硬化性保護膜形成層的能量線硬化性變得更良好。 In the composition (IV-1) for a protective film-forming layer, the energy-ray-curable component (a) and the polymer (b) having no energy-ray-curable group relative to the total content (total mass) of components other than the solvent ) (that is, the total content of the energy-ray-curable component (a) and the polymer (b) without an energy-ray-curable group in the energy-ray-curable protective film-forming layer) is preferably 5 mass % to 90 mass %, more preferably 10 to 80 mass %, particularly preferably 20 to 70 mass %. When the said ratio of content of an energy ray curable component is such a range, the energy ray curability of an energy ray curable protective film forming layer becomes more favorable.

前述能量線硬化性成分(a)的含量相對於保護膜形成層用組成物(IV-1)中的溶劑以外的成分的總質量，較佳為1質量%至80質量%。 The content of the energy ray-curable component (a) is preferably 1 to 80% by mass relative to the total mass of components other than the solvent in the composition (IV-1) for a protective film-forming layer.

前述能量線硬化性成分(a1)的含量相對於保護膜形成層用組成物(IV-1)中的溶劑以外的成分的總質量，較佳為1質量%至80質量%。 The content of the energy ray-curable component (a1) is preferably 1% by mass to 80% by mass relative to the total mass of components other than the solvent in the composition (IV-1) for a protective film-forming layer.

前述能量線硬化性成分(a2)的含量相對於保護膜形成層用組成物(IV-1)中的溶劑以外的成分的總質量，較佳為1質量%至80質量%。 The content of the energy ray curable component (a2) is preferably 1 to 80% by mass relative to the total mass of components other than the solvent in the composition (IV-1) for protective film-forming layers.

前述不具有能量線硬化性基之聚合物(b)的含量相對於保護膜形成層用組成物(IV-1)中的溶劑以外的成分的總質量，較佳為1質量%至80質量%。 The content of the polymer (b) having no energy ray-curable group is preferably 1% by mass to 80% by mass relative to the total mass of the components other than the solvent in the composition (IV-1) for a protective film-forming layer. .

再者，上述成分(a1)、成分(a2)、成分(b)的合計含量不超過100質量%。 In addition, the total content of the said component (a1), component (a2), and component (b) does not exceed 100 mass %.

保護膜形成層用組成物(IV-1)中，除前述能量線硬化性成分以外，亦可進一步根據目的含有選自由熱硬化性成分、光聚合起始劑、填充材料、偶合劑、交聯劑、著色劑及通用添加劑所組成之群組中的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及熱硬化性成分之保護膜形成層用組成物(IV-1)，所形成之能量線硬化性保護膜形成層藉由加熱而對被黏著體之接著力提高，由該能量線硬化性保護膜形成層形成之保護膜的強度亦提高。 The composition (IV-1) for a protective film-forming layer may further contain a thermosetting component, a photopolymerization initiator, a filler, a coupling agent, a crosslinking agent, in addition to the aforementioned energy ray curable component, according to the purpose. One or more of the group consisting of a colorant, a colorant, and a general-purpose additive. For example, by using the composition for protective film-forming layer (IV-1) containing the above-mentioned energy-ray-curable component and thermosetting component, the formed energy-ray-curable protective film-forming layer is heated to the adherend. The adhesive force is improved, and the intensity|strength of the protective film formed by this energy-beam curable protective film-forming layer is also improved.

作為保護膜形成層用組成物(IV-1)中的前述熱硬化性成分、光聚合起始劑、填充材料、偶合劑、交聯劑、著色劑及通用添加劑，分別可列舉與保護膜形成層用組成物(III-1)中的熱硬化性成分(B)、光聚合起始劑(H)、填充材料(D)、偶合劑(E)、交聯劑(F)、著色劑(I)及通用添加劑(J)相同的化合物。 Examples of the above-mentioned thermosetting component, photopolymerization initiator, filler, coupling agent, crosslinking agent, colorant, and general-purpose additive in the composition (IV-1) for a protective film-forming layer include those used for forming a protective film. Thermosetting component (B), photopolymerization initiator (H), filler (D), coupling agent (E), crosslinking agent (F), colorant ( I) and the same compounds as general additive (J).

保護膜形成層用組成物(IV-1)中，前述熱硬化性成分、光聚合起始劑、填充材料、偶合劑、交聯劑、著色劑及通用添加劑分別可單獨使用1種，亦可併用2種以上；於併用2種以上之情形時，這些之組合及比率可任意選擇。 In the composition (IV-1) for a protective film-forming layer, the above-mentioned thermosetting components, photopolymerization initiators, fillers, coupling agents, crosslinking agents, colorants and general additives may be used alone, or may be used alone. Two or more types are used in combination; when two or more types are used in combination, the combination and ratio of these can be arbitrarily selected.

保護膜形成層用組成物(IV-1)中的前述熱硬化性成分、光聚合起始劑、填充材料、偶合劑、交聯劑、著色劑及通用添加劑的含量根據目的適宜調節即可，並無特別限定。 The contents of the aforementioned thermosetting components, photopolymerization initiators, fillers, coupling agents, cross-linking agents, colorants and general additives in the composition (IV-1) for a protective film-forming layer may be appropriately adjusted according to the purpose, There is no particular limitation.

保護膜形成層用組成物(IV-1)較佳為進一步含有溶劑，原因在於，藉由稀釋而使該保護膜形成層用組成物(IV-1)的操作性提高。 It is preferable that the composition (IV-1) for protective film forming layers further contains a solvent because the workability of the composition (IV-1) for forming protective film forming layers is improved by dilution.

作為保護膜形成層用組成物(IV-1)所含有之溶劑，例如可列舉與保護膜形成層用組成物(III-1)中的溶劑相同的溶劑。 Examples of the solvent contained in the composition (IV-1) for a protective film-forming layer include the same solvents as those in the composition (III-1) for a protective film-forming layer.

保護膜形成層用組成物(IV-1)所含有之溶劑可僅為1種，亦可為2種以上。 The solvent contained in the composition (IV-1) for a protective film forming layer may be only one type or two or more types.

<<能量線硬化性保護膜形成層用組成物的製造方法>> <<The manufacturing method of the composition for energy ray curable protective film forming layers>>

保護膜形成層用組成物(IV-1)等能量線硬化性保護膜形成層用組成物藉由將用以構成該組成物之各成分加以調配而獲得。 The composition for energy ray-curable protective film-forming layers, such as the composition for protective film-forming layers (IV-1), is obtained by blending each component for constituting the composition.

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

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

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

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

○剝離膜 ○Release film

前述剝離膜只要滿足上述靜摩擦力的條件(29N以下)，則並無特別限定。作為較佳的剝離膜，例如可列舉該領域中所使用之具有剝離處理面之公知的剝離膜等。作為針 對前述剝離處理面的剝離處理，可列舉利用以下各種剝離劑之處理：醇酸系、聚矽氧系、氟系、不飽和聚酯系、聚烯烴系或蠟系等。就具有耐熱性之方面而言，前述剝離劑較佳為醇酸系、聚矽氧系或氟系的剝離劑。 The said peeling film will not be specifically limited if it satisfies the conditions of the said static friction force (29 N or less). As a preferable peeling film, the well-known peeling film etc. which have a peeling process surface used in this field are mentioned, for example. as a needle The peeling treatment on the peeling treated surface includes the following various peeling agents: alkyd-based, polysiloxane-based, fluorine-based, unsaturated polyester-based, polyolefin-based, wax-based, and the like. In terms of having heat resistance, the aforementioned release agent is preferably an alkyd-based, polysiloxane-based or fluorine-based release agent.

剝離膜的厚度並無特別限定，較佳為20μm至85μm，更佳為25μm至75μm。藉由剝離膜的厚度為前述下限值以上，變得更容易於目標階段將剝離膜剝離，另外，將保護膜形成用片捲取成輥後，捲痕不易附著於剝離膜。另一方面，藉由剝離膜的厚度為前述上限值以下，抑制剝離膜於目標外的階段剝離之功效變得更高。 The thickness of the release film is not particularly limited, but is preferably 20 to 85 μm, more preferably 25 to 75 μm. When the thickness of the peeling film is more than the aforementioned lower limit value, the peeling film becomes easier to peel at the target stage, and after the sheet for forming a protective film is wound up into a roll, the roll marks are less likely to adhere to the peeling film. On the other hand, when the thickness of a peeling film is below the said upper limit, the effect of suppressing peeling of a peeling film at the stage outside the objective becomes higher.

保護膜形成用片中，剝離膜中的與具備有前述保護膜形成層之側為相反側的表面(露出面)只要前述靜摩擦力為29N以下，則可為平滑面及凹凸面之任一者，例如考慮支持片中的與具備有保護膜形成層之側為相反側的表面(露出面)的表面粗糙度而適宜選擇即可。 In the sheet for protective film formation, the surface (exposed surface) on the opposite side of the release film to the side provided with the protective film forming layer may be either a smooth surface or a concavo-convex surface as long as the static friction force is 29 N or less For example, it may be appropriately selected in consideration of the surface roughness of the surface (exposed surface) on the opposite side to the side provided with the protective film forming layer in the support sheet.

本發明之保護膜形成用片中，前述支持片中的與具備有前述保護膜形成層之側為相反側的表面(露出面)以及前述剝離膜中的與具備有前述保護膜形成層之側為相反側的表面(露出面)之間的靜摩擦力如上所述為29N以下，較佳為25N以下，更佳為20N以下，進一步較佳為15N以下，尤佳為13N以下，例如亦可設為10N以下、8.5N以下等。 In the sheet for forming a protective film of the present invention, the surface (exposed surface) of the support sheet on the opposite side to the side provided with the protective film forming layer and the side provided with the protective film forming layer in the release film The static friction force between the surfaces on the opposite side (exposed surfaces) is 29N or less as described above, preferably 25N or less, more preferably 20N or less, further preferably 15N or less, particularly preferably 13N or less. 10N or less, 8.5N or less, etc.

另一方面，前述靜摩擦力的下限值並無特別限定，例如可設為1N、2N、3N等，但並不限定於這些。 On the other hand, the lower limit of the static friction force is not particularly limited, and may be, for example, 1N, 2N, 3N, or the like, but is not limited to these.

亦即，前述靜摩擦力為1N至29N即可，較佳為1N至25N，更佳為2N至20N，進一步更佳為2N至15N，尤佳為3N至13N。 That is, the aforementioned static friction force may be 1N to 29N, preferably 1N to 25N, more preferably 2N to 20N, still more preferably 2N to 15N, and particularly preferably 3N to 13N.

另外，前述靜摩擦力可為5N至12N，亦可為5N至7N。 In addition, the aforementioned static friction force may be 5N to 12N, or 5N to 7N.

前述靜摩擦力例如可藉由考慮支持片的前述表面(露出面)的平滑度與剝離膜的前述表面(露出面)的平滑度，選擇支持片及剝離膜之組合而進行調節。另外，前述靜摩擦力亦可藉由考慮支持片的前述表面(露出面)的材質與剝離膜的前述表面(露出面)的材質，選擇支持片及剝離膜之組合而進行調節。 The static friction force can be adjusted by, for example, selecting a combination of the support sheet and the release film in consideration of the smoothness of the surface (exposed surface) of the support sheet and the smoothness of the surface (exposed surface) of the release film. In addition, the static friction force may be adjusted by selecting a combination of the support sheet and the release film in consideration of the material of the surface (exposed surface) of the support sheet and the material of the surface (exposed surface) of the release film.

<保護膜形成用片的製造方法> <The manufacturing method of the sheet for protective film formation>

本發明之保護膜形成用片例如可藉由包含有以下步驟之製造方法而進行製造：以前述支持片中的與具備有前述保護膜形成層之側為相反側的表面的表面粗糙度成為0.5μm以下之方式，形成前述支持片與前述保護膜形成層之積層結構之步驟(以下，有時稱為「積層步驟(P1)」)；以及以前述支持片中的與具備有前述保護膜形成層之側為相反側的表面以及前述剝離膜中的與具備有前述保護膜形成層之側為相反側的表面之間的靜摩擦力成為29N以下之方式，形成前述保護膜形成層與前述剝離膜之積層 結構之步驟(以下，有時稱為「積層步驟(P2)」)。 The sheet for forming a protective film of the present invention can be produced, for example, by a production method comprising the step of setting the surface roughness of the surface of the support sheet on the opposite side to the side provided with the protective film forming layer to 0.5 A step of forming a layered structure of the support sheet and the protective film forming layer in a manner of not more than μm (hereinafter, sometimes referred to as "lamination step (P1)"); and forming the support sheet with the protective film The protective film forming layer and the peeling film were formed such that the static friction force between the surface on the opposite side of the layer and the surface on the opposite side of the peeling film and the surface on the opposite side with the protective film forming layer became 29 N or less. layer of The step of structure (hereinafter, it may be referred to as "layering step (P2)").

於支持片由複數層構成之情形時，將這些多個層積層而製造支持片即可。 When the support sheet is composed of a plurality of layers, the support sheet may be produced by laminating these multiple layers.

於製造於基材上積層其他層(例如，黏著劑層、中間層、塗層等)而成之支持片之情形時，例如將含有用以構成前述其他層之成分之組成物(例如，黏著劑組成物、中間層形成用組成物、塗佈組成物等)塗敷於基材的表面，視需要使之乾燥，藉此於基材積層前述其他層即可。另外，於製造於基材上積層其他層而成之支持片之情形時，例如將含有用以構成前述其他層之成分之組成物塗敷於剝離材料的剝離處理面，視需要使之乾燥，藉此於剝離材料上預先形成前述其他層後，將所形成之前述其他層的表面(露出面)與前述基材的表面貼合，藉此亦可於基材積層前述其他層。該情形時，視需要例如將保護膜形成層積層於前述其他層時等，對前述其他層進行某種操作時之前移除前述剝離材料即可。 In the case of manufacturing a support sheet formed by laminating other layers (for example, an adhesive layer, an intermediate layer, a coating layer, etc.) on a substrate, for example, a composition (for example, an adhesive layer) containing components for forming the other layers is included. Agent composition, intermediate layer-forming composition, coating composition, etc.) are applied to the surface of the base material, and the other layers described above may be laminated on the base material by drying if necessary. In addition, in the case of manufacturing a support sheet formed by laminating other layers on a base material, for example, a composition containing components for forming the other layers is applied to the release-treated surface of the release material, and dried as necessary. Thereby, after forming the said other layer in advance on the peeling material, the surface (exposed surface) of the said other layer formed and the surface of the said base material are bonded together, and the said other layer can also be laminated|stacked on the base material. In this case, if necessary, for example, when a protective film is formed to be laminated on the other layers, the peeling material may be removed before any operation is performed on the other layers.

作為前述剝離材料，使用該領域中公知的剝離材料即可，例如可使用與構成本發明之保護膜形成用片之上述剝離膜相同的剝離膜。 As said release material, what is known in the field may be used, and for example, the same release film as the above-mentioned release film constituting the sheet for forming a protective film of the present invention can be used.

例如，可對一表面或兩表面已積層有前述其他層之基材，直接塗敷目標組成物，進一步形成其他層。其中，此種情形時，較佳為採用如上所述般，將於剝離材料上預先 形成之前述其他層以及基材或已積層於基材上之其他層貼合之方法。 For example, the target composition can be directly applied to the substrate on which the other layers have been laminated on one surface or both surfaces, and further layers can be formed. Among them, in this case, it is preferable to use the above-mentioned method, which is pre-painted on the peeling material. A method for laminating the above-mentioned other layers and substrates or other layers that have been laminated on the substrates.

前述積層步驟(P1)中，支持片與保護膜形成層之積層結構例如可藉由下述方式而形成：於支持片的表面塗敷保護膜形成層用組成物，視需要使之乾燥，形成保護膜形成層(以下，有時將本步驟特別稱為「積層步驟(P1)-11」)。其中，本步驟中，以支持片中的未塗敷保護膜形成層用組成物之面(非塗敷面)的表面粗糙度成為0.5μm以下之方式，選擇支持片中之保護膜形成層用組成物之塗敷面。例如，於支持片的一表面的表面粗糙度為0.5μm以下，另一表面的表面粗糙度大於0.5μm之情形時，將該表面粗糙度大於0.5μm之表面設為保護膜形成層用組成物之塗敷面。另一方面，於支持片的兩表面的表面粗糙度均為0.5μm以下之情形時，將任一表面設為保護膜形成層用組成物之塗敷面均可。 In the aforementioned lamination step (P1), the lamination structure of the support sheet and the protective film-forming layer can be formed, for example, by the following manner: coating the surface of the support sheet with the composition for the protective film-forming layer, drying it as needed, and forming A protective film formation layer (Hereinafter, this step may be specifically referred to as "lamination step (P1)-11"). Among them, in this step, the surface roughness of the surface (non-coating surface) on which the composition for forming a protective film forming layer is not applied in the supporting sheet is selected to be 0.5 μm or less. The coating surface of the composition. For example, when the surface roughness of one surface of the support sheet is 0.5 μm or less and the surface roughness of the other surface is larger than 0.5 μm, the surface with the surface roughness larger than 0.5 μm is used as the composition for forming a protective film. the coating surface. On the other hand, when the surface roughness of both surfaces of a support sheet is 0.5 micrometer or less, any surface may be used as the coating surface of the composition for protective film-forming layers.

另外，前述積層步驟(P1)中，支持片與保護膜形成層之積層結構例如亦可利用與製作上述由複數層構成之支持片之情形相同的方法而形成。亦即，於剝離材料的剝離處理面塗敷保護膜形成層用組成物，視需要使之乾燥，藉此於前述剝離材料上預先形成保護膜形成層後，將所形成之該保護膜形成層中的未設置前述剝離材料之側的表面與支持片的表面貼合，藉此亦可形成支持片與保護膜形成 層之積層結構(以下，有時將本步驟特別稱為「積層步驟(P1)-12」)。其中，本步驟中，以支持片中的未貼合保護膜形成層之側的表面(以下，有時簡稱為「非貼合面」)的表面粗糙度成為0.5μm以下之方式，選擇支持片中之保護膜形成層之貼合面(以下，有時簡稱為「貼合面」)。此時，前述貼合面之選擇與上述之於支持片的表面塗敷保護膜形成層用組成物之情形之塗敷面之選擇同樣地進行即可。 Moreover, in the said lamination|stacking process (P1), the lamination structure of a support sheet and a protective film formation layer can also be formed by the same method as the case of making the above-mentioned support sheet which consists of a plurality of layers, for example. That is, after coating the composition for protective film-forming layer on the peeling treatment surface of the peeling material, and drying it as necessary, the protective film-forming layer is preliminarily formed on the peeling material, and then the formed protective film-forming layer is The surface of the side that is not provided with the aforementioned peeling material is attached to the surface of the support sheet, whereby the support sheet and the protective film can also be formed. Lamination structure of layers (hereinafter, this step may be specifically referred to as "lamination step (P1)-12"). However, in this step, the support sheet is selected so that the surface roughness of the surface on the side of the support sheet on which the protective film forming layer is not bonded (hereinafter, sometimes abbreviated as "non-bonding surface") becomes 0.5 μm or less. The bonding surface of the protective film forming layer (hereinafter, sometimes abbreviated as "bonding surface"). In this case, the selection of the bonding surface may be performed in the same manner as the selection of the coating surface in the case where the composition for forming a protective film forming layer is applied to the surface of the support sheet described above.

作為本方法中的前述剝離材料，使用該領域中公知的剝離材料即可，例如較佳為與構成本發明之保護膜形成用片之上述剝離膜相同的剝離膜。 As the peeling material in the present method, any known peeling material in the field may be used, and for example, the same peeling film as the peeling film constituting the protective film forming sheet of the present invention is preferable.

例如，於前述支持片為於基材的一表面或兩表面積層前述其他層而成之情形時，亦可將保護膜形成層用組成物直接塗敷於此種支持片上，形成保護膜形成層。其中，此種情形時，亦較佳為採用如積層步驟(P1)中所述般，將於剝離材料上預先形成之保護膜形成層與支持片貼合之方法。 For example, when the aforementioned support sheet is formed by layers of the aforementioned other layers on one surface or both surface areas of the substrate, the composition for a protective film-forming layer can also be directly coated on such a support sheet to form a protective film-forming layer . Among them, in this case, as described in the lamination step (P1), a method of laminating the protective film-forming layer formed in advance on the release material and the support sheet is also preferred.

於採用上述積層步驟(P1)-11作為積層步驟(P1)之情形時，前述積層步驟(P2)中，於保護膜形成層中的未設置支持片之側的表面貼合前述剝離膜即可。其中，本步驟中，以支持片的表面粗糙度為0.5μm以下之露出面以及剝離膜中的與貼合保護膜形成層之側為相反側的表面之間的靜摩擦力成為29N以下之方式，選擇剝離膜的種類。 When using the above-mentioned lamination step (P1)-11 as the lamination step (P1), in the above-mentioned lamination step (P2), in the protective film forming layer, the surface of the side where the support sheet is not provided is attached to the aforementioned peeling film. . Among them, in this step, the static friction force between the exposed surface of the support sheet with the surface roughness of 0.5 μm or less and the surface of the release film on the opposite side to the side where the protective film-forming layer is attached becomes 29 N or less, Select the type of release film.

另一方面，於採用上述積層步驟(P1)-12作為積層步驟(P1)之情形時，前述積層步驟(P2)中，將保護膜形成層中的與設置有支持片之側為相反側的表面所設置之剝離材料移除，使保護膜形成層的一表面露出後，於該保護膜形成層的露出面貼合前述剝離膜即可。其中，本步驟中，亦以支持片的表面粗糙度為0.5μm以下之露出面以及剝離膜中的與貼合保護膜形成層之側為相反側的表面之間的靜摩擦力成為29N以下之方式，選擇剝離膜的種類。 On the other hand, in the case where the above-mentioned lamination step (P1)-12 is used as the lamination step (P1), in the above-mentioned lamination step (P2), the protective film-forming layer on the opposite side to the side on which the support sheet is provided is disposed The peeling material provided on the surface is removed to expose a surface of the protective film forming layer, and then the peeling film can be attached to the exposed surface of the protective film forming layer. However, in this step, the static friction force between the exposed surface of the support sheet whose surface roughness is 0.5 μm or less and the surface on the opposite side of the release film to the side where the protective film-forming layer is attached is also set to be 29 N or less. , select the type of release film.

另外，於採用上述積層步驟(P1)-12作為積層步驟(P1)之情形時，作為預先形成保護膜形成層之前述剝離材料，採用前述剝離膜(構成本發明之保護膜形成用片之剝離膜)，藉此該積層步驟(P1)-12亦兼作前述積層步驟(P2)。可謂該製造方法就可將製造步驟簡化之方面而言較佳。以下，有時將利用該製造方法形成支持片與保護膜形成層之積層結構之步驟特別稱為「積層步驟(P1')」。 In addition, in the case where the above-mentioned lamination step (P1)-12 is used as the lamination step (P1), as the release material for forming the protective film-forming layer in advance, the above-mentioned release film (the release material constituting the protective film-forming sheet of the present invention) is used. film), whereby the lamination steps (P1)-12 also serve as the aforementioned lamination step (P2). It can be said that this manufacturing method is preferable in that the manufacturing steps can be simplified. Hereinafter, the step of forming the laminated structure of the support sheet and the protective film forming layer by this manufacturing method may be specifically referred to as "lamination step (P1')".

亦即，本發明之保護膜形成用片亦可利用以下製造方法而製造，該製造方法具有以下步驟：使用前述保護膜形成層用組成物，於前述剝離膜的剝離處理面上形成保護膜形成層，將所形成之前述保護膜形成層中的未設置前述剝離膜之側的表面以及前述支持片的表面貼合(積層步驟(P1'))；且以前述支持片中的未貼合前述保護膜形成層之側的表面的表面粗糙度成為0.5μm以下之方式，選擇前述 支持片的貼合面，以前述支持片的表面粗糙度為0.5μm以下之前述表面以及前述剝離膜中的與剝離處理面為相反側的表面之間的靜摩擦力成為29N以下之方式，選擇前述剝離膜。 That is, the sheet for forming a protective film of the present invention can also be produced by the following production method having the step of forming a protective film on the peeling-treated surface of the peeling film using the composition for a protective film-forming layer. layer, the surface of the side that is not provided with the aforementioned peeling film and the surface of the aforementioned support sheet in the aforementioned protective film forming layer formed are bonded (lamination step (P1')); and the aforementioned support sheet is not attached to the aforementioned The above-mentioned is selected so that the surface roughness of the surface on the side of the protective film forming layer becomes 0.5 μm or less The bonding surface of the support sheet, with the surface roughness of the aforementioned support sheet being the aforementioned surface below 0.5 μm and the aforementioned peeling film and the peeling treatment surface between the surfaces on the opposite side become the mode below 29N, select the aforementioned Peel off the film.

例如，如圖7等所示，於製造下述保護膜形成用片時，亦即自剝離膜側往下看而俯視保護膜形成用片時，保護膜形成層的表面積小於黏著劑層之保護膜形成用片之情形時，上述製造方法中，將預先切成預定的大小及形狀之保護膜形成層設置於黏著劑層上即可。 For example, as shown in FIG. 7 and the like, when the sheet for forming a protective film is produced, that is, when the sheet for forming a protective film is planarly viewed from the release film side, the surface area of the protective film forming layer is smaller than that of the adhesive layer. In the case of the film-forming sheet, in the above-mentioned production method, the protective film-forming layer cut into a predetermined size and shape in advance may be provided on the adhesive layer.

製造本發明之保護膜形成用片時，例如保護膜形成層可藉由下述方式而形成：將前述保護膜形成層用組成物塗敷於保護膜形成層之形成對象面，較佳為使之乾燥。利用公知的方法塗敷保護膜形成層用組成物即可，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。 When the sheet for forming a protective film of the present invention is produced, for example, the protective film forming layer can be formed by applying the composition for a protective film forming layer to the surface to be formed of the protective film forming layer, preferably such that of dryness. What is necessary is just to coat the composition for protective film-forming layers by a well-known method, for example, the method using the following various coaters: air knife coater, knife coater, bar coater, gravure coater, Roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, wire rod coater, contact coater, etc. .

保護膜形成層用組成物的乾燥條件並無特別限定，保護膜形成層用組成物較佳為進行加熱乾燥，該情形時，較佳為於例如70℃至130℃且1分鐘至5分鐘之條件下進行乾燥。 The drying conditions of the composition for a protective film-forming layer are not particularly limited, and the composition for a protective film-forming layer is preferably dried by heating. dry under conditions.

製造本發明之保護膜形成用片時，例如黏著劑層可藉由下述方式而形成：將前述黏著劑組成物塗敷於黏著劑層之形成對象面，較佳為進行乾燥。黏著劑組成物可利用與保護膜形成層用組成物之情形相同的方法進行塗敷。 When producing the sheet for forming a protective film of the present invention, for example, the adhesive layer can be formed by applying the above-mentioned adhesive composition to the surface to be formed of the adhesive layer, preferably drying. The adhesive composition can be applied by the same method as in the case of the composition for protective film-forming layers.

所塗敷之黏著劑組成物可藉由進行加熱而交聯，該利用加熱之交聯亦可與乾燥一起進行。加熱條件例如可設為100℃至130℃且1分鐘至5分鐘，但並不限定於此。 The applied adhesive composition may be cross-linked by heating, and the cross-linking by heating may be performed together with drying. The heating conditions can be set to, for example, 100° C. to 130° C. for 1 minute to 5 minutes, but are not limited thereto.

製造本發明之保護膜形成用片時，例如塗層可藉由下述方式而形成：將前述塗佈組成物塗敷於塗層之形成對象面，較佳為進行乾燥，視需要使藉由塗敷而形成之塗膜硬化。塗佈組成物可利用與保護膜形成層用組成物之情形相同的方法進行塗敷。 When the sheet for forming a protective film of the present invention is produced, for example, a coating layer can be formed by applying the coating composition to the surface to be formed of the coating layer, preferably drying, and, if necessary, by applying the coating composition. The coating film formed by coating hardens. The coating composition can be coated by the same method as in the case of the composition for protective film-forming layers.

塗佈組成物的乾燥條件並無特別限定，例如較佳為於與保護膜形成層用組成物之情形相同的條件下進行乾燥。 The drying conditions of the coating composition are not particularly limited, but for example, drying is preferably performed under the same conditions as in the case of the composition for forming a protective film.

由塗佈組成物形成之前述塗膜的硬化條件並無特別限定，利用公知的方法進行即可。 The hardening conditions of the said coating film formed from the coating composition are not specifically limited, What is necessary is just to carry out by a well-known method.

於藉由照射能量線而進行硬化之情形時，例如當照射紫外線時，使用高壓水銀燈、融合H型燈或氙氣燈等作為紫外線源，將照射量設為較佳為100mJ/cm2至500mJ/cm2 而進行照射即可。另一方面，當照射電子束時，藉由電子束加速器等產生電子束，將照射量設為較佳為150kV至350kV而進行照射即可。其中，較佳為藉由照射紫外線而形成塗層。 In the case of curing by irradiating energy rays, for example, when irradiating ultraviolet rays, a high-pressure mercury lamp, a fusion H-type lamp, a xenon lamp, etc. are used as the ultraviolet source, and the irradiation amount is preferably 100mJ/cm 2 to 500mJ/ cm 2 can be irradiated. On the other hand, when an electron beam is irradiated, an electron beam may be generated by an electron beam accelerator or the like, and the irradiation may be performed by setting the irradiation amount to preferably 150 kV to 350 kV. Among them, it is preferable to form a coating layer by irradiating ultraviolet rays.

於以被覆基材等的凹凸面而提高支持片的表面平滑度為目的而形成塗層之情形時，較佳為將塗佈組成物直接塗敷於前述凹凸面，形成塗層。藉此，可抑制於塗層的表面與凹凸面之間產生空隙部，例如可抑制光於塗層的表面與凹凸面之界面發生漫反射，從而可更良好地對半導體晶片進行上述紅外線檢測。 When a coating layer is formed for the purpose of coating the uneven surface of the substrate or the like to improve the surface smoothness of the support sheet, it is preferable to directly apply the coating composition to the uneven surface to form a coating layer. Thereby, generation of voids between the surface of the coating layer and the concave-convex surface can be suppressed, for example, diffuse reflection of light at the interface between the surface of the coating layer and the concave-convex surface can be suppressed, and the above-mentioned infrared detection of the semiconductor wafer can be performed more favorably.

為了抑制前述空隙部之產生，例如較佳為使用黏度小的塗佈組成物。另外，含有能量線聚合性化合物之塗佈組成物通常適於抑制前述空隙部之產生。 In order to suppress the generation of the aforementioned voids, it is preferable to use, for example, a coating composition with a low viscosity. In addition, the coating composition containing the energy ray polymerizable compound is generally suitable for suppressing the generation of the aforementioned voids.

於必須調節支持片的表面的表面粗糙度之情形時，利用公知的方法進行調節即可。例如，作為表面粗糙度之調節對象之層為藉由塗敷前述保護膜形成層用組成物、黏著劑組成物、塗佈組成物等組成物而形成之層之情形時，該層的表面粗糙度可藉由調節前述組成物之塗敷面的表面粗糙度而進行調節。 When it is necessary to adjust the surface roughness of the surface of the support sheet, it may be adjusted by a known method. For example, when the layer to be adjusted for the surface roughness is a layer formed by applying a composition such as the above-mentioned composition for forming a protective film, an adhesive composition, a coating composition, etc., the surface of the layer is rough. The degree can be adjusted by adjusting the surface roughness of the coated surface of the aforementioned composition.

另外，於作為表面粗糙度之調節對象之層於該層的表面含有藉由加熱而熔融之填充材料等熔融成分之情形時，藉由將該表面加熱，使前述熔融成分熔融，可降低表面 粗糙度。於作為表面粗糙度之調節對象之層於該層的表面不含前述熔融成分之情形時，藉由加熱使該層的整個表面平滑化，藉此亦可降低表面粗糙度。 In addition, when a layer to be adjusted for surface roughness contains a molten component such as a filler that is melted by heating on the surface of the layer, the surface can be reduced by heating the surface to melt the molten component. roughness. When the layer to be adjusted for surface roughness does not contain the aforementioned molten component on the surface of the layer, the surface roughness can also be reduced by smoothing the entire surface of the layer by heating.

另外，藉由於作為表面粗糙度之調節對象之層的表面如上所述般形成塗層，亦可降低表面粗糙度。 In addition, surface roughness can also be reduced by forming a coating layer on the surface of the layer to be adjusted for surface roughness as described above.

另一方面，針對作為表面粗糙度之調節對象之層，藉由噴砂加工等進行表面粗化處理，藉此亦可增大表面粗糙度。 On the other hand, it is also possible to increase the surface roughness by carrying out surface roughening treatment by sandblasting or the like for the layer to be adjusted for the surface roughness.

為了調節前述靜摩擦力(亦稱為靜摩擦係數)，而必須調節剝離膜中的與剝離處理面為相反側的表面的表面粗糙度之情形時以及上述支持片之情形同樣地，利用公知的方法進行調節即可。剝離膜的前述表面通常多數情況下平滑度高，因此例如於欲增大表面粗糙度之情形時，藉由噴砂加工等進行表面粗化處理即可。 When it is necessary to adjust the surface roughness of the surface on the opposite side to the release-treated surface in the release film in order to adjust the aforementioned static friction force (also referred to as the static friction coefficient), as in the case of the above-mentioned support sheet, it is performed by a known method. Adjust it. Since the said surface of a peeling film is usually high in smoothness in many cases, for example, when surface roughness is to be enlarged, surface roughening treatment by sandblasting or the like may be performed.

其中，通常，支持片的表面相較於剝離膜的前述表面而言，更容易調節表面粗糙度。因此，較佳為藉由調節支持片的表面的表面粗糙度，而調節前述靜摩擦力。 Among them, the surface of the support sheet is generally easier to adjust the surface roughness than the aforementioned surface of the release film. Therefore, it is preferable to adjust the aforementioned static frictional force by adjusting the surface roughness of the surface of the support sheet.

以下，作為本發明之保護膜形成用片中的一例的圖2所示之構成的保護膜形成用片的製造方法，參照圖9對具有前述積層步驟(P1')之製造方法進行說明。再者，此處所說明之製造方法為一例，於圖2所示之構成的保護膜形成用片的另一製造方法或另一保護膜形成用片的製造方法 具有與以下所說明之步驟相同或類似的步驟之情形時，此種步驟亦可與以下所說明之步驟同樣地進行。 Hereinafter, as an example of the sheet for forming a protective film of the present invention, a method for producing a sheet for forming a protective film having the structure shown in FIG. 2 will be described with reference to FIG. 9 . In addition, the manufacturing method demonstrated here is an example, and another manufacturing method of the sheet for protective film formation of the structure shown in FIG. 2, or the manufacturing method of another sheet for protective film formation In the case where the steps are the same as or similar to the steps described below, such steps may be performed in the same manner as the steps described below.

本方法中，將熱硬化性保護膜形成層用組成物或能量線硬化性保護膜形成層用組成物塗敷於剝離膜15的剝離處理面15b，如圖9中的(a)所示，形成保護膜形成層13。此時，以基材11的表面粗糙度為0.5μm以下之面(表面11b)以及剝離膜15中的與剝離處理面15b為相反側的面(表面15a)之間的靜摩擦力成為29N以下之方式，選擇剝離膜15。再者，此處，為了容易與保護膜形成用片1B進行比較，而表示以保護膜形成層13成為剝離膜15的下層之方式進行配置之示例，但這並不意味著塗敷保護膜形成組成物時剝離膜15中的剝離處理面15b的朝向限定於如圖9中的(a)所示之朝下，亦可為與該朝下相反的朝上，且較佳為朝上。 In this method, the composition for a thermosetting protective film-forming layer or the composition for an energy ray-curable protective film-forming layer is applied to the peeling-treated surface 15b of the peeling film 15, as shown in FIG. 9(a), The protective film forming layer 13 is formed. At this time, the static friction force between the surface (surface 11b ) of the base material 11 having a surface roughness of 0.5 μm or less and the surface (surface 15a ) of the release film 15 on the opposite side to the release-treated surface 15b is 29N or less. mode, the release film 15 is selected. In addition, here, in order to compare easily with the sheet 1B for protective film formation, the example in which the protective film forming layer 13 is arranged so that the lower layer of the peeling film 15 is shown is shown, but this does not mean that the protective film is formed by applying the protective film. The direction of the peeling-processed surface 15b in the peeling film 15 is limited to the downward direction as shown in FIG. 9(a) when the composition is formed, and may be the upward direction opposite to the downward direction, and is preferably upward.

另外，於所形成之保護膜形成層13中的與和剝離膜15接觸之側為相反側的表面(露出面)，亦可另行貼合剝離材料(省略圖示)。此處，所謂剝離材料，可列舉與後述之作為黏著劑組成物之塗敷對象之剝離材料相同的剝離材料。 In addition, a release material (illustration omitted) may be attached to the surface (exposed surface) opposite to the side in contact with the release film 15 in the formed protective film forming layer 13 . Here, as a peeling material, the same peeling material as the peeling material which is the object of application|coating of an adhesive composition mentioned later can be mentioned.

本方法中，繼而，將黏著劑組成物塗敷於剝離材料90的剝離處理面90b，如圖9中的(b)所示，形成黏著劑層12。此處，亦為了容易與保護膜形成用片1B進行比較，而表示以黏著劑層12成為剝離材料90的下層之方式進行配 置之示例，但這並不意味著塗敷黏著劑組成物時剝離材料90的剝離處理面90b的朝向限定於如圖9中的(b)所示之朝下，亦可為與該朝下相反的朝上，且較佳為朝上。 In this method, the adhesive composition is then applied to the peeling-processed surface 90b of the peeling material 90, and as shown in FIG. 9(b), the adhesive layer 12 is formed. Here, for the sake of easy comparison with the protective film-forming sheet 1B, it is shown that the adhesive layer 12 is prepared so that the adhesive layer 12 becomes the lower layer of the release material 90 . As an example, this does not mean that the direction of the peeled surface 90b of the peeling material 90 when the adhesive composition is applied is limited to the downward direction as shown in (b) in FIG. The opposite is upward, and preferably upward.

本方法中，繼而，如圖9中的(c)所示，於黏著劑層12中的與和剝離材料90接觸之側為相反側的表面(露出面)貼合基材11。此時，以基材11中的未貼合黏著劑層12之側的表面11b的表面粗糙度成為0.5μm以下之方式，選擇基材11中黏著劑層12的貼合面。 In this method, then, as shown in FIG. 9( c ), the base material 11 is bonded to the surface (exposed surface) opposite to the side in contact with the release material 90 in the adhesive layer 12 . At this time, the bonding surface of the adhesive layer 12 in the substrate 11 is selected so that the surface roughness of the surface 11b of the substrate 11 on the side where the adhesive layer 12 is not bonded becomes 0.5 μm or less.

藉由以上步驟，獲得支持片10。 Through the above steps, the support sheet 10 is obtained.

本方法中，繼而，如圖9中的(d)所示，藉由將支持片10中的黏著劑層12上所設置之剝離材料90移除而使黏著劑層12露出，將該黏著劑層12的露出面與保護膜形成層13的露出面貼合，藉此如圖9中的(e)所示，獲得保護膜形成用片1B。於保護膜形成層13中的與和剝離膜15接觸之側為相反側的表面(露出面)，另行貼合上述剝離材料之情形時，移除該剝離材料後，將保護膜形成層13的露出面與黏著劑層12的露出面貼合即可。 In this method, then, as shown in (d) of FIG. 9 , the adhesive layer 12 is exposed by removing the release material 90 provided on the adhesive layer 12 in the support sheet 10 , and the adhesive By bonding the exposed surface of the layer 12 and the exposed surface of the protective film forming layer 13, as shown in FIG. 9( e ), a protective film forming sheet 1B is obtained. In the case where the side of the protective film forming layer 13 that is in contact with the peeling film 15 is the opposite side (exposed surface), when the above-mentioned peeling material is separately attached, after removing the peeling material, the protective film forming layer 13 is removed. The exposed surface may be bonded to the exposed surface of the adhesive layer 12 .

其次，對本發明之保護膜形成用片中圖1所示之構成的保護膜形成用片的製造方法進行說明(省略圖示)。 Next, the manufacturing method of the sheet for protective film formation of the structure shown in FIG. 1 among the sheet for protective film formation of this invention is demonstrated (illustration abbreviate|omitted).

本方法中，可利用上述之保護膜形成用片1B的製造方法。 In this method, the manufacturing method of the sheet 1B for protective film formation mentioned above can be utilized.

首先，使用於用以形成治具用接著劑層16之接著帶的單面積層有剝離膜15之積層片，於接著帶的目標部位以成為目標形狀之方式形成切口。此處，所謂目標形狀，例如為以往下看之方式俯視該積層片的表面時成為圓形之形狀。 First, a single-area layered sheet of the adhesive tape for forming the adhesive layer 16 for a jig with the release film 15 is used to form an incision at a target portion of the adhesive tape to have a desired shape. Here, the target shape is, for example, a shape that is circular when the surface of the laminated sheet is viewed from below.

繼而，將該目標形狀(例如，前述俯視下為圓形)的接著帶自積層片移除，移除了該接著帶之區域中，成為前述剝離材料露出之狀態的加工完畢之積層片。亦即，於移除前述俯視下為圓形的接著帶之情形時，該加工完畢之積層片於目標部位中去除了圓形的接著帶。 Then, the adhesive tape of the target shape (for example, the above-mentioned circular shape in plan view) is removed from the laminate sheet, and the processed laminate sheet in the state where the release material is exposed in the region where the adhesive tape is removed is removed. That is, when the aforementioned circular adhesive tape is removed from a plan view, the processed laminated sheet has the circular adhesive tape removed from the target portion.

繼而，自上述所獲得之保護膜形成用片1B移除剝離膜15，將保護膜形成層13的露出面與該加工完畢之積層片的接著帶貼合，藉此獲得圖1所示之保護膜形成用片1A。本方法中，於使用捲取成輥狀之保護膜形成用片1B之情形時，作為前述加工完畢之積層片之貼合對象，亦可使用以下保護膜形成用片，該保護膜形成用片除具備有該剝離膜15以外的公知的剝離材料代替剝離膜15之方面以外以及保護膜形成用片1B的構成相同。 Then, the peeling film 15 was removed from the sheet 1B for forming a protective film obtained above, and the exposed surface of the protective film forming layer 13 was bonded to the adhesive tape of the processed laminated sheet, thereby obtaining the protection shown in FIG. 1 . Sheet 1A for film formation. In this method, in the case of using the protective film forming sheet 1B wound into a roll shape, the following protective film forming sheet may also be used as the lamination object of the above-mentioned processed laminated sheet. The configuration of the sheet 1B for forming a protective film is the same except that a known release material other than the release film 15 is provided in place of the release film 15 .

但是，上述製造方法為一例，保護膜形成用片1A的製造方法並不限定於此。 However, the above-mentioned manufacturing method is an example, and the manufacturing method of the sheet 1A for protective film formation is not limited to this.

<保護膜形成用片的使用方法> <How to use the sheet for forming a protective film>

本發明之保護膜形成用片的使用方法例如如以下所示。 The usage method of the sheet for protective film formation of this invention is as follows, for example.

首先，對保護膜形成層為熱硬化性之情形時保護膜形成用片的使用方法進行說明。 First, the usage method of the sheet for protective film formation when a protective film formation layer is thermosetting is demonstrated.

該情形時，首先，於保護膜形成用片的保護膜形成層貼附半導體晶圓的背面，並且將保護膜形成用片固定於切割裝置。 In this case, first, the back surface of the semiconductor wafer is attached to the protective film forming layer of the protective film forming sheet, and the protective film forming sheet is fixed to the dicing device.

繼而，藉由加熱使保護膜形成層硬化而成為保護膜。於半導體晶圓的表面(電極形成面)貼附有背面研磨帶之情形時，通常將該背面研磨帶自半導體晶圓移除後形成保護膜。 Next, the protective film-forming layer is cured by heating to form a protective film. When a back grinding tape is attached to the surface (electrode forming surface) of a semiconductor wafer, a protective film is usually formed after the back grinding tape is removed from the semiconductor wafer.

繼而，將半導體晶圓與保護膜一起切割而製成半導體晶片。形成保護膜起至進行切割之期間，可自保護膜形成用片的支持片側，對保護膜照射雷射光，而對保護膜的表面進行印字(雷射印字)。 Next, the semiconductor wafer is diced together with the protective film to obtain a semiconductor wafer. During the period from when the protective film is formed until the dicing, the protective film can be irradiated with laser light from the support sheet side of the protective film forming sheet to print (laser printing) on the surface of the protective film.

本發明之保護膜形成用片中，該保護膜形成用片的支持片中的與具備有保護膜形成層之側為相反側的表面(亦稱為支持片的背面)的表面粗糙度為0.5μm以下，前述表面(支持片的背面)為平滑面，或者成為凹凸度低的面。因此，對進行切割而獲得之半導體晶片，自該半導體晶片的背面(半導體晶片中的貼附有保護膜形成用片之面)側，藉由紅外線相機等進行觀察之情形時，可抑制紅外線於支持片的前述表面(背面)發生散射，因此可獲取清晰的檢測圖 像，從而可對上述半導體晶片良好地進行紅外線檢測。結果為，例如亦可容易地識別半導體晶片有無缺損或破裂等破損。 In the sheet for forming a protective film of the present invention, the surface roughness of the surface on the opposite side to the side provided with the protective film forming layer in the support sheet of the sheet for forming a protective film (also referred to as the back surface of the support sheet) is 0.5 μm or less, the surface (back surface of the support sheet) is a smooth surface or a surface with a low degree of unevenness. Therefore, when the semiconductor wafer obtained by dicing is observed by an infrared camera or the like from the back surface of the semiconductor wafer (the surface on which the protective film forming sheet is attached in the semiconductor wafer) side, infrared rays can be suppressed from being emitted into the semiconductor wafer. The aforementioned surface (back surface) of the support sheet is scattered, so a clear detection pattern can be obtained As a result, infrared detection of the above-mentioned semiconductor wafer can be performed favorably. As a result, for example, the presence or absence of damage such as chipping or cracking of the semiconductor wafer can be easily recognized.

繼而，自支持片，將半導體晶片與貼附於該半導體晶片的背面之切斷後的保護膜一起剝離而進行拾取，藉此獲得附保護膜之半導體晶片。例如，於支持片為由基材及黏著劑層積層而成之片，且前述黏著劑層為能量線硬化性之層之情形時，藉由照射能量線而使黏著劑層硬化，自該硬化後的黏著劑層，將半導體晶片與貼附於該半導體晶片的背面之保護膜一起拾取，藉此更容易獲得附保護膜之半導體晶片。 Next, the semiconductor wafer with the protective film attached to the back surface of the semiconductor wafer is peeled off from the support sheet and picked up together with the cut protective film attached to the back surface of the semiconductor wafer, thereby obtaining a protective film-attached semiconductor wafer. For example, when the support sheet is a sheet formed by laminating a base material and an adhesive, and the adhesive layer is an energy ray-curable layer, the adhesive layer is cured by irradiating the energy ray, and the adhesive layer is cured. After the adhesive layer, the semiconductor chip is picked up together with the protective film attached to the backside of the semiconductor chip, so that the semiconductor chip with the protective film can be more easily obtained.

以下，利用與以往方法相同的方法，將所獲得之附保護膜之半導體晶片的半導體晶片以倒裝晶片之方式連接於基板的電路面後，藉由樹脂將整體密封，藉此製成半導體封裝。然後，使用該半導體封裝，製作目標半導體裝置即可。 Next, by the same method as the conventional method, after the semiconductor chip of the obtained semiconductor chip with protective film is flip-chip connected to the circuit surface of the substrate, the whole is sealed with resin, thereby producing a semiconductor package . Then, using this semiconductor package, a target semiconductor device may be fabricated.

再者，上文對使保護膜形成層硬化而形成保護膜後進行切割之情形進行了說明，但亦可不使保護膜形成層硬化而進行切割，於該切割後使保護膜形成層硬化而形成保護膜。 In addition, the case where the protective film-forming layer is hardened to form the protective film and then diced has been described above, but the protective film-forming layer may be diced without hardening, and the protective film-forming layer may be hardened and formed after the dicing. protective film.

另外，上文對於對切割後的半導體晶片進行紅外線檢測之情形進行了說明，但亦可對貼附有保護膜形成用片之 狀態的進行切割之前的半導體晶圓，進行紅外線檢測。並且，該情形時之紅外線檢測可於使保護膜形成層硬化而形成保護膜之前及形成之後的任一階段進行。 In addition, the case where infrared detection is performed on the diced semiconductor wafer has been described above, but the sheet to which the protective film forming sheet is attached may be The state of the semiconductor wafer before dicing is carried out, and infrared detection is carried out. In addition, the infrared detection in this case can be performed at any stage before the protective film is formed by curing the protective film forming layer and after the formation.

其次，對保護膜形成層為能量線硬化性之情形時保護膜形成用片的使用方法進行說明。 Next, the usage method of the sheet for protective film formation in the case where the protective film forming layer is energy ray curable will be described.

該情形時，首先以及上述之保護膜形成層為熱硬化性之情形同樣地，於保護膜形成用片的保護膜形成層貼附半導體晶圓的背面，並且將保護膜形成用片固定於切割裝置。 In this case, firstly, similarly to the case where the above-mentioned protective film forming layer is thermosetting, the back surface of the semiconductor wafer is attached to the protective film forming layer of the protective film forming sheet, and the protective film forming sheet is fixed to the dicing device.

繼而，藉由照射能量線使保護膜形成層硬化而成為保護膜。於半導體晶圓的表面(電極形成面)貼附有背面研磨帶之情形時，通常將該背面研磨帶自半導體晶圓移除後，形成保護膜。 Then, the protective film-forming layer is cured by irradiating energy rays to form a protective film. When a back grinding tape is attached to the surface (electrode forming surface) of a semiconductor wafer, a protective film is usually formed after the back grinding tape is removed from the semiconductor wafer.

繼而，將半導體晶圓與保護膜一起切割而製成半導體晶片。形成保護膜起至進行切割之期間，可自保護膜形成用片的支持片側，對保護膜照射雷射光，而對保護膜的表面進行印字。並且，在此期間，可與上述之保護膜形成層為熱硬化性之情形同樣地，對進行切割之前的半導體晶圓或進行切割而獲得之半導體晶片，藉由紅外線相機等高精度地進行紅外線檢測。 Next, the semiconductor wafer is diced together with the protective film to obtain a semiconductor wafer. During the period from when the protective film is formed to when the dicing is performed, the protective film can be irradiated with laser light from the support sheet side of the protective film forming sheet, and the surface of the protective film can be printed. During this period, the semiconductor wafer before dicing or the semiconductor wafer obtained by dicing can be accurately subjected to infrared radiation by an infrared camera or the like, as in the case where the above-mentioned protective film forming layer is thermosetting. detection.

繼而，自支持片，將半導體晶片與貼附於該半導體晶 片的背面之切斷後的保護膜一起剝離而進行拾取，藉此獲得附保護膜之半導體晶片。 Then, the self-supporting sheet attaches the semiconductor chip to the semiconductor chip. The protective film after the cut|disconnection of the back surface of a sheet|seat is peeled together, and it picks up, and the semiconductor wafer with a protective film is obtained by this.

該方法例如於以下情形時尤佳：使用支持片由基材及黏著劑層積層而成，且前述黏著劑層為能量線硬化性以外之片作為保護膜形成用片。 This method is particularly preferable when, for example, a support sheet is used in which a base material and an adhesive are laminated, and the adhesive layer is a sheet other than energy ray curable as a protective film-forming sheet.

例如，於使用支持片由基材及黏著劑層積層而成，且前述黏著劑層為能量線硬化性之保護膜形成用片之情形時，較佳為以下說明之方法。 For example, in the case where a support sheet is formed by laminating a base material and an adhesive, and the adhesive layer is an energy ray-curable protective film-forming sheet, the method described below is preferably used.

亦即，首先以及上述情形同樣地，於保護膜形成用片的保護膜形成層貼附半導體晶圓的背面，並且將保護膜形成用片固定於切割裝置。 That is, first, similarly to the above-mentioned case, the back surface of the semiconductor wafer is adhered to the protective film forming layer of the sheet for forming a protective film, and the sheet for forming a protective film is fixed to a dicing device.

繼而，視需要，自保護膜形成用片的支持片側，對保護膜形成層照射雷射光，而對保護膜形成層的表面進行印字後，對半導體晶圓進行切割而製成半導體晶片。在此期間，可與上述之保護膜形成層為熱硬化性之情形同樣地，對進行切割之前的半導體晶圓或進行切割而獲得之半導體晶片，藉由紅外線相機等高精度地進行紅外線檢測。 Then, if necessary, the protective film forming layer is irradiated with laser light from the support sheet side of the protective film forming sheet to print on the surface of the protective film forming layer, and then the semiconductor wafer is diced to obtain a semiconductor wafer. During this period, the semiconductor wafer before dicing or the semiconductor wafer obtained by dicing can be subjected to infrared detection with high accuracy by an infrared camera or the like, as in the case where the above-mentioned protective film forming layer is thermosetting.

繼而，藉由照射能量線，使保護膜形成層硬化而成為保護膜，並且使黏著劑層硬化，自該硬化後的黏著劑層，將半導體晶片與貼附於該半導體晶片的背面之保護膜一起拾取，藉此獲得附保護膜之半導體晶片。保護膜形成層的表面所施加之印字於保護膜中亦維持相同狀態。 Then, by irradiating the energy ray, the protective film forming layer is hardened to become a protective film, and the adhesive layer is hardened, and the semiconductor chip and the protective film attached to the back surface of the semiconductor chip are attached from the hardened adhesive layer. Pick up together to obtain a semiconductor wafer with a protective film. The printing applied to the surface of the protective film-forming layer is also maintained in the same state in the protective film.

以下，利用與以往方法相同的方法，將所獲得之附保護膜之半導體晶片的半導體晶片以倒裝晶片之方式連接於基板的電路面後，藉由樹脂將整體密封，藉此製成半導體封裝。然後，使用該半導體封裝，製作目標半導體裝置即可。於保護膜形成層為能量線硬化性之情形時，該方法於任一情形均相同。 Next, by the same method as the conventional method, after the semiconductor chip of the obtained semiconductor chip with protective film is flip-chip connected to the circuit surface of the substrate, the whole is sealed with resin, thereby producing a semiconductor package . Then, using this semiconductor package, a target semiconductor device may be fabricated. When the protective film forming layer is energy ray curable, the method is the same in any case.

再者，對於此處所說明之方法以及上述之保護膜形成層為熱硬化性之情形同樣地，可施加變更。亦即，上文對使保護膜形成層硬化而形成保護膜後進行切割之情形進行了說明，但亦可不使保護膜形成層硬化而進行切割，於該切割後使保護膜形成層硬化而形成保護膜。 In addition, in the case where the method demonstrated here and the above-mentioned protective film forming layer are thermosetting similarly, a change can be added. That is, the case where the protective film-forming layer is hardened to form the protective film and then diced has been described above, but the protective film-forming layer may be diced without being hardened, and the protective film-forming layer may be hardened and formed after the dicing. protective film.

另外，上文對於對切割後的半導體晶片進行紅外線檢測之情形進行了說明，但亦可對貼附有保護膜形成用片之狀態的進行切割之前的半導體晶圓，進行紅外線檢測。並且，該情形時之紅外線檢測可於使保護膜形成層硬化而形成保護膜之前及形成之後的任一階段進行。 In addition, although the case where infrared detection is performed on the semiconductor wafer after dicing has been described above, infrared detection may also be performed on the semiconductor wafer before dicing in the state where the sheet for forming a protective film is attached. In addition, the infrared detection in this case can be performed at any stage before the protective film is formed by curing the protective film forming layer and after the formation.

另一方面，於捲取長條的保護膜形成用片之情形時，通常使用於保護膜形成層中的與具備有支持片之面為相反側的露出面上積層有剝離膜(例如，圖1至圖8中為剝離膜15)之狀態的保護膜形成用片。並且，本發明之保護膜形成用片無論為何種構成(例如為圖1至圖8所示之保護膜 形成用片之任一者)，隨著將保護膜形成用片捲取成輥狀，依序積層有支持片、保護膜形成層及剝離膜之積層單元均沿輥的徑向依次層疊。結果為，在輥的徑向上相互接觸之積層單元彼此之間，成為一積層單元的剝離膜的表面(剝離膜中的與設置有保護膜形成層之側為相反側的面)以及另一積層單元的支持片的表面(支持片中的與設置有保護膜形成層之面為相反側的面)接觸、擠壓之狀態，保護膜形成用片之輥直接以該狀態進行保存。但是，本發明之保護膜形成用片藉由如此接觸之剝離膜的前述表面與支持片的前述表面之間的靜摩擦力為29N以下，可抑制於積層單元彼此之間產生黏連，從而可自輥良好地捲出。 On the other hand, when winding up a long sheet for forming a protective film, a release film is usually laminated on the exposed surface of the protective film forming layer on the opposite side to the surface provided with the support sheet (for example, Fig. 1 to FIG. 8 are the protective film forming sheets in the state of the release film 15). In addition, the sheet for forming a protective film of the present invention has any structure (for example, the protective film shown in FIGS. 1 to 8 ) Any one of the sheet for forming), as the sheet for forming a protective film is wound into a roll shape, the lamination units in which the support sheet, the protective film forming layer and the release film are laminated in this order are sequentially laminated in the radial direction of the roll. As a result, the lamination units that are in contact with each other in the radial direction of the roll become the surface of the release film of one lamination unit (the surface on the opposite side to the side where the protective film forming layer is provided in the release film) and the other lamination unit. The surface of the support sheet of the unit (the surface on the opposite side of the support sheet on which the protective film forming layer is provided) is in contact and pressed, and the roll of the protective film forming sheet is stored in this state as it is. However, in the sheet for forming a protective film of the present invention, since the static frictional force between the surface of the release film and the surface of the support sheet in contact in this way is 29 N or less, the lamination units can be prevented from sticking to each other, and the self-contained The roll rolled out well.

[半導體裝置的製造方法] [Manufacturing method of semiconductor device]

如上所述，本發明之保護膜形成用片適於在製造半導體裝置時使用。亦即，作為使用本發明之保護膜形成用片之半導體裝置的製造方法的一實施形態，例如可列舉包含有以下步驟之半導體裝置的製造方法：自前述保護膜形成用片移除前述剝離膜後，將前述保護膜形成層貼附於半導體晶圓中的與設置有電路之面為相反側的背面之步驟；使貼附於前述半導體晶圓後的前述保護膜形成層硬化而形成保護膜之步驟；對形成有前述保護膜之半導體晶圓進行切割而形成半導體晶片之步驟；自前述保護膜形成用片的前述支持片側對前述半導體晶片照射紅外線，而對前述半導體晶片進行檢測之步驟；自前述支持片將前述半導體晶 片貼附於該半導體晶片的背面之保護膜一起剝離，藉此獲得附保護膜之半導體晶片之步驟；以及將前述附保護膜之半導體晶片的半導體晶片以倒裝晶片之方式連接於基板的電路面之步驟。 As described above, the sheet for forming a protective film of the present invention is suitable for use in the manufacture of semiconductor devices. That is, as one embodiment of the method for manufacturing a semiconductor device using the sheet for forming a protective film of the present invention, for example, a method for manufacturing a semiconductor device including the step of removing the peeling film from the sheet for forming a protective film can be exemplified. Then, the step of attaching the protective film forming layer to the back surface of the semiconductor wafer on the opposite side to the surface on which the circuit is arranged; curing the protective film forming layer attached to the semiconductor wafer to form a protective film the step of dicing the semiconductor wafer formed with the protective film to form a semiconductor chip; the step of irradiating the semiconductor chip with infrared rays from the support sheet side of the protective film forming sheet to detect the semiconductor chip; The above-mentioned semiconductor crystals are separated from the above-mentioned support sheet The protective film attached to the backside of the semiconductor chip is peeled off together to obtain a semiconductor chip with a protective film; and the semiconductor chip of the semiconductor chip with a protective film is flip-chip connected to the circuit of the substrate face steps.

作為本發明之一實施形態之保護膜形成用片之一態樣係以下保護膜形成用片，該保護膜形成用片係於本發明之支持片上具備有保護膜形成層，並於前述保護膜形成層上具備有剝離膜；前述支持片中的與具備有前述保護膜形成層之側為相反側的表面的表面粗糙度為0μm至0.5μm，較佳為0μm至0.45μm，更佳為0.01μm至0.4μm，進一步更佳為0.01μm至0.35μm，尤佳為0.03μm至0.3μm；前述支持片中的前述表面以及前述剝離膜中的與具備有前述保護膜形成層之側為相反側的表面之間，依據JIS K7125所測定之靜摩擦力為1N至29N，較佳為1N至25N，更佳為2N至20N，進一步更佳為2N至15N，尤佳為3N至13N，或者亦可為5N至12N，還可為5N至7N。 One aspect of the sheet for forming a protective film, which is an embodiment of the present invention, is a sheet for forming a protective film, which includes a protective film forming layer on the support sheet of the present invention, and which is formed on the protective film. A release film is provided on the forming layer; the surface roughness of the surface opposite to the side with the protective film forming layer in the support sheet is 0 μm to 0.5 μm, preferably 0 μm to 0.45 μm, more preferably 0.01 μm μm to 0.4 μm, more preferably 0.01 μm to 0.35 μm, still more preferably 0.03 μm to 0.3 μm; the surface of the support sheet and the release film are opposite to the side provided with the protective film forming layer Between the surfaces, the static friction force measured according to JIS K7125 is 1N to 29N, preferably 1N to 25N, more preferably 2N to 20N, still more preferably 2N to 15N, particularly preferably 3N to 13N, or 5N to 12N, and also 5N to 7N.

[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 with reference to specific examples. However, the present invention is not limited at all by the examples shown below.

以下表示製造保護膜形成層用組成物時所使用之原料。 The raw materials used in the production of the composition for protective film-forming layers are shown below.

[聚合物成分(A)] [Polymer component (A)]

(A)-1：使丙烯酸正丁酯10質量份、丙烯酸甲酯70質量份、甲基丙烯酸縮水甘油酯5質量份及丙烯酸2-羥基乙酯15質量份進行共聚合而成之丙烯酸系樹脂(重量平均分子量400000，玻璃轉移溫度-1℃)。 (A)-1: Acrylic resin obtained by copolymerizing 10 parts by mass of n-butyl acrylate, 70 parts by mass of methyl acrylate, 5 parts by mass of glycidyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight 400000, glass transition temperature -1°C).

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

‧環氧樹脂(B1) ‧Epoxy resin (B1)

(B1)-1：雙酚A型環氧樹脂(三菱化學公司製造之「JER828」，環氧當量183g/eq至194g/eq，數量平均分子量370)。 (B1)-1: Bisphenol A epoxy resin (“JER828” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 183 g/eq to 194 g/eq, number average molecular weight 370).

(B1)-2：雙酚A型環氧樹脂(三菱化學公司製造之「JER1055」，環氧當量800g/cq至900g/eq，數量平均分子量1600)。 (B1)-2: Bisphenol A epoxy resin (“JER1055” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 800 g/cq to 900 g/eq, number average molecular weight 1600).

(B1)-3：二環戊二烯型環氧樹脂(DIC公司製造之「Epiclon HP-7200HH」，環氧當量274g/eq至286g/eq)。 (B1)-3: Dicyclopentadiene-type epoxy resin (“Epiclon HP-7200HH” manufactured by DIC Corporation, epoxy equivalent: 274 g/eq to 286 g/eq).

‧熱硬化劑(B2) ‧Thermosetting agent (B2)

(B2)-1：二氰二胺(熱活性潛伏性環氧樹脂硬化劑，ADEKA公司製造之「Adeka Hardener EH-3636AS」，活性氫量21g/eq)。 (B2)-1: Dicyandiamide (heat-active latent epoxy resin hardener, "Adeka Hardener EH-3636AS" manufactured by ADEKA, active hydrogen amount 21 g/eq).

[硬化促進劑(C)] [Hardening accelerator (C)]

(C)-1：2-苯基-4,5-二羥基甲基咪唑(四國化成工業公司製造之「Curezol 2PHZ」)。 (C)-1: 2-phenyl-4,5-dihydroxymethylimidazole (“Curezol 2PHZ” manufactured by Shikoku Chemical Industry Co., Ltd.).

[填充材料(D)] [filler (D)]

(D)-1：二氧化矽填料(Admatechs公司之「SC2050MA 」，利用環氧系化合物進行了表面修飾，平均粒徑0.5μm)。 (D)-1: Silica filler (“SC2050MA of Admatechs” ”, surface-modified with epoxy compounds, with an average particle size of 0.5 μm).

[偶合劑(E)] [Coupling agent (E)]

(E)-1：3-縮水甘油氧基丙基三甲氧基矽烷(3-縮水甘油氧基丙基三甲氧基矽烷)(矽烷偶合劑，信越化學工業公司製造之「KBM403」)。 (E)-1: 3-glycidyloxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane) (silane coupling agent, "KBM403" manufactured by Shin-Etsu Chemical Co., Ltd.).

[著色劑(I)] [Colorant (I)]

(I)-1：碳黑(三菱化學公司製造之「MA600B」，平均粒徑28nm)。 (I)-1: Carbon black (“MA600B” manufactured by Mitsubishi Chemical Corporation, average particle size: 28 nm).

以下表示製造支持片時所使用之基材。 The substrates used in the manufacture of the support sheet are shown below.

基材(r1)：一表面為表面粗糙度(Ra)為0.1μm的平滑面，另一表面為表面粗糙度(Ra)為0.3μm的消光處理面之聚丙烯製基材(Gunze公司製造，厚度80μm)。 Substrate (r1): One surface is a smooth surface with a surface roughness (Ra) of 0.1 μm, and the other surface is a matte-treated surface with a surface roughness (Ra) of 0.3 μm. Polypropylene substrate (manufactured by Gunze Corporation, thickness 80 μm).

基材(r2)：雙面為表面粗糙度(Ra)為0.03μm的平滑面之聚氯乙烯製基材(Achilles公司製造，厚度80μm)。 Substrate (r2): A polyvinyl chloride substrate (manufactured by Achilles, 80 μm in thickness) having a smooth surface with a surface roughness (Ra) of 0.03 μm on both sides.

基材(r3)：一表面為表面粗糙度(Ra)為0.1μm的平滑面，另一表面為表面粗糙度(Ra)為0.6μm的消光處理面之乙烯-甲基丙烯酸共聚物製基材(Du Pont-Mitsui Polychemicals公司製造，厚度80μm)。 Substrate (r3): One surface is a smooth surface with a surface roughness (Ra) of 0.1 μm, and the other surface is a matte-treated surface with a surface roughness (Ra) of 0.6 μm. A substrate made of ethylene-methacrylic acid copolymer (manufactured by Du Pont-Mitsui Polychemicals, thickness 80 μm).

基材(r4)：一表面為表面粗糙度(Ra)為0.1μm的平滑面，另一表面為表面粗糙度(Ra)為1.0μm的消光處理面之聚丙烯製基材(三菱樹脂公司製造，厚度80μm)。 Substrate (r4): One surface is a smooth surface with a surface roughness (Ra) of 0.1 μm, and the other surface is a matte-treated surface with a surface roughness (Ra) of 1.0 μm. Polypropylene substrate (manufactured by Mitsubishi Plastics Corporation) , thickness 80 μm).

以下表示製造保護膜形成用片時各步驟中所使用之剝離膜。 The release film used in each step at the time of manufacturing the sheet for protective film formation is shown below.

剝離膜(s1)：一表面為經剝離處理，另一表面為未經剝離處理的平滑面之聚對苯二甲酸乙二酯製剝離膜(Lintec公司製造之「SP-PET382150」，厚度38μm)。 Release film (s1): a release film made of polyethylene terephthalate (“SP-PET382150” manufactured by Lintec Co., Ltd., thickness 38 μm) with one surface treated for release and the other surface being a smooth surface without release treatment. .

剝離膜(s2)：一表面為經剝離處理，另一表面為未經剝離處理的平滑面之聚對苯二甲酸乙二酯製剝離膜(Lintec公司製造之「SP-PET381130」，厚度38μm)。 Release film (s2): a release film made of polyethylene terephthalate with one surface subjected to release treatment and the other surface being a smooth surface without release treatment (“SP-PET381130” manufactured by Lintec, thickness 38 μm) .

剝離膜(s3)：一表面為經剝離處理，另一表面為未經剝離處理的消光處理面之聚對苯二甲酸乙二酯製剝離膜(Lintec公司製造之「SP-PMF381031H」，厚度38μm)。 Release film (s3): a release film made of polyethylene terephthalate (“SP-PMF381031H” manufactured by Lintec Corporation, thickness 38 μm) with one surface subjected to release treatment and the other surface with matte treatment surface without release treatment ).

再者，前述基材的表面粗糙度(Ra)、及前述基材與前述剝離膜之間的靜摩擦力分別利用以下之方法進行測定。 In addition, the surface roughness (Ra) of the said base material and the static frictional force between the said base material and the said release film were measured by the following methods, respectively.

(表面粗糙度之測定) (Measurement of Surface Roughness)

前述基材的表面粗糙度(Ra)係依據JIS B 0601：2001，使用接觸式表面形狀測定裝置(Mitsutoyo公司製造之「SURFTESTSV-3000」)，將臨界值λ c設為0.8μm，將評價長度Ln設為10mm，進行測定。 The surface roughness (Ra) of the aforementioned base material is based on JIS B 0601:2001, using a contact-type surface profile measuring device (“SURFTEST SV-3000” manufactured by Mitsutoyo Corporation), the critical value λ c is set to 0.8 μm, and the evaluation length is Ln was measured at 10 mm.

結果示於表1。 The results are shown in Table 1.

(靜摩擦力之測定) (Measurement of Static Friction)

使用萬能材料試驗機(A&D公司製造之「RTG-1225」) ，依據JIS K7125，利用下述方法測定前述靜摩擦力。 Use a universal material testing machine ("RTG-1225" manufactured by A&D Corporation) , according to JIS K7125, using the following method to measure the aforementioned static friction force.

亦即，將前述剝離膜切成10cm×20cm之大小，將前述基材切成6cm×10cm之大小，分別製成試片。 That is, the peeling film was cut into a size of 10 cm×20 cm, and the base material was cut into a size of 6 cm×10 cm to prepare test pieces, respectively.

使用帶將剝離膜試片固定於平板狀的靜摩擦力測定用治具。此時，以使剝離膜試片的剝離處理面朝向前述治具的固定面側，且於剝離膜試片不產生褶皺之方式進行固定。然後，將該狀態之前述治具設置於前述萬能材料試驗機。 The release film test piece was fixed to a flat static friction force measurement jig using a tape. At this time, it fixed so that the peeling process surface of a peeling film test piece may face the fixing surface side of the said jig, and a wrinkle may not generate|occur|produce in a peeling film test piece. Then, the above-mentioned jig in this state is installed in the above-mentioned universal material testing machine.

將基材試片固定於大小為6cm×10cm×2cm且重量為1kg之金屬錘的6cm×10cm之面。此時，於基材試片中的與靜摩擦力之測定對象面為相反側的面貼附雙面帶，經由該雙面帶，將基材試片固定於前述金屬錘。 The base material test piece was fixed on the surface of 6 cm×10 cm of a metal hammer with a size of 6 cm×10 cm×2 cm and a weight of 1 kg. At this time, a double-sided tape was attached to the surface of the base material test piece on the opposite side to the surface to be measured for the static friction force, and the base material test piece was fixed to the metal hammer via the double-sided tape.

繼而，以基材試片中的靜摩擦力之測定對象面直接接觸於已固定的剝離膜試片中的靜摩擦力之測定對象面(與剝離處理面為相反側的面)，將已固定的基材試片載置於金屬錘，依序積層剝離膜試片、基材試片及金屬錘。然後，沿著水平方向，亦即剝離膜試片中的相對於靜摩擦力之測定對象面平行的方向，使金屬錘以10mm/分鐘之速度移動，測定此時金屬錘即將開始移動前的荷重(PEAK試驗力)，設為靜摩擦力。 Next, the fixed base material was placed in direct contact with the fixed surface of the test piece for static friction measurement (the surface on the opposite side to the peel-treated surface) of the static friction force in the base material test piece. The material test piece is placed on the metal hammer, and the release film test piece, the base material test piece and the metal hammer are sequentially laminated. Then, move the metal hammer at a speed of 10 mm/min along the horizontal direction, that is, the direction parallel to the measurement object surface of the static friction force in the peel-off film test piece, and measure the load immediately before the metal hammer starts to move ( PEAK test force), set as static friction force.

結果示於表1。 The results are shown in Table 1.

[實施例1] [Example 1]

<保護膜形成用片之製造> <Manufacture of sheet for forming protective film>

(熱硬化性保護膜形成層用組成物之製造) (Manufacture of composition for thermosetting protective film forming layer)

如表1所示，將聚合物成分(A)-1(150質量份)、環氧樹脂(B1)-1(60質量份)、環氧樹脂(B1)-2(10質量份)、環氧樹脂(B1)-3(30質量份)、熱硬化劑(B2)-1(2質量份)、硬化促進劑(C)-1(2質量份)、填充材料(D)-1(320質量份)、偶合劑(E)-1(2質量份)、及著色劑(I)-1(1.2質量份)進行混合，進一步混合甲基乙基酮，於23℃下攪拌60分鐘，藉此獲得固形物成分的含量為53.0質量%之保護膜形成層用組成物(III-1)。再者，此處表1所示之甲基乙基酮以外的成分的調配量全部為固形物成分量。 As shown in Table 1, a polymer component (A)-1 (150 parts by mass), an epoxy resin (B1)-1 (60 parts by mass), an epoxy resin (B1)-2 (10 parts by mass), a ring Oxygen resin (B1)-3 (30 parts by mass), thermosetting agent (B2)-1 (2 parts by mass), hardening accelerator (C)-1 (2 parts by mass), filler (D)-1 (320 parts by mass), coupling agent (E)-1 (2 parts by mass), and coloring agent (I)-1 (1.2 parts by mass) were mixed, methyl ethyl ketone was further mixed, and the mixture was stirred at 23° C. for 60 minutes. This obtained the composition (III-1) for protective film forming layers whose content of solid content is 53.0 mass %. In addition, the compounding quantity of the components other than methyl ethyl ketone shown in Table 1 here is all solid content amount.

(保護膜形成層之形成) (Formation of protective film forming layer)

於剝離膜(s1)的剝離處理面上，藉由刀式塗佈機，塗敷上述所獲得之保護膜形成層用組成物(III-1)，於110℃下乾燥2分鐘，藉此形成厚度為25μm之保護膜形成層。進一步，於該保護膜形成層中的與設置有剝離膜(s1)之側為相反側的露出面，貼合剝離膜(s2)的剝離處理面。 The above-obtained protective film-forming layer composition (III-1) was applied on the peeling-treated surface of the peeling film (s1) by a knife coater, and dried at 110° C. for 2 minutes, thereby forming A protective film-forming layer with a thickness of 25 μm is formed. Furthermore, the peeling process surface of the peeling film (s2) is bonded to the exposed surface on the opposite side to the side where the peeling film (s1) is provided in the protective film forming layer.

(黏著劑組成物之製造) (Manufacture of adhesive composition)

將(甲基)丙烯酸烷基酯共聚物(重量平均分子量400000，玻璃轉移溫度-1℃)(100質量份)、及三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」)(5質量份)進行混合，進一步混合甲基乙基酮，於23℃下攪拌30分鐘，藉此獲得固形物成分的含量 為30.0質量%之黏著劑組成物(iii)。此處，前述(甲基)丙烯酸烷基酯共聚物係使甲基丙烯酸甲酯(30質量份)、丙烯酸2-乙基己酯(60質量份)及丙烯酸2-羥基乙酯(10質量份)進行共聚合而成。再者，此處所示之甲基乙基酮以外的成分的調配量全部為固形物成分量。 Alkyl (meth)acrylate copolymer (weight average molecular weight 400,000, glass transition temperature -1°C) (100 parts by mass), and trifunctional xylylene diisocyanate-based crosslinking agent (manufactured by Mitsui Takeda Chemical Co., Ltd. "Takenate D110N") (5 parts by mass) was mixed, methyl ethyl ketone was further mixed, and the solid content was obtained by stirring at 23° C. for 30 minutes. It is 30.0 mass % of adhesive composition (iii). Here, the alkyl (meth)acrylate copolymer is made of methyl methacrylate (30 parts by mass), 2-ethylhexyl acrylate (60 parts by mass), and 2-hydroxyethyl acrylate (10 parts by mass) ) are copolymerized. In addition, the compounding quantities of the components other than methyl ethyl ketone shown here are all solid content amounts.

(黏著劑層之形成、支持片之製造) (formation of adhesive layer, manufacture of support sheet)

於剝離膜(s1)的剝離處理面上，藉由刀式塗佈機，塗敷上述所獲得之黏著劑組成物(iii)，於110℃下乾燥2分鐘，藉此形成厚度為10μm之黏著劑層。 On the peeling-treated surface of the peeling film (s1), the adhesive composition (iii) obtained above was applied by a knife coater, and dried at 110° C. for 2 minutes to form an adhesive with a thickness of 10 μm. agent layer.

繼而，於該黏著劑層中的與設置有剝離膜(s1)之側為相反側的露出面，貼合基材(r1)的平滑面，獲得支持片。 Next, the smooth surface of the base material (r1) is bonded to the exposed surface on the opposite side to the side on which the release film (s1) is provided in the adhesive layer to obtain a support sheet.

(保護膜形成用片之製造) (Manufacture of protective film forming sheet)

自上述所獲得之保護膜形成層的一表面移除剝離膜(s2)，且移除支持片中的黏著劑層上所設置之剝離膜(s1)，將保護膜形成層的露出面以及黏著劑層的露出面進行層壓，藉此獲得圖2所示之構成的保護膜形成用片，該保護膜形成用片由基材(r1)、前述黏著劑層、前述保護膜形成層及剝離膜(s1)依序積層而成，且支持片中的與設置有前述黏著劑層之側為相反側的表面(露出面)為基材(r1)的消光處理面，剝離膜中的與設置有保護膜形成層之側為相反側的表面(露出面)為平滑面。 The peeling film (s2) is removed from one surface of the protective film-forming layer obtained above, and the peeling film (s1) provided on the adhesive layer in the support sheet is removed, and the exposed surface of the protective film-forming layer and the adhesive layer are removed. The exposed surface of the agent layer was laminated to obtain a protective film-forming sheet having the configuration shown in FIG. The film (s1) is laminated in sequence, and the surface (exposed surface) on the opposite side to the side where the aforementioned adhesive layer is provided in the support sheet is the matte-treated surface of the substrate (r1), and the surface (exposed surface) of the support sheet is the matte treated surface of the substrate (r1). The surface (exposed surface) on the opposite side on the side with the protective film forming layer is a smooth surface.

<保護膜形成用片之評價> <Evaluation of the sheet for forming a protective film>

(自輥之捲出性) (roll-out from the roll)

將上述所獲得之寬度0.4m、長度100m之長條的保護膜形成用片捲取成輥。製作10個此種輥，將這些輥於23℃下保存30天後，嘗試捲出保護膜形成用片。並且，將保護膜形成用片於全部輥中無問題地捲出之情形判定為A，存在1個或2個無法在使用上無問題之範圍內將保護膜形成用片順利地捲出之輥之情形判定為B，於全部輥中因產生黏連而無法將保護膜形成用片捲出，或者將保護膜形成用片捲出時確認到剝離膜剝離等某些異常之情形判定為C。結果示於表1。 The above-obtained long sheet for forming a protective film having a width of 0.4 m and a length of 100 m was wound up into a roll. Ten such rolls were produced, and after storing these rolls at 23° C. for 30 days, an attempt was made to roll out the sheet for forming a protective film. In addition, the case where the sheet for forming a protective film was unwound from all the rolls without a problem was determined as A, and there were one or two rolls in which the sheet for forming a protective film could not be unwound smoothly within the range where there was no problem in use. The case was judged as B, and the case where the sheet for forming a protective film could not be unwound due to blocking occurred in all the rolls, or when some abnormality such as peeling of the release film was observed when the sheet for forming a protective film was unwound was judged as C. The results are shown in Table 1.

(紅外線檢測性) (infrared detection)

自上述所獲得之保護膜形成用片移除剝離膜(s1)，使用貼帶機(tape mounter)(Lintec公司製造之「Adwill RAD-2700」)，將保護膜形成用片中的保護膜形成層一面加熱至70℃一面貼附於矽晶圓(直徑200mm，厚度350μm)的#2000研磨面。進一步，將保護膜形成層於130℃下加熱2小時使之硬化而形成保護膜。藉由以上步驟，獲得由支持片(基材及黏著劑層之積層片)、保護膜及矽晶圓依序積層而成之積層體。 The release film (s1) was removed from the sheet for forming a protective film obtained above, and a tape mounter (“Adwill RAD-2700” manufactured by Lintec) was used to form a protective film in the sheet for forming a protective film. The layer was heated to 70°C and attached to the #2000 polished surface of a silicon wafer (diameter 200mm, thickness 350μm). Furthermore, the protective film-forming layer was heated and cured at 130° C. for 2 hours to form a protective film. Through the above steps, a laminate is obtained in which a support sheet (a laminate of a substrate and an adhesive layer), a protective film and a silicon wafer are sequentially laminated.

繼而，使用紅外線顯微鏡(Olympus公司製造之「BX-51」)，自所獲得之積層體的支持片側觀察該積層體，經由支持片及保護膜可視認到矽晶圓的前述研磨面中的研削 痕跡之情形判定為A，未視認到之情形判定為B。結果示於表1。 Next, using an infrared microscope (“BX-51” manufactured by Olympus), the obtained laminate was observed from the support sheet side of the obtained laminated body, and the grinding on the above-mentioned polished surface of the silicon wafer was recognized through the support sheet and the protective film. The case of the trace was judged as A, and the case of unrecognized was judged as B. The results are shown in Table 1.

再者，表1中記載為「-」時意指該項目未測定或未評價。 In addition, when it describes as "-" in Table 1, it means that this item was not measured or not evaluated.

[實施例2] [Example 2]

<保護膜形成用片之製造> <Manufacture of sheet for forming protective film>

(熱硬化性保護膜形成層用組成物之製造、黏著劑組成物之製造) (Manufacture of composition for thermosetting protective film forming layer, manufacture of adhesive composition)

利用與實施例1相同的方法，製造保護膜形成層用組成物(III-1)及黏著劑組成物(iii)。 By the same method as Example 1, the composition (III-1) for protective film forming layers and the adhesive composition (iii) were produced.

(保護膜形成層之形成) (Formation of protective film forming layer)

於剝離膜(s3)的剝離處理面上，藉由刀式塗佈機，塗敷上述所獲得之保護膜形成層用組成物(III-1)，於110℃下乾燥2分鐘，藉此形成厚度為25μm之保護膜形成層。進一步，於該保護膜形成層中的與設置有剝離膜(s3)之側為相反側的露出面，貼合剝離膜(s2)的剝離處理面。 The protective film-forming layer composition (III-1) obtained above was applied on the peeling-treated surface of the peeling film (s3) by a knife coater, and dried at 110° C. for 2 minutes, thereby forming A protective film-forming layer with a thickness of 25 μm is formed. Furthermore, the peeling process surface of the peeling film (s2) is bonded to the exposed surface on the opposite side to the side where the peeling film (s3) is provided in the protective film forming layer.

(黏著劑層之形成、支持片之製造) (formation of adhesive layer, manufacture of support sheet)

於剝離膜(s1)的剝離處理面上，藉由刀式塗佈機，塗敷上述所獲得之黏著劑組成物(iii)，於110℃下乾燥2分鐘，藉此形成厚度為10μm之黏著劑層。 On the peeling-treated surface of the peeling film (s1), the adhesive composition (iii) obtained above was applied by a knife coater, and dried at 110° C. for 2 minutes to form an adhesive with a thickness of 10 μm. agent layer.

繼而，於該黏著劑層中的與設置有剝離膜(s1)之側為相反側的露出面，貼合基材(r2)的一平滑面，獲得支持片。 Next, the exposed surface on the opposite side to the side where the release film (s1) is provided in the adhesive layer is bonded to a smooth surface of the base material (r2) to obtain a support sheet.

(保護膜形成用片之製造) (Manufacture of protective film forming sheet)

自上述所獲得之保護膜形成層的一表面移除剝離膜(s2)，且移除支持片中的黏著劑層上所設置之剝離膜(s1)，將保護膜形成層的露出面以及黏著劑層的露出面進行層壓，藉此獲得保護膜形成用片，該保護膜形成用片由基材(r2)、前述黏著劑層、前述保護膜形成層及剝離膜(s3)依序積層而成，且支持片中的與設置有前述黏著劑層之側為相反側的表面(露出面)為基材(r2)的另一平滑面，剝離膜中的與設置有保護膜形成層之側為相反側的表面(露出面)為消光處理面。 The peeling film (s2) is removed from one surface of the protective film-forming layer obtained above, and the peeling film (s1) provided on the adhesive layer in the support sheet is removed, and the exposed surface of the protective film-forming layer and the adhesive layer are removed. The exposed surface of the agent layer is laminated to obtain a sheet for forming a protective film, the sheet for forming a protective film comprising the substrate (r2), the adhesive layer, the protective film forming layer and the release film (s3) laminated in this order form, and the surface (exposed surface) on the opposite side to the side provided with the aforementioned adhesive layer in the support sheet is another smooth surface of the base material (r2), and the surface (exposed surface) of the support sheet and the side provided with the protective film forming layer is another smooth surface of the base material (r2). The surface (exposed surface) whose side is the opposite side is a matte processing surface.

<保護膜形成用片之評價> <Evaluation of the sheet for forming a protective film>

針對上述所獲得之保護膜形成用片，利用與實施例1相同的方法進行評價。結果示於表1。 About the sheet for protective film formation obtained above, it evaluated by the method similar to Example 1. The results are shown in Table 1.

[實施例3] [Example 3]

<保護膜形成用片之製造> <Manufacture of sheet for forming protective film>

(熱硬化性保護膜形成層用組成物之製造、黏著劑組成物之製造) (Manufacture of composition for thermosetting protective film forming layer, manufacture of adhesive composition)

利用與實施例1相同的方法，製造保護膜形成層用組 成物(III-1)及黏著劑組成物(iii)。 By the same method as in Example 1, a group for protective film forming layers was produced The finished product (III-1) and the adhesive composition (iii).

(保護膜形成層之形成) (Formation of protective film forming layer)

於剝離膜(s3)的剝離處理面上，藉由刀式塗佈機，塗敷上述所獲得之保護膜形成層用組成物(III-1)，於110℃下乾燥2分鐘，藉此形成厚度為25μm之保護膜形成層。進一步，於該保護膜形成層中的與設置有剝離膜(s3)之側為相反側的露出面，貼合剝離膜(s2)的剝離處理面。 The protective film-forming layer composition (III-1) obtained above was applied on the peeling-treated surface of the peeling film (s3) by a knife coater, and dried at 110° C. for 2 minutes, thereby forming A protective film-forming layer with a thickness of 25 μm is formed. Furthermore, the peeling process surface of the peeling film (s2) is bonded to the exposed surface on the opposite side to the side where the peeling film (s3) is provided in the protective film forming layer.

(黏著劑層之形成、支持片之製造) (formation of adhesive layer, manufacture of support sheet)

於剝離膜(s1)的剝離處理面上，藉由刀式塗佈機，塗敷上述所獲得之黏著劑組成物(iii)，於110℃下乾燥2分鐘，藉此形成厚度為10μm之黏著劑層。 On the peeling-treated surface of the peeling film (s1), the adhesive composition (iii) obtained above was applied by a knife coater, and dried at 110° C. for 2 minutes to form an adhesive with a thickness of 10 μm. agent layer.

繼而，於該黏著劑層中的與設置有剝離膜(s1)之側為相反側的露出面，貼合基材(r3)的消光處理面，獲得支持片。 Next, the matte processing surface of the base material (r3) is bonded to the exposed surface on the opposite side to the side where the release film (s1) is provided in the adhesive layer to obtain a support sheet.

(保護膜形成用片之製造) (Manufacture of protective film forming sheet)

自上述所獲得之保護膜形成層的一表面移除剝離膜(s2)，且移除支持片中的黏著劑層上所設置之剝離膜(s1)，將保護膜形成層的露出面以及黏著劑層的露出面進行層壓，藉此獲得保護膜形成用片，該保護膜形成用片由基材(r3)、前述黏著劑層、前述保護膜形成層及剝離膜(s3)依序積層而成，且支持片中的與設置有前述黏著劑層之側為相 反側的表面(露出面)為基材(r3)的平滑面，剝離膜中的與設置有保護膜形成層之側為相反側的表面(露出面)為消光處理面。 The peeling film (s2) is removed from one surface of the protective film-forming layer obtained above, and the peeling film (s1) provided on the adhesive layer in the support sheet is removed, and the exposed surface of the protective film-forming layer and the adhesive layer are removed. The exposed surface of the agent layer is laminated to obtain a sheet for forming a protective film, the sheet for forming a protective film comprising the substrate (r3), the adhesive layer, the protective film forming layer, and the release film (s3) laminated in this order formed, and the side in the support sheet is in phase with the side provided with the aforementioned adhesive layer. The surface (exposed surface) on the opposite side is the smooth surface of the base material (r3), and the surface (exposed surface) on the opposite side to the side where the protective film forming layer is provided in the release film is the matte treated surface.

<保護膜形成用片之評價> <Evaluation of the sheet for forming a protective film>

針對上述所獲得之保護膜形成用片，利用與實施例1相同的方法進行評價。結果示於表1。 About the sheet for protective film formation obtained above, it evaluated by the method similar to Example 1. The results are shown in Table 1.

[實施例4] [Example 4]

<保護膜形成用片之製造> <Manufacture of sheet for forming protective film>

(熱硬化性保護膜形成層用組成物之製造、保護膜形成層之形成、黏著劑組成物之製造) (Production of composition for thermosetting protective film-forming layer, formation of protective film-forming layer, production of adhesive composition)

利用與實施例1相同的方法，製造保護膜形成層用組成物(III-1)，獲得於一表面具備有剝離膜(s1)，於另一表面具備有剝離膜(s2)之保護膜形成層。 By the same method as Example 1, the composition (III-1) for protective film forming layers was produced, and the protective film formation provided with the peeling film (s1) on one surface and the peeling film (s2) on the other surface was obtained. layer.

另外，利用與實施例1相同的方法，製造黏著劑組成物(iii)。 Moreover, by the same method as Example 1, the adhesive composition (iii) was produced.

(黏著劑層之形成、支持片之製造) (formation of adhesive layer, manufacture of support sheet)

利用與實施例1相同的方法，於剝離膜(s1)的剝離處理面上，形成厚度為10μm之黏著劑層。 By the same method as Example 1, the adhesive bond layer with a thickness of 10 micrometers was formed on the peeling process surface of the peeling film (s1).

繼而，於該黏著劑層中的與設置有剝離膜(s1)之側為相反側的露出面，貼合基材(r4)的消光處理面，獲得支持片。 Next, the matte processing surface of the base material (r4) was bonded to the exposed surface on the opposite side to the side where the release film (s1) was provided in the adhesive layer to obtain a support sheet.

(保護膜形成用片之製造) (Manufacture of protective film forming sheet)

自上述所獲得之保護膜形成層的一表面移除剝離膜(s2)，且移除支持片中的黏著劑層上所設置之剝離膜(s1)，將保護膜形成層的露出面以及黏著劑層的露出面進行層壓，藉此獲得保護膜形成用片，該保護膜形成用片由基材(r4)、前述黏著劑層、前述保護膜形成層及剝離膜(s1)依序積層而成，且支持片中的與設置有前述黏著劑層之側為相反側的表面(露出面)為基材(r4)的平滑面，剝離膜中的與設置有保護膜形成層之側為相反側的表面(露出面)為平滑面。 The peeling film (s2) is removed from one surface of the protective film-forming layer obtained above, and the peeling film (s1) provided on the adhesive layer in the support sheet is removed, and the exposed surface of the protective film-forming layer and the adhesive layer are removed. The exposed surface of the agent layer is laminated to obtain a sheet for forming a protective film, the sheet for forming a protective film comprising the substrate (r4), the adhesive layer, the protective film forming layer, and the release film (s1) laminated in this order form, and the surface (exposed surface) opposite to the side provided with the aforementioned adhesive layer in the support sheet is the smooth surface of the substrate (r4), and the side provided with the protective film forming layer in the release film is The surface on the opposite side (exposed surface) is a smooth surface.

<保護膜形成用片之評價> <Evaluation of the sheet for forming a protective film>

針對上述所獲得之保護膜形成用片，利用與實施例1相同的方法進行評價。結果示於表1。 About the sheet for protective film formation obtained above, it evaluated by the method similar to Example 1. The results are shown in Table 1.

[比較例1] [Comparative Example 1]

<保護膜形成用片之製造> <Manufacture of sheet for forming protective film>

(熱硬化性保護膜形成層用組成物之製造、保護膜形成層之形成、黏著劑組成物之製造) (Production of composition for thermosetting protective film-forming layer, formation of protective film-forming layer, production of adhesive composition)

利用與實施例1相同的方法，製造保護膜形成層用組成物(III-1)，獲得於一表面具備有剝離膜(s1)，於另一表面具備有剝離膜(s2)之保護膜形成層。 By the same method as Example 1, the composition (III-1) for protective film forming layers was produced, and the protective film formation provided with the peeling film (s1) on one surface and the peeling film (s2) on the other surface was obtained. layer.

另外，利用與實施例1相同的方法，製造黏著劑組成 物(iii)。 In addition, by the same method as Example 1, an adhesive composition was produced item (iii).

(黏著劑層之形成、支持片之製造) (formation of adhesive layer, manufacture of support sheet)

利用與實施例1相同的方法，於剝離膜(s1)的剝離處理面上，形成厚度為10μm之黏著劑層。 By the same method as Example 1, the adhesive bond layer with a thickness of 10 micrometers was formed on the peeling process surface of the peeling film (s1).

繼而，於該黏著劑層中的與設置有剝離膜(s1)之側為相反側的露出面，貼合基材(r4)的平滑面，獲得支持片。 Next, the smooth surface of the base material (r4) is bonded to the exposed surface on the opposite side to the side on which the release film (s1) is provided in the adhesive layer to obtain a support sheet.

(保護膜形成用片之製造) (Manufacture of protective film forming sheet)

自上述所獲得之保護膜形成層的一表面移除剝離膜(s2)，且移除支持片中的黏著劑層上所設置之剝離膜(s1)，將保護膜形成層的露出面以及黏著劑層的露出面進行層壓，藉此獲得保護膜形成用片，該保護膜形成用片由基材(r4)、前述黏著劑層、前述保護膜形成層及剝離膜(s1)依序積層而成，且支持片中的與設置有前述黏著劑層之側為相反側的表面(露出面)為基材(r4)的消光處理面，剝離膜中的與設置有保護膜形成層之側為相反側的表面(露出面)為平滑面。 The peeling film (s2) is removed from one surface of the protective film-forming layer obtained above, and the peeling film (s1) provided on the adhesive layer in the support sheet is removed, and the exposed surface of the protective film-forming layer and the adhesive layer are removed. The exposed surface of the agent layer is laminated to obtain a sheet for forming a protective film, the sheet for forming a protective film comprising the substrate (r4), the adhesive layer, the protective film forming layer, and the release film (s1) laminated in this order Formed, and the surface (exposed surface) opposite to the side provided with the aforementioned adhesive layer in the support sheet is the matte processing surface of the substrate (r4), and the side provided with the protective film forming layer in the release film The surface on the opposite side (exposed surface) is a smooth surface.

<保護膜形成用片之評價> <Evaluation of the sheet for forming a protective film>

針對上述所獲得之保護膜形成用片，利用與實施例1相同的方法進行評價。結果示於表1。 About the sheet for protective film formation obtained above, it evaluated by the method similar to Example 1. The results are shown in Table 1.

[比較例2] [Comparative Example 2]

<保護膜形成用片之製造> <Manufacture of sheet for forming protective film>

(熱硬化性保護膜形成層用組成物之製造、保護膜形成層之形成、黏著劑組成物之製造) (Production of composition for thermosetting protective film-forming layer, formation of protective film-forming layer, production of adhesive composition)

利用與實施例1相同的方法，製造保護膜形成層用組成物(III-1)，獲得於一表面具備有剝離膜(s1)，於另一表面具備有剝離膜(s2)之保護膜形成層。 By the same method as Example 1, the composition (III-1) for protective film forming layers was produced, and the protective film formation provided with the peeling film (s1) on one surface and the peeling film (s2) on the other surface was obtained. layer.

另外，利用與實施例1相同的方法，製造黏著劑組成物(iii)。 Moreover, by the same method as Example 1, the adhesive composition (iii) was produced.

(黏著劑層之形成) (formation of adhesive layer)

利用與實施例1相同的方法，於剝離膜(s1)的剝離處理面上，形成厚度為10μm之黏著劑層。 By the same method as Example 1, the adhesive bond layer with a thickness of 10 micrometers was formed on the peeling process surface of the peeling film (s1).

(塗佈組成物之製造) (Manufacture of coating composition)

將(甲基)丙烯酸烷基酯共聚物(重量平均分子量400000，玻璃轉移溫度-1℃)(100質量份)、及三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」)(40質量份)進行混合，進一步混合甲基乙基酮，於23℃下攪拌30分鐘，藉此獲得固形物成分的含量為30.0質量%之塗佈組成物。此處，前述(甲基)丙烯酸烷基酯共聚物係使甲基丙烯酸甲酯(30質量份)、丙烯酸2-乙基己酯(60質量份)及丙烯酸2-羥基乙酯(10質量份)進行共聚合而成。再者，此處所示之甲基乙基酮以外的成分的調配量全部為固形物成分量。 Alkyl (meth)acrylate copolymer (weight average molecular weight 400,000, glass transition temperature -1°C) (100 parts by mass), and trifunctional xylylene diisocyanate-based crosslinking agent (manufactured by Mitsui Takeda Chemical Co., Ltd. "Takenate D110N") (40 mass parts) was mixed, methyl ethyl ketone was further mixed, and it stirred at 23 degreeC for 30 minutes, and the coating composition whose content of solid content was 30.0 mass % was obtained. Here, the alkyl (meth)acrylate copolymer is made of methyl methacrylate (30 parts by mass), 2-ethylhexyl acrylate (60 parts by mass), and 2-hydroxyethyl acrylate (10 parts by mass) ) are copolymerized. In addition, the compounding quantities of the components other than methyl ethyl ketone shown here are all solid content amounts.

(塗層之形成、支持片之製造) (Formation of coating, manufacture of support sheet)

於基材(r1)的消光處理面，藉由刀式塗佈機，塗敷上述所獲得之塗佈組成物，於110℃下乾燥2分鐘，藉此形成厚度為10μm之塗層。 The coating composition obtained above was applied to the matte-treated surface of the substrate (r1) by a knife coater, and dried at 110° C. for 2 minutes to form a coating layer having a thickness of 10 μm.

繼而，於上述所獲得之黏著劑層中的與設置有剝離膜(s1)之側為相反側的露出面，貼合基材(r1)中的與設置有塗層之側為相反側的平滑面，獲得支持片。 Next, in the adhesive layer obtained above, on the exposed surface on the opposite side to the side on which the release film (s1) is provided, the smooth surface on the opposite side from the side on which the coating layer is provided on the base material (r1) is attached. face, get a support sheet.

(保護膜形成用片之製造) (Manufacture of protective film forming sheet)

自上述所獲得之保護膜形成層的一表面移除剝離膜(s2)，且移除支持片中的黏著劑層上所設置之剝離膜(s1)，將保護膜形成層的露出面以及黏著劑層的露出面進行層壓，藉此獲得保護膜形成用片，該保護膜形成用片由前述塗層、基材(r1)、前述黏著劑層、前述保護膜形成層及剝離膜(s1)依序積層而成，支持片中的與設置有前述黏著劑層之側為相反側的表面(露出面)為塗層的表面，剝離膜中的與設置有保護膜形成層之側為相反側的表面(露出面)為平滑面。 The peeling film (s2) is removed from one surface of the protective film-forming layer obtained above, and the peeling film (s1) provided on the adhesive layer in the support sheet is removed, and the exposed surface of the protective film-forming layer and the adhesive layer are removed. The exposed surface of the agent layer is laminated to obtain a sheet for forming a protective film comprising the coating layer, the base material (r1), the adhesive layer, the protective film forming layer, and the release film (s1). ) is formed by lamination in sequence, the surface (exposed surface) of the opposite side in the support sheet and the side provided with the aforementioned adhesive layer is the surface of the coating, and the side provided with the protective film forming layer in the peeling film is opposite to the side The side surface (exposed surface) is a smooth surface.

<保護膜形成用片之評價> <Evaluation of the sheet for forming a protective film>

針對上述所獲得之保護膜形成用片，利用與實施例1相同的方法進行評價。結果示於表1。 About the sheet for protective film formation obtained above, it evaluated by the method similar to Example 1. The results are shown in Table 1.

[比較例3] [Comparative Example 3]

<保護膜形成用片之製造> <Manufacture of sheet for forming protective film>

(熱硬化性保護膜形成層用組成物之製造、保護膜形成層之形成、黏著劑組成物之製造) (Production of composition for thermosetting protective film-forming layer, formation of protective film-forming layer, production of adhesive composition)

利用與實施例1相同的方法，製造保護膜形成層用組成物(III-1)，獲得於一表面具備有剝離膜(s1)，於另一表面具備有剝離膜(s2)之保護膜形成層。 By the same method as Example 1, the composition (III-1) for protective film forming layers was produced, and the protective film formation provided with the peeling film (s1) on one surface and the peeling film (s2) on the other surface was obtained. layer.

另外，利用與實施例1相同的方法，製造黏著劑組成物(iii)。 Moreover, by the same method as Example 1, the adhesive composition (iii) was produced.

(黏著劑層之形成、支持片之製造) (formation of adhesive layer, manufacture of support sheet)

於剝離膜(s1)的剝離處理面上，藉由刀式塗佈機，塗敷上述所獲得之黏著劑組成物(iii)，於110℃下乾燥2分鐘，藉此形成厚度為10μm之黏著劑層。 On the peeling-treated surface of the peeling film (s1), the adhesive composition (iii) obtained above was applied by a knife coater, and dried at 110° C. for 2 minutes to form an adhesive with a thickness of 10 μm. agent layer.

繼而，於該黏著劑層中的與設置有剝離膜(s1)之側為相反側的露出面，貼合基材(r2)的一平滑面，獲得支持片。 Next, the exposed surface on the opposite side to the side where the release film (s1) is provided in the adhesive layer is bonded to a smooth surface of the base material (r2) to obtain a support sheet.

(保護膜形成用片之製造) (Manufacture of protective film forming sheet)

自上述所獲得之保護膜形成層的一表面移除剝離膜(s2)，且移除支持片中的黏著劑層上所設置之剝離膜(s1)，將保護膜形成層的露出面以及黏著劑層的露出面進行層壓，藉此獲得保護膜形成用片，該保護膜形成用片由基材(r2)、前述黏著劑層、前述保護膜形成層及剝離膜(s1)依序 積層而成，且支持片中的與設置有前述黏著劑層之側為相反側的表面(露出面)為基材(r2)的另一平滑面，剝離膜中的與設置有保護膜形成層之側為相反側的表面(露出面)為平滑面。 The peeling film (s2) is removed from one surface of the protective film-forming layer obtained above, and the peeling film (s1) provided on the adhesive layer in the support sheet is removed, and the exposed surface of the protective film-forming layer and the adhesive layer are removed. The exposed surface of the agent layer is laminated to obtain a sheet for forming a protective film comprising the substrate (r2), the adhesive layer, the protective film forming layer, and the release film (s1) in this order. It is formed by lamination, and the surface (exposed surface) on the opposite side to the side provided with the aforementioned adhesive layer in the support sheet is the other smooth surface of the base material (r2), and in the release film, the protective film forming layer is provided with The surface (exposed surface) on the opposite side is a smooth surface.

<保護膜形成用片之評價> <Evaluation of the sheet for forming a protective film>

針對上述所獲得之保護膜形成用片，利用與實施例1相同的方法進行評價。結果示於表1。 About the sheet for protective film formation obtained above, it evaluated by the method similar to Example 1. The results are shown in Table 1.

[比較例4] [Comparative Example 4]

<保護膜形成用片之製造> <Manufacture of sheet for forming protective film>

(熱硬化性保護膜形成層用組成物之製造、保護膜形成層之形成、黏著劑組成物之製造) (Production of composition for thermosetting protective film-forming layer, formation of protective film-forming layer, production of adhesive composition)

利用與實施例1相同的方法，製造保護膜形成層用組成物(III-1)，獲得於一表面具備有剝離膜(s1)，於另一表面具備有剝離膜(s2)之保護膜形成層。 By the same method as Example 1, the composition (III-1) for protective film forming layers was produced, and the protective film formation provided with the peeling film (s1) on one surface and the peeling film (s2) on the other surface was obtained. layer.

另外，利用與實施例1相同的方法，製造黏著劑組成物(iii)。 Moreover, by the same method as Example 1, the adhesive composition (iii) was produced.

(黏著劑層之形成、支持片之製造) (formation of adhesive layer, manufacture of support sheet)

於剝離膜(s1)的剝離處理面上，藉由刀式塗佈機，塗敷上述所獲得之黏著劑組成物(iii)，於110℃下乾燥2分鐘，藉此形成厚度為10μm之黏著劑層。 On the peeling-treated surface of the peeling film (s1), the adhesive composition (iii) obtained above was applied by a knife coater, and dried at 110° C. for 2 minutes to form an adhesive with a thickness of 10 μm. agent layer.

繼而，於該黏著劑層中的與設置有剝離膜(s1)之側為 相反側的露出面，貼合基材(r3)的消光處理面，獲得支持片。 Then, in the adhesive layer, the side where the release film (s1) is provided is The exposed surface on the opposite side was bonded to the matte-treated surface of the base material (r3) to obtain a support sheet.

(保護膜形成用片之製造) (Manufacture of protective film forming sheet)

自上述所獲得之保護膜形成層的一表面移除剝離膜(s2)，且移除支持片中的黏著劑層上所設置之剝離膜(s1)，將保護膜形成層的露出面以及黏著劑層的露出面進行層壓，藉此獲得保護膜形成用片，該保護膜形成用片由基材(r3)、前述黏著劑層、前述保護膜形成層及剝離膜(s1)依序積層而成，且支持片中的與設置有前述黏著劑層之側為相反側的表面(露出面)為基材(r3)的平滑面，剝離膜中的與設置有保護膜形成層之側為相反側的表面(露出面)為平滑面。 The peeling film (s2) is removed from one surface of the protective film-forming layer obtained above, and the peeling film (s1) provided on the adhesive layer in the support sheet is removed, and the exposed surface of the protective film-forming layer and the adhesive layer are removed. The exposed surface of the agent layer is laminated to obtain a sheet for forming a protective film, the sheet for forming a protective film comprising the substrate (r3), the adhesive layer, the protective film forming layer, and the release film (s1) laminated in this order form, and the surface (exposed surface) on the opposite side of the support sheet and the side provided with the aforementioned adhesive layer is the smooth surface of the substrate (r3), and the side provided with the protective film forming layer in the release film is The surface on the opposite side (exposed surface) is a smooth surface.

<保護膜形成用片之評價> <Evaluation of the sheet for forming a protective film>

針對上述所獲得之保護膜形成用片，利用與實施例1相同的方法進行評價。結果示於表1。 About the sheet for protective film formation obtained above, it evaluated by the method similar to Example 1. The results are shown in Table 1.

Figure 106105584-A0305-02-0145-3
Figure 106105584-A0305-02-0145-3
Figure 106105584-A0305-02-0146-4
Figure 106105584-A0305-02-0146-4

根據上述結果可明確，實施例1至實施例4之保護膜形成用片中，支持片中的與具備有保護膜形成層之側為相反側的表面(露出面)的表面粗糙度小，為0.3μm以下，藉此可良好地對半導體晶片進行紅外線檢測，另外，支持片的前述表面(露出面)以及剝離膜中的與具備有前述保護膜形成層之側為相反側的表面(露出面)之間的靜摩擦力小，為12N以下，藉此可良好地進行自輥之捲出。 From the above results, it is clear that in the protective film forming sheets of Examples 1 to 4, the surface roughness of the surface (exposed surface) on the opposite side to the side provided with the protective film forming layer in the support sheet is small, and is 0.3 μm or less, whereby infrared detection of the semiconductor wafer can be performed well, and the surface (exposed surface) of the support sheet and the surface (exposed surface) opposite to the side provided with the protective film forming layer of the support sheet ), the static friction force between the two is small, and is 12 N or less, whereby the unwinding from the roll can be performed well.

根據這些結果可明確，確認到將支持片的前述露出面設為平滑面或凹凸度低的凹凸面，將剝離膜的前述露出面設為平滑面或凹凸面，調節這些露出面彼此之組合，藉此可降低前述靜摩擦力，從而可良好地進行自輥之捲出。 From these results, it was confirmed that the exposed surface of the support sheet was a smooth surface or a concave-convex surface with low unevenness, and the exposed surface of the release film was a smooth surface or a concave-convex surface, and the combination of these exposed surfaces was adjusted. Thereby, the said static frictional force can be reduced, and unwinding from a roll can be performed favorably.

相對於此，比較例1之保護膜形成用片中，前述靜摩 擦力小，藉此可良好地進行自輥之捲出，但由於前述表面粗糙度大，故而無法對半導體晶片正常地進行紅外線檢測。 On the other hand, in the sheet for protective film formation of the comparative example 1, the said static friction The rubbing force is small, so that unwinding from the roll can be performed well, but since the aforementioned surface roughness is large, the infrared detection of the semiconductor wafer cannot be performed normally.

另外，比較例2之保護膜形成用片中，可對半導體晶片良好地進行紅外線檢測，但自輥捲出時發現異常。推測原因在於，被覆基材的消光處理面之塗層的表面的表面粗糙度雖未測定，但推測足夠小，相對於此，該塗層的材質不適宜，儘管剝離膜的前述露出面為平滑面，前述靜摩擦力亦變大。 Moreover, in the sheet for protective film formation of the comparative example 2, the infrared detection of a semiconductor wafer was favorable, but abnormality was recognized when it was unrolled from a roll. The reason is presumed to be that the surface roughness of the surface of the coating on the matte-treated surface of the coating substrate was not measured, but it was presumed to be sufficiently small. In contrast, the material of the coating was not suitable, although the exposed surface of the release film was smooth. On the surface, the aforementioned static friction force also increases.

另外，比較例3之保護膜形成用片中，前述表面粗糙度小，藉此可對半導體晶片良好地進行紅外線檢測，但前述靜摩擦力大，因此自輥捲出時發現異常。 Moreover, in the sheet for protective film formation of the comparative example 3, the said surface roughness was small, and the infrared detection of a semiconductor wafer was favorable, but the said static friction force was large, so abnormality was found when unrolling from a roll.

比較例4之保護膜形成用片中，前述表面粗糙度小，藉此可對半導體晶片良好地進行紅外線檢測，但前述靜摩擦力大，因此與比較例3之情形同樣地，自輥捲出時發現異常。 In the sheet for forming a protective film of Comparative Example 4, the surface roughness was small, so that infrared detection of semiconductor wafers could be performed well, but the static friction force was large. An exception was found.

(產業可利用性) (Industrial Availability)

本發明可用於製造背面由保護膜保護之半導體晶片等，因此在產業上極其重要。 The present invention is industrially extremely important because it can be used to manufacture a semiconductor wafer etc. whose back surface is protected by a protective film.

1A:保護膜形成用片 1A: Sheet for forming protective film

10:支持片 10: Support Sheet

10a:支持片的表面 10a: Surface of support sheet

10b:支持片的背面(露出面) 10b: Back side of support sheet (exposed side)

11:基材 11: Substrate

11a:基材的表面 11a: Surface of the substrate

11b:基材的背面 11b: Backside of substrate

12:黏著劑層 12: Adhesive layer

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

13:保護膜形成層 13: Protective film forming layer

13a:保護膜形成層的表面 13a: Surface of protective film-forming layer

15:剝離膜 15: Peel off film

15a:剝離膜的表面 15a: Surface of 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 adhesive layer for jig

Claims (7)

一種保護膜形成用片，係於支持片上具備有保護膜形成層，並於前述保護膜形成層上具備有剝離膜；前述支持片中的與具備有前述保護膜形成層之側為相反側的表面的表面粗糙度為0.5μm以下；前述支持片中的前述表面以及前述剝離膜中的與具備有前述保護膜形成層之側為相反側的表面之間，依據JIS K7125所測定之靜摩擦力為2N以上至29N以下。 A protective film forming sheet is provided with a protective film forming layer on the support sheet, and a peeling film is provided on the aforementioned protective film forming layer; in the aforementioned supporting sheet, the side that is provided with the aforementioned protective film forming layer is the opposite side The surface roughness of the surface is 0.5 μm or less; the static friction force measured according to JIS K7125 is Above 2N to below 29N. 如請求項1所記載之保護膜形成用片，其中前述支持片具備有基材，且前述基材的表面經實施利用噴砂處理之凹凸化處理。 The sheet for forming a protective film according to claim 1, wherein the support sheet includes a base material, and the surface of the base material is subjected to unevenness treatment by sandblasting. 如請求項1所記載之保護膜形成用片，其中前述支持片為於基材上積層黏著劑層而成。 The sheet for forming a protective film according to claim 1, wherein the support sheet is formed by laminating an adhesive layer on a base material. 如請求項2所記載之保護膜形成用片，其中前述支持片為於前述基材上積層黏著劑層而成。 The sheet for forming a protective film according to claim 2, wherein the support sheet is formed by laminating an adhesive layer on the base material. 如請求項3或4所記載之保護膜形成用片，其中前述黏著劑層的厚度為1μm至100μm。 The sheet for forming a protective film according to claim 3 or 4, wherein the thickness of the adhesive layer is 1 μm to 100 μm. 一種保護膜形成用片的製造方法，前述保護膜形成用片為如請求項1至5中任一項所記載之保護膜形成用片；該保護膜形成用片的製造方法係包含有以下步驟：以前述支持片中的與具備有前述保護膜形成層 之側為相反側的表面的表面粗糙度成為0.5μm以下之方式，形成前述支持片與前述保護膜形成層之積層結構之步驟；以及以前述支持片中的與具備有前述保護膜形成層之側為相反側的表面以及前述剝離膜中的與具備有前述保護膜形成層之側為相反側的表面之間，以依據JIS K7125所測定之靜摩擦力成為2N以上至29N以下之方式，形成前述保護膜形成層與前述剝離膜之積層結構。 A method for producing a sheet for forming a protective film, wherein the sheet for forming a protective film is the sheet for forming a protective film as described in any one of claims 1 to 5; the method for producing a sheet for forming a protective film comprises the following steps : With the above-mentioned support sheet and the above-mentioned protective film-forming layer The step of forming the laminated structure of the aforementioned support sheet and the aforementioned protective film-forming layer in such a way that the surface roughness of the surface on the opposite side becomes 0.5 μm or less; Between the surface on the opposite side and the surface on the opposite side of the release film and the side on which the protective film forming layer is provided, the static friction force measured in accordance with JIS K7125 is 2N or more and 29N or less. A laminated structure of the protective film forming layer and the aforementioned release film. 一種半導體裝置的製造方法，係包含有以下步驟：自如請求項1至4中任一項所記載之保護膜形成用片移除前述剝離膜後，將前述保護膜形成層貼附於半導體晶圓中的與設置有電路之面為相反側的背面之步驟；使貼附於前述半導體晶圓後的前述保護膜形成層硬化而形成保護膜之步驟；對形成有前述保護膜之半導體晶圓進行切割而形成半導體晶片之步驟；自前述保護膜形成用片的前述支持片側對前述半導體晶片照射紅外線，而對前述半導體晶片進行檢測之步驟；自前述支持片將前述半導體晶片與貼附於該半導體晶片的背面之保護膜一起剝離，藉此獲得附保護膜之半導體晶片之步驟；以及 將前述附保護膜之半導體晶片的半導體晶片以倒裝晶片之方式連接於基板的電路面之步驟。 A method of manufacturing a semiconductor device, comprising the steps of: after removing the peeling film from the protective film forming sheet described in any one of claims 1 to 4, attaching the protective film forming layer to a semiconductor wafer The step of forming the protective film by hardening the protective film-forming layer attached to the semiconductor wafer; the step of forming the protective film on the semiconductor wafer on which the protective film is formed. The step of dicing to form a semiconductor wafer; the step of irradiating the semiconductor wafer with infrared rays from the support sheet side of the protective film forming sheet to detect the semiconductor wafer; the step of attaching the semiconductor wafer to the semiconductor wafer from the support sheet The steps of peeling off the protective film on the backside of the wafer together, thereby obtaining a semiconductor wafer with a protective film; and The step of connecting the semiconductor chip of the semiconductor chip with the protective film to the circuit surface of the substrate by flip-chip.
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