TW202027993A - Composite sheet for forming protective film and method for manufacturing semiconductor chip - Google Patents

Composite sheet for forming protective film and method for manufacturing semiconductor chip Download PDF

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TW202027993A
TW202027993A TW108144085A TW108144085A TW202027993A TW 202027993 A TW202027993 A TW 202027993A TW 108144085 A TW108144085 A TW 108144085A TW 108144085 A TW108144085 A TW 108144085A TW 202027993 A TW202027993 A TW 202027993A
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protective film
forming
film
composite sheet
aforementioned
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TW108144085A
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小橋力也
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日商琳得科股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • 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
    • H01L21/67092—Apparatus for mechanical treatment
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68377—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support with parts of the auxiliary support remaining in the finished device

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Dicing (AREA)
  • Adhesive Tapes (AREA)

Abstract

The half-life of a charged voltage of a composite film for protective film formation 101 comprising a support sheet 10 and a film for protective film formation 13 formed on the 1st surface 10a of the support sheet 10 is set to 20 seconds or less.

Description

保護膜形成用複合片、以及半導體晶片之製造方法Composite sheet for forming protective film and method for manufacturing semiconductor wafer

本發明係關於一種保護膜形成用複合片、以及半導體晶片之製造方法。本申請案基於2018年12月5日在日本提出申請之日本專利特願2018-228525號主張優先權，且將該申請案的內容引用至本文中。The present invention relates to a composite sheet for forming a protective film and a method for manufacturing a semiconductor wafer. This application claims priority based on Japanese Patent Application No. 2018-228525 filed in Japan on December 5, 2018, and the content of this application is cited herein.

近年來，業界應用稱為所謂的倒裝(face down)方式之安裝方法而製造半導體裝置。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，有時半導體晶片中之與電路面為相反側的內面裸露。In recent years, the industry has applied a so-called face down mounting method to manufacture semiconductor devices. In the flip chip method, a semiconductor wafer having electrodes such as bumps on the circuit surface is used, and the aforementioned electrodes are joined to the substrate. Therefore, the inner surface of the semiconductor wafer opposite to the circuit surface may be exposed.

有時於該裸露的半導體晶片的內面，形成含有有機材料之樹脂膜作為保護膜，以附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之後半導體晶片產生龜裂。Sometimes a resin film containing an organic material is formed on the inner surface of the exposed semiconductor chip as a protective film, which is incorporated into a semiconductor device in the form of a semiconductor chip with a protective film. The protective film is used to prevent the semiconductor chip from cracking after the dicing step or packaging.

為了形成此種保護膜，例如使用於支撐片上具備用以形成保護膜之保護膜形成用膜而構成之保護膜形成用複合片。保護膜形成用膜可藉由硬化而形成保護膜。另外，支撐片可用於將內面具備保護膜形成用膜或保護膜之半導體晶圓分割為半導體晶片時，固定半導體晶圓。進而，支撐片亦可用作切割片，且保護膜形成用複合片亦可用作保護膜形成用膜與切割片形成為一體之複合片。In order to form such a protective film, the composite sheet for protective film formation comprised with the film for protective film formation for forming a protective film on a support sheet is used, for example. The protective film formation film can be cured to form a protective film. In addition, the support sheet can be used to fix the semiconductor wafer when the semiconductor wafer provided with the protective film forming film or the protective film on the inner surface is divided into semiconductor wafers. Furthermore, the support sheet can also be used as a dicing sheet, and the composite sheet for protective film formation can also be used as a composite sheet in which the film for protective film formation and the dicing sheet are integrated.

保護膜形成用複合片通常進而於保護膜形成用膜上具備剝離膜而構成。剝離膜係於使用保護膜形成用膜時，在合適的時間點移除。剝離膜藉由被覆保護膜形成用膜的表面，在使用保護膜形成用膜時之前，防止保護膜形成用膜朝目標外的部位之貼附，或者將保護膜形成用膜維持為適當的狀態。例如，於將保護膜形成用複合片捲取成捲筒狀而進行保管時，必須使保護膜形成用複合片具備剝離膜。The composite sheet for forming a protective film is usually configured by further including a release film on the film for forming a protective film. The release film is used when the protective film formation film is used, and it is removed at an appropriate point in time. The peeling film covers the surface of the protective film forming film to prevent the protective film forming film from sticking to the target area before using the protective film forming film, or to maintain the protective film forming film in an appropriate state . For example, when the composite sheet for protective film formation is wound into a roll shape and stored, the composite sheet for protective film formation must be provided with a release film.

例如，於使用保護膜形成用複合片時，移除該保護膜形成用複合片中的剝離膜，將新產生之保護膜形成用膜的露出面貼合於半導體晶圓的內面，藉此將保護膜形成用複合片貼附於半導體晶圓的內面。然後，在合適的時間點，適宜進行如下操作：藉由使保護膜形成用膜硬化而形成保護膜、切斷保護膜形成用膜或保護膜、將半導體晶圓分割為半導體晶片、自支撐片拾取內面具備切斷後的保護膜形成用膜或保護膜之半導體晶片(附保護膜形成用膜之半導體晶片或附保護膜之半導體晶片)等。並且，於拾取附保護膜形成用膜之半導體晶片之情形時，係藉由使保護膜形成用膜硬化，成為附保護膜之半導體晶片，最終使用附保護膜之半導體晶片，製造半導體裝置。For example, when a composite sheet for forming a protective film is used, the release film in the composite sheet for forming a protective film is removed, and the exposed surface of the newly produced protective film forming film is attached to the inner surface of the semiconductor wafer, thereby The composite sheet for forming a protective film is attached to the inner surface of the semiconductor wafer. Then, at an appropriate point in time, it is appropriate to perform the following operations: forming a protective film by curing the protective film forming film, cutting the protective film forming film or protective film, dividing the semiconductor wafer into semiconductor wafers, and self-supporting sheets Pick up a semiconductor wafer (semiconductor wafer with a protective film forming film or a semiconductor wafer with a protective film) provided with a cut protective film forming film or a protective film on the inner surface. In addition, when picking up a semiconductor wafer with a protective film forming film, the protective film forming film is cured to become a semiconductor wafer with a protective film, and finally the semiconductor wafer with a protective film is used to manufacture a semiconductor device.

但是，有如下問題：如上所述般將保護膜形成用複合片貼附於半導體晶圓的內面後，於保護膜形成用複合片中的保護膜形成用膜與半導體晶圓之間容易混入小的異物。若如此般混入異物，則有時最終所獲得之附保護膜之半導體晶片無法發揮目標性能。However, there is a problem that after the composite sheet for forming a protective film is attached to the inner surface of the semiconductor wafer as described above, the film for forming a protective film in the composite sheet for forming a protective film and the semiconductor wafer are easily mixed Small foreign body. If foreign matter is mixed in in this way, the semiconductor chip with protective film finally obtained may not exhibit the target performance.

本發明者對前述問題的原因進行了研究，結果發現原因在於，在將保護膜形成用複合片貼附於半導體晶圓的內面之前，自保護膜形成用複合片中的保護膜形成用膜移除剝離膜時，殘留的保護膜形成用複合片帶電。帶電的保護膜形成用複合片於該保護膜形成用複合片朝半導體晶圓之貼附前的階段，於該保護膜形成用複合片的保護膜形成用膜上容易吸附小的異物，因此於保護膜形成用膜與半導體晶圓之間容易混入異物。本說明書中，有時將此種因相互接觸的層彼此的剝離而導致這些層帶電之現象稱為「剝離帶電」。The inventors of the present invention have studied the causes of the aforementioned problems, and found that the cause is that the protective film forming film in the protective film forming composite sheet before attaching the protective film forming composite sheet to the inner surface of the semiconductor wafer When the release film is removed, the remaining composite sheet for forming a protective film is charged. The charged composite sheet for forming a protective film is at a stage before the composite sheet for forming a protective film is attached to the semiconductor wafer, and small foreign matter is easily adsorbed on the film for forming a protective film of the composite sheet for forming a protective film. Foreign matter is likely to be mixed between the protective film forming film and the semiconductor wafer. In this specification, the phenomenon that such layers are charged due to the peeling of layers in contact with each other is sometimes referred to as "peeling charging".

另一方面，作為抑制剝離帶電之半導體加工用片，揭示有一種切割帶一體型接著片，具有於基材上積層有黏著劑層之切割帶(相當於前述支撐片)、及形成於前述黏著劑層上之接著片，並且以剝離速度10m/分鐘、剝離角度150°，將前述黏著劑層與前述接著片剝離時的剝離帶電壓的絕對值為0.5kV以下(參照專利文獻1)。根據專利文獻1，藉由使用該切割帶一體型接著片，於拾取步驟中，將附著有接著片之半導體元件自切割帶剝離時，能夠抑制接著片與切割帶之間的剝離帶電，抑制產生靜電，抑制因該靜電所致之半導體元件上的電路的破壞。 [先前技術文獻] [專利文獻]On the other hand, as a semiconductor processing sheet for suppressing peeling and electrification, there is disclosed a dicing tape-integrated adhesive sheet, which has a dicing tape (equivalent to the aforementioned support sheet) on which an adhesive layer is laminated on a substrate, and a sheet formed on the aforementioned adhesive The adhesive sheet on the agent layer has a peeling speed of 10 m/min and a peeling angle of 150°, and the absolute value of the peeling charge voltage when the adhesive layer is peeled from the adhesive sheet is 0.5 kV or less (see Patent Document 1). According to Patent Document 1, by using this dicing tape-integrated adhesive sheet, when the semiconductor element to which the adhesive sheet is attached is peeled from the dicing tape in the pickup step, the peeling charge between the adhesive sheet and the dicing tape can be suppressed, and the generation Static electricity suppresses the destruction of the circuit on the semiconductor element caused by the static electricity. [Prior Technical Literature] [Patent Literature]

[專利文獻1]日本專利第6077922號公報。[Patent Document 1] Japanese Patent No. 6077922.

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

但是，關於專利文獻1中所揭示之切割帶一體型接著片，尚不明確能否抑制如上文所說明之自接著片移除剝離膜時的剝離帶電、及由此帶來之接著片與半導體晶圓之間的異物的混入。However, regarding the dicing tape-integrated adhesive sheet disclosed in Patent Document 1, it is not clear whether it is possible to suppress the peeling charge when the release film is removed from the adhesive sheet as described above, and the resulting adhesive sheet and semiconductor The mixing of foreign matter between wafers.

本發明的目的在於提供一種保護膜形成用複合片、以及使用前述保護膜形成用複合片之半導體晶片之製造方法，前述保護膜形成用複合片具備支撐片及保護膜形成用膜，並且能夠抑制將設置於保護膜形成用膜上之剝離膜自保護膜形成用膜移除時的剝離帶電，能夠抑制因該剝離帶電所致之保護膜形成用膜與半導體晶圓之間的異物的混入。 [用以解決課題之手段]The object of the present invention is to provide a composite sheet for forming a protective film and a method for manufacturing a semiconductor wafer using the composite sheet for forming a protective film. The composite sheet for forming a protective film includes a support sheet and a film for forming a protective film, and can suppress The peeling charge when the peeling film provided on the protective film forming film is removed from the protective film forming film can suppress the mixing of foreign matter between the protective film forming film and the semiconductor wafer due to the peeling charge. [Means to solve the problem]

本發明提供一種保護膜形成用複合片，具備支撐片、及形成於前述支撐片的一面上之保護膜形成用膜，並且前述保護膜形成用複合片的帶電壓的半衰期為20秒以下。The present invention provides a composite sheet for forming a protective film, comprising a support sheet and a film for forming a protective film formed on one side of the support sheet, and the composite sheet for forming a protective film has a charged half-life of 20 seconds or less.

依據JIS L 1094：2014所測定之本發明的保護膜形成用複合片的最大帶電壓亦可為1kV以下。 本發明的保護膜形成用複合片中，亦可前述支撐片具備基材、及形成於前述基材的單面或雙面上之抗靜電層，或者前述支撐片具備具有抗靜電性之基材作為抗靜電層。 本發明的保護膜形成用複合片中，亦可形成於前述基材的單面或雙面上之抗靜電層的厚度為100nm以下。The maximum charging voltage of the composite sheet for forming a protective film of the present invention measured in accordance with JIS L 1094:2014 may be 1 kV or less. In the composite sheet for forming a protective film of the present invention, the support sheet may include a substrate and an antistatic layer formed on one or both sides of the substrate, or the support sheet may include a substrate with antistatic properties As an antistatic layer. In the composite sheet for forming a protective film of the present invention, the thickness of the antistatic layer formed on one or both sides of the aforementioned base material may be 100 nm or less.

本發明的保護膜形成用複合片中，亦可前述支撐片的全光線透過率為80%以上。 本發明的保護膜形成用複合片中，亦可於具有面積為2cm×2cm且為平面狀之按壓面之按壓機構的前述按壓面，被覆法蘭絨布，將被覆有前述法蘭絨布之前述按壓面壓抵於前述抗靜電層的表面，以該狀態，一邊藉由前述按壓機構對前述抗靜電層施加125g/cm2 之荷重而進行按壓，一邊使前述按壓機構以10cm之直線距離往返運動10次，藉此摩擦前述抗靜電層之後，目視觀察前述抗靜電層的該摩擦面中面積為2cm×2cm之區域時，未確認到傷痕。 另外，本發明提供一種半導體晶片之製造方法，具有：使用於保護膜形成用複合片中的保護膜形成用膜上具備剝離膜之保護膜形成用複合片作為前述保護膜形成用複合片，自前述保護膜形成用膜移除前述剝離膜之步驟；將移除前述剝離膜後的前述保護膜形成用複合片中的保護膜形成用膜貼附於半導體晶圓之步驟；使貼附於前述半導體晶圓後的前述保護膜形成用膜硬化而形成保護膜之步驟；分割前述半導體晶圓，切斷前述保護膜或保護膜形成用膜，獲得具備切斷後的保護膜或保護膜形成用膜之多個半導體晶片之步驟；以及將具備前述切斷後的保護膜或保護膜形成用膜之半導體晶片自前述支撐片扯離而進行拾取之步驟。 [發明功效]In the composite sheet for forming a protective film of the present invention, the total light transmittance of the support sheet may be 80% or more. In the composite sheet for forming a protective film of the present invention, the pressing surface of the pressing mechanism having a planar pressing surface with an area of 2cm×2cm may be covered with a flannel cloth, and the pressing surface covered with the flannel cloth may be covered. The surface is pressed against the surface of the antistatic layer. In this state, while applying a load of 125 g/cm 2 to the antistatic layer by the pressing mechanism, the pressing mechanism is moved back and forth at a linear distance of 10 cm. Next, after rubbing the antistatic layer by this, when visually observing the area of the rubbed surface of the antistatic layer having an area of 2 cm×2 cm, no scratches were confirmed. In addition, the present invention provides a method for manufacturing a semiconductor wafer, comprising: a composite sheet for forming a protective film provided with a release film on a film for forming a protective film used in a composite sheet for forming a protective film as the composite sheet for forming a protective film, The step of removing the peeling film from the protective film forming film; the step of attaching the protective film forming film in the composite sheet for forming the protective film after the peeling film is removed to the semiconductor wafer; The step of curing the protective film forming film after the semiconductor wafer to form a protective film; dividing the semiconductor wafer, cutting the protective film or protective film forming film, and obtaining a protective film or protective film forming film after cutting The step of multiple semiconductor wafers; and the step of picking up the semiconductor wafer with the protective film or protective film forming film after cutting from the supporting sheet. [Invention Effect]

根據本發明，提供一種保護膜形成用複合片、以及使用前述保護膜形成用複合片之半導體晶片之製造方法，前述保護膜形成用複合片具備支撐片及保護膜形成用膜，並且能夠抑制將設置於保護膜形成用膜上之剝離膜自保護膜形成用膜移除時的剝離帶電，能夠抑制因該剝離帶電所致之保護膜形成用膜與半導體晶圓之間的異物的混入。According to the present invention, there is provided a composite sheet for forming a protective film and a method for manufacturing a semiconductor wafer using the composite sheet for forming a protective film. The composite sheet for forming a protective film includes a support sheet and a film for forming a protective film, and can suppress The peeling charge when the peeling film provided on the protective film forming film is removed from the protective film forming film can suppress the incorporation of foreign matter between the protective film forming film and the semiconductor wafer due to the peeling charge.

◇保護膜形成用複合片 本發明的一實施形態的保護膜形成用複合片具備支撐片、及形成於前述支撐片的一面上之保護膜形成用膜，並且前述保護膜形成用複合片的帶電壓的半衰期為20秒以下。 前述保護膜形成用複合片如此般帶電壓的半衰期為20秒以下，前述保護膜形成用複合片的帶電壓迅速衰減(降低)。因此，前述保護膜形成用複合片於將設置於前述保護膜形成用複合片中的保護膜形成用膜上之剝離膜自保護膜形成用膜移除時，剝離帶電的狀態迅速消除，結果能夠抑制剝離帶電。並且，能夠抑制因該剝離帶電所致之保護膜形成用膜與半導體晶圓之間的異物的混入。◇Composite sheet for forming protective film A composite sheet for forming a protective film according to an embodiment of the present invention includes a support sheet and a film for forming a protective film formed on one surface of the support sheet, and the charged half-life of the composite sheet for forming a protective film is 20 seconds or less . The composite sheet for forming a protective film has a voltage half-life of 20 seconds or less in this way, and the charging voltage of the composite sheet for forming a protective film is rapidly attenuated (decreased). Therefore, when the protective film forming composite sheet is removed from the protective film forming film on the protective film forming film provided in the protective film forming composite sheet, the peeling charged state is quickly eliminated, and as a result Suppress peeling charge. In addition, it is possible to suppress mixing of foreign substances between the protective film forming film and the semiconductor wafer due to the peeling charge.

本實施形態的保護膜形成用複合片例如藉由該保護膜形成用複合片中的任一層含有抗靜電劑，具有剝離帶電的抑制效果。 前述保護膜形成用複合片中，前述保護膜形成用複合片的剝離帶電的抑制效果、換言之帶電壓的半衰期的長度例如可藉由調節含有抗靜電劑之層(本說明書中，有時概括性地稱為「抗靜電層」)中的抗靜電劑的含量而進行調節。另外，前述帶電壓的半衰期的長度有時亦可藉由前述抗靜電層的厚度而進行調節。The composite sheet for forming a protective film of the present embodiment, for example, has an antistatic agent in any of the layers of the composite sheet for forming a protective film, thereby having an effect of suppressing peeling charge. In the composite sheet for forming a protective film, the suppression effect of the peeling charge of the composite sheet for forming a protective film, in other words, the length of the half-life of the charged voltage can be adjusted, for example, by adjusting the layer containing an antistatic agent (in this specification, it may be generalized (Referred to as "antistatic layer") to adjust the content of the antistatic agent. In addition, the length of the half-life of the charged voltage may sometimes be adjusted by the thickness of the antistatic layer.

[保護膜形成用複合片的帶電壓的半衰期] 前述保護膜形成用複合片的帶電壓的半衰期為20秒以下，較佳為18秒以下，更佳為16秒以下，例如可為12秒以下、7秒以下、以及4秒以下之任一者。藉由前述半衰期為前述上限值以下，保護膜形成用複合片的剝離帶電的抑制效果變高，結果保護膜形成用膜與半導體晶圓之間的異物混入的抑制效果變高。[The half-life of the composite sheet for forming a protective film with voltage] The charged half-life of the composite sheet for forming a protective film is 20 seconds or less, preferably 18 seconds or less, more preferably 16 seconds or less, for example, can be any of 12 seconds or less, 7 seconds or less, and 4 seconds or less . When the half-life is less than or equal to the upper limit, the effect of suppressing the peeling charge of the protective film forming composite sheet becomes higher, and as a result, the effect of suppressing foreign matter mixing between the protective film forming film and the semiconductor wafer becomes higher.

前述保護膜形成用複合片的帶電壓的半衰期的下限值並無特別限定，越短越佳。若考慮保護膜形成用複合片的製造容易度、以及保護膜形成用複合片的構成自由度的高度等，則保護膜形成用複合片的帶電壓的半衰期較佳為0.1秒以上。The lower limit of the charged half-life of the composite sheet for forming a protective film is not particularly limited, and the shorter the better. Considering the ease of manufacture of the composite sheet for forming a protective film, the degree of freedom in the configuration of the composite sheet for forming a protective film, and the like, the charged half-life of the composite sheet for forming a protective film is preferably 0.1 second or more.

前述保護膜形成用複合片的帶電壓的半衰期可適宜調節為將上述之較佳的下限值及上限值任意組合而設定之範圍內。例如，一實施形態中，前述半衰期較佳為0.1秒至20秒，更佳為0.1秒至18秒，進而較佳為0.1秒至16秒，例如可為0.1秒至12秒、0.1秒至7秒、以及0.1秒至4秒之任一者。但這些係前述半衰期的一例。The charged half-life of the composite sheet for forming a protective film can be suitably adjusted to be within a range set by arbitrarily combining the above-mentioned preferable lower limit and upper limit. For example, in one embodiment, the aforementioned half-life is preferably 0.1 second to 20 seconds, more preferably 0.1 second to 18 seconds, and still more preferably 0.1 second to 16 seconds, for example, 0.1 second to 12 seconds, 0.1 second to 7 seconds. Seconds, and any of 0.1 seconds to 4 seconds. But these are examples of the aforementioned half-life.

前述保護膜形成用複合片的帶電壓的半衰期如後文實施例中所述，可依據JIS L 1094：2014進行測定。The charged half-life of the composite sheet for forming a protective film can be measured in accordance with JIS L 1094:2014 as described in the examples below.

[保護膜形成用複合片的最大帶電壓] 依據JIS L 1094：2014所測定之前述保護膜形成用複合片的最大帶電壓較佳為1kV以下，更佳為900V以下，進而較佳為800V以下，例如可為600V以下、400V以下、以及300V以下之任一者。前述最大帶電壓為前述上限值以下之保護膜形成用複合片於剛將剝離膜自保護膜形成用膜移除後，剝離帶電之產生輕微，因此特性更良好。並且，藉由使用此種保護膜形成用複合片，保護膜形成用膜與半導體晶圓之間的異物混入的抑制效果變高。[Maximum charging voltage of composite sheet for protective film formation] According to JIS L 1094:2014, the maximum charging voltage of the composite sheet for forming a protective film is preferably 1kV or less, more preferably 900V or less, and more preferably 800V or less, for example, 600V or less, 400V or less, and 300V Any of the following. The composite sheet for forming a protective film whose maximum charging voltage is less than the foregoing upper limit has a slight peeling charge immediately after the peeling film is removed from the film for forming a protective film, and therefore has better characteristics. In addition, by using such a composite sheet for forming a protective film, the effect of suppressing the mixing of foreign substances between the film for forming a protective film and the semiconductor wafer becomes high.

依據JIS L 1094：2014所測定之前述保護膜形成用複合片的最大帶電壓的下限值並無特別限定，越低越佳。若考慮保護膜形成用複合片的製造容易度、以及保護膜形成用複合片的構成自由度的高度等，則保護膜形成用複合片的最大帶電壓較佳為3V以上。The lower limit of the maximum charged voltage of the composite sheet for forming a protective film, measured in accordance with JIS L 1094:2014, is not particularly limited, and the lower the better. Considering the ease of manufacture of the composite sheet for protective film formation, the height of the degree of freedom of the composition of the composite sheet for protective film formation, etc., the maximum charging voltage of the composite sheet for protective film formation is preferably 3V or more.

依據JIS L 1094：2014所測定之前述保護膜形成用複合片的最大帶電壓可適宜調節為將上述之較佳的下限值及上限值任意組合而設定之範圍內。例如，一實施形態中，前述最大帶電壓較佳為3V至1kV，更佳為3V至900V，進而較佳為3V至800V，例如可為3V至600V、3V至400V、以及3V至300V之任一者。但這些係前述最大帶電壓的一例。The maximum charged voltage of the aforementioned composite sheet for forming a protective film, measured in accordance with JIS L 1094:2014, can be appropriately adjusted to a range set by arbitrarily combining the above-mentioned preferable lower limit and upper limit. For example, in one embodiment, the aforementioned maximum charging voltage is preferably 3V to 1kV, more preferably 3V to 900V, and more preferably 3V to 800V, for example, it can be any of 3V to 600V, 3V to 400V, and 3V to 300V. One. But these are examples of the aforementioned maximum charged voltage.

所謂「依據JIS L 1094：2014所測定之前述保護膜形成用複合片的最大帶電壓為1kV以下」，意指利用該方法測定保護膜形成用複合片的帶電壓時，該帶電壓的測定值始終為1kV以下(換言之，始終不超過1kV)。 利用該方法所測定之保護膜形成用複合片的最大帶電壓的數值另外成為於將設置於保護膜形成用複合片中的保護膜形成用膜上之剝離膜自保護膜形成用膜移除時，保護膜形成用複合片剝離帶電時的最大帶電壓的數值的標準。 此處，列舉保護膜形成用複合片的最大帶電壓為1kV之情形為例而進行了說明，但保護膜形成用複合片的最大帶電壓為1kV以外的值之情形亦相同。The "maximum charging voltage of the composite sheet for forming a protective film measured in accordance with JIS L 1094: 2014 is 1kV or less" means the measured value of the charging voltage when the charging voltage of the composite sheet for forming a protective film is measured by this method Always below 1kV (in other words, never exceed 1kV). The value of the maximum charged voltage of the protective film formation composite sheet measured by this method is also used when the release film on the protective film formation film provided in the protective film formation composite sheet is removed from the protective film formation film , The standard for the value of the maximum charged voltage when the composite sheet for protective film formation is peeled off and charged. Here, the case where the maximum charging voltage of the composite sheet for forming a protective film is 1 kV was described as an example, but the same applies to the case where the maximum charging voltage of the composite sheet for forming a protective film is a value other than 1 kV.

於依據JIS L 1094：2014測定保護膜形成用複合片的帶電壓之情形時，本說明書中，有時將該測定開始時的帶電壓稱為「初始帶電壓」。於依據JIS L 1094：2014測定保護膜形成用複合片的帶電壓之情形時，通常初始帶電壓與上述最大帶電壓相同。 另一方面，於將剝離膜自保護膜形成用膜移除之情形時，保護膜形成用複合片的帶電壓於剛將剝離膜自保護膜形成用膜移除後成為最大。When measuring the charging voltage of the composite sheet for forming a protective film in accordance with JIS L 1094:2014, the charging voltage at the start of the measurement may be referred to as the "initial charging voltage" in this specification. When measuring the charging voltage of the composite sheet for forming a protective film in accordance with JIS L 1094:2014, the initial charging voltage is usually the same as the above-mentioned maximum charging voltage. On the other hand, when the release film is removed from the protective film formation film, the charged voltage of the composite sheet for protective film formation becomes the maximum immediately after the release film is removed from the protective film formation film.

以下，對構成前述保護膜形成用複合片之各層詳細地進行說明。Hereinafter, each layer constituting the aforementioned composite sheet for forming a protective film will be described in detail.

◎支撐片 前述支撐片可由1層(單層)所構成，亦可由2層以上之多層所構成。於支撐片由多層所構成之情形時，這些多層的構成材料及厚度相互可相同亦可不同，這些多層的組合只要無損本發明的效果，則並無特別限定。◎Support sheet The aforementioned support sheet may be composed of one layer (single layer), or may be composed of two or more layers. When the support sheet is composed of multiple layers, the constituent materials and thickness of these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited as long as the effect of the present invention is not impaired.

此外，本說明書中，並不限於支撐片之情形，所謂「多層相互可相同亦可不同」，意指「可全部層相同，亦可全部層皆不同，還可僅一部分層相同」，進而，所謂「多層相互不同」，意指「各層的構成材料及厚度的至少一者相互不同」。In addition, in this specification, it is not limited to the case of the support sheet. The so-called "multilayers may be the same or different from each other" means "all layers may be the same, or all layers may be different, and only a part of the layers may be the same." The term "multilayers are different from each other" means "at least one of the constituent materials and thicknesses of the layers is different from each other".

支撐片可為透明，亦可為不透明，還可根據目的而著色。 例如，於保護膜形成用膜具有能量線硬化性之情形時，支撐片較佳為使能量線透過之支撐片。 例如，為了對保護膜形成用複合片中的保護膜形成用膜經由支撐片進行光學檢查，支撐片較佳為透明。The support sheet can be transparent or opaque, and can be colored according to the purpose. For example, when the film for forming a protective film has energy ray curability, the support sheet is preferably a support sheet that allows energy rays to pass through. For example, in order to optically inspect the protective film formation film in the protective film formation composite sheet via the support sheet, the support sheet is preferably transparent.

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。作為能量線的示例，可列舉紫外線、放射線、電子束等。紫外線例如可藉由使用高壓水銀燈、熔合燈、氙氣燈、黑光燈或LED(Light Emitting Diode；發光二極體)燈等作為紫外線源進行照射。電子束可照射藉由電子束加速器等產生之電子束。 另外，本說明書中，所謂「能量線硬化性」，意指藉由照射能量線而硬化之性質，所謂「非能量線硬化性」，意指即便照射能量線亦不硬化之性質。In this specification, the "energy line" refers to electromagnetic waves or charged particle beams with energy quantum. Examples of energy rays include ultraviolet rays, radiation rays, electron beams, and the like. The ultraviolet light can be irradiated by using a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light lamp, or an LED (Light Emitting Diode) lamp as an ultraviolet source, for example. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like. In addition, in this specification, the "energy ray curability" means the property of being hardened by irradiation with energy rays, and the "non-energy ray hardening property" means the property of not being hardened even if energy rays are irradiated.

作為支撐片，例如可列舉：具備基材、及形成於前述基材上之黏著劑層之支撐片；僅由基材所構成之支撐片等。As the support sheet, for example, a support sheet provided with a substrate and an adhesive layer formed on the aforementioned substrate; a support sheet composed of only the substrate, and the like.

另一方面，如上所述，前述保護膜形成用複合片中，可將該保護膜形成用複合片中的任一層設為抗靜電層。 此種情形時，作為較佳的前述支撐片，例如可列舉：具備基材，且具備於保護膜形成用複合片中形成於前述基材中之位於前述保護膜形成用膜側之相反側的面上之抗靜電層(本說明書中，有時簡稱為「背面抗靜電層」)之支撐片；具備具有抗靜電性之基材(本說明書中，有時簡稱為「抗靜電性基材」)作為抗靜電層之支撐片；具備基材，且具備於保護膜形成用複合片中形成於前述基材中之位於前述保護膜形成用膜側的面上之抗靜電層(本說明書中，有時簡稱為「表面抗靜電層」)之支撐片。前述抗靜電層(背面抗靜電層、抗靜電性基材及表面抗靜電層)均含有抗靜電劑。On the other hand, as described above, in the composite sheet for forming a protective film, any layer in the composite sheet for forming a protective film may be an antistatic layer. In this case, a preferable support sheet includes, for example, a substrate provided with a protective film forming composite sheet formed on the substrate and located on the opposite side of the protective film forming film side. Support sheet for the antistatic layer on the surface (in this manual, sometimes referred to as "backside antistatic layer"); with a substrate with antistatic properties (in this manual, sometimes referred to as "antistatic substrate" ) As a support sheet for the antistatic layer; provided with a substrate, and provided with an antistatic layer formed on the substrate in the protective film forming composite sheet on the side of the protective film forming film (in this specification, Sometimes referred to as "surface antistatic layer") support sheet. The aforementioned antistatic layer (backside antistatic layer, antistatic base material and surface antistatic layer) all contain an antistatic agent.

亦即，作為較佳的前述保護膜形成用複合片，可列舉：前述支撐片具備基材、及形成於前述基材的單面或雙面上之抗靜電層之保護膜形成用複合片；前述支撐片具備具有抗靜電性之基材(亦即，抗靜電性基材)作為抗靜電層之保護膜形成用複合片。 本說明書中，所謂「形成於基材的單面上之抗靜電層」，意指「前述背面抗靜電層或表面抗靜電層」。並且，所謂「形成於基材的雙面上之抗靜電層」，意指「前述背面抗靜電層及表面抗靜電層之組合」。 這些之中，更佳為前述支撐片具備前述基材及背面抗靜電層之保護膜形成用複合片、或者前述支撐片具備前述抗靜電性基材之保護膜形成用複合片。That is, as a preferable composite sheet for forming a protective film, a composite sheet for forming a protective film in which the support sheet includes a substrate and an antistatic layer formed on one or both sides of the substrate; The aforementioned support sheet is provided with a base material having antistatic properties (that is, an antistatic base material) as a composite sheet for forming a protective film of the antistatic layer. In this specification, the "antistatic layer formed on one side of the substrate" means "the aforementioned back antistatic layer or surface antistatic layer". In addition, the "antistatic layer formed on both sides of the substrate" means "the combination of the aforementioned back antistatic layer and the surface antistatic layer". Among these, more preferable is a composite sheet for forming a protective film in which the support sheet includes the substrate and a back antistatic layer, or a composite sheet for forming a protective film in which the support sheet includes the antistatic substrate.

作為前述保護膜形成用複合片，亦可列舉：具備不符合前述背面抗靜電層、前述抗靜電性基材、及前述表面抗靜電層之任一者之層作為抗靜電層之片。 例如，抗靜電層可設置於保護膜形成用膜中之與支撐片側為相反側的面上，亦可保護膜形成用膜具有抗靜電性。但是，於使用此種保護膜形成用複合片，一邊充分地抑制剝離帶電，一邊製造半導體裝置之情形時，經由抗靜電層(亦即，設置於保護膜形成用膜中之與支撐片側為相反側的面上之抗靜電層、或者具有抗靜電性之保護膜形成用膜)被貼附於半導體晶片之狀態，將抗靜電層組入至半導體裝置。此種情形時，於製造半導體裝置之過程中，有可能無法穩定地維持經由抗靜電層將保護膜形成用膜或保護膜貼附於半導體晶圓或半導體晶片之狀態、以及／或者將具有抗靜電性之保護膜形成用膜或保護膜貼附於半導體晶圓或半導體晶片之狀態。另外，半導體裝置中，抗靜電層有可能會對半導體裝置的結構的穩定性、或半導體裝置的性能造成不良影響。 另外，例如抗靜電層亦可設置於保護膜形成用膜中之支撐片側的面上。但是，於使用此種保護膜形成用複合片製造半導體裝置之情形時，將貼附有保護膜形成用膜或保護膜之半導體晶片自支撐片上的抗靜電層扯離而進行拾取時，有可能因介存有抗靜電層而產生步驟異常。 另一方面，藉由使用前述背面抗靜電層、前述抗靜電性基材或前述表面抗靜電層作為抗靜電層，不僅於將剝離膜自保護膜形成用膜移除時，而且於保護膜形成用複合片的製造過程以及／或者保存過程中的更多情況下，能夠抑制因帶電而產生不良情況。 就如上之觀點而言，前述保護膜形成用複合片較佳為具備前述背面抗靜電層、前述抗靜電性基材或前述表面抗靜電層作為抗靜電層。The composite sheet for forming a protective film may also include a sheet having a layer that does not conform to any of the back antistatic layer, the antistatic base material, and the surface antistatic layer as an antistatic layer. For example, the antistatic layer may be provided on the surface opposite to the support sheet side of the film for protective film formation, or the film for protective film formation may have antistatic properties. However, when using such a composite sheet for forming a protective film to sufficiently suppress peeling and charging while manufacturing a semiconductor device, the antistatic layer (that is, the one provided in the protective film forming film opposite to the support sheet side) The state where the antistatic layer on the side surface or the antistatic protective film forming film) is attached to the semiconductor wafer, and the antistatic layer is incorporated into the semiconductor device. In this case, in the process of manufacturing the semiconductor device, it may not be possible to stably maintain the state in which the protective film forming film or the protective film is attached to the semiconductor wafer or semiconductor wafer via the antistatic layer, and/or it may be resistant A state in which the electrostatic protective film formation film or protective film is attached to the semiconductor wafer or semiconductor chip. In addition, in the semiconductor device, the antistatic layer may adversely affect the structural stability of the semiconductor device or the performance of the semiconductor device. In addition, for example, an antistatic layer may be provided on the surface on the side of the support sheet in the film for forming a protective film. However, when manufacturing a semiconductor device using such a composite sheet for forming a protective film, the semiconductor wafer to which the protective film forming film or protective film is attached is separated from the antistatic layer on the supporting sheet and picked up. The steps are abnormal due to the presence of an antistatic layer. On the other hand, by using the back surface antistatic layer, the antistatic substrate, or the surface antistatic layer as the antistatic layer, not only when the release film is removed from the protective film forming film, but also when the protective film is formed In more cases in the manufacturing process and/or storage process of the composite sheet, it is possible to suppress the occurrence of defects due to electrification. From the above viewpoints, the composite sheet for forming a protective film preferably includes the back surface antistatic layer, the antistatic base material, or the surface antistatic layer as an antistatic layer.

以下，按照抗靜電層的每種配置形態，一邊參照圖式一邊說明前述保護膜形成用複合片的整體構成的示例。此外，以下之說明中所使用之圖中，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，而並不限於各構成要素的尺寸比率等與實際相同。Hereinafter, an example of the overall configuration of the composite sheet for forming a protective film will be described with reference to the drawings for each arrangement form of the antistatic layer. In addition, in the figures used in the following description, in order to facilitate understanding of the characteristics of the present invention and for convenience, the main parts may be enlarged and shown, and the dimensional ratios and the like of each component are not limited to the same as the actual ones.

首先，先對具備前述背面抗靜電層作為抗靜電層之保護膜形成用複合片進行說明。First, the composite sheet for forming a protective film provided with the back surface antistatic layer as the antistatic layer will be described.

圖1係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 此處所示之保護膜形成用複合片101具備支撐片10、及形成於支撐片10的一面(本說明書中，有時稱為「第1面」)10a上之保護膜形成用膜13。Fig. 1 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. The composite sheet 101 for forming a protective film shown here includes a supporting sheet 10 and a protective film forming film 13 formed on one surface (in this specification, sometimes referred to as "first surface") 10a of the supporting sheet 10.

支撐片10具備基材11、形成於基材11的一面(本說明書中，有時稱為「第1面」)11a上之黏著劑層12、及形成於基材11的另一面(本說明書中，有時稱為「第2面」)11b上之背面抗靜電層17。亦即，支撐片10係背面抗靜電層17、基材11及黏著劑層12依序於這些層的厚度方向上積層而構成。換言之，支撐片10的第1面10a係黏著劑層12中之與基材11側為相反側的面(本說明書中，有時稱為「第1面」)12a。The support sheet 10 includes a substrate 11, an adhesive layer 12 formed on one side of the substrate 11 (in this specification, sometimes referred to as the "first side") 11a, and an adhesive layer 12 formed on the other side of the substrate 11 (in this specification) Among them, sometimes referred to as "the second surface") the back antistatic layer 17 on the 11b. That is, the support sheet 10 is formed by stacking the back antistatic layer 17, the base material 11, and the adhesive layer 12 sequentially in the thickness direction of these layers. In other words, the first surface 10a of the support sheet 10 is the surface 12a on the side opposite to the substrate 11 side in the adhesive layer 12 (in this specification, it may be referred to as the "first surface").

亦即，保護膜形成用複合片101係背面抗靜電層17、基材11、黏著劑層12及保護膜形成用膜13依序於這些層的厚度方向上積層而構成。另外，保護膜形成用複合片101進而於保護膜形成用膜13上具備剝離膜15。That is, the composite sheet 101 for forming a protective film is constituted by stacking the back antistatic layer 17, the base material 11, the adhesive layer 12, and the film 13 for forming the protective film in order in the thickness direction of these layers. In addition, the composite sheet 101 for forming a protective film further includes a release film 15 on the film 13 for forming a protective film.

保護膜形成用複合片101中，於黏著劑層12的第1面12a的整面或大致整面積層有保護膜形成用膜13，於保護膜形成用膜13中之與黏著劑層12側為相反側的面(本說明書中，有時稱為「第1面」)13a的一部分、亦即周緣部附近的區域積層有治具用接著劑層16，於保護膜形成用膜13的第1面13a中未積層有治具用接著劑層16之面及治具用接著劑層16中之與黏著劑層12側為相反側的面(本說明書中，有時稱為「第1面」)16a積層有剝離膜15。In the protective film forming composite sheet 101, the protective film forming film 13 is layered on the entire surface or substantially the entire area of the first surface 12a of the adhesive layer 12, and the protective film forming film 13 is on the side of the adhesive layer 12 An adhesive layer 16 for jigs is laminated on a part of the opposite surface (in this specification, sometimes referred to as the "first surface") 13a, that is, the area near the peripheral edge, and on the first surface of the protective film forming film 13 One surface 13a is not laminated with the jig adhesive layer 16 and the jig adhesive layer 16 is on the opposite side to the adhesive layer 12 side (in this specification, sometimes referred to as "the first surface ") 16a has a release film 15 laminated.

保護膜形成用複合片101中，亦可於剝離膜15與和該剝離膜15直接接觸之層之間產生一部分間隙。 例如，此處表示於治具用接著劑層16的側面16c接觸(積層)有剝離膜15之狀態，但亦有於前述側面16c未接觸有剝離膜15之情況。另外，此處表示於保護膜形成用膜13的第1面13a中之治具用接著劑層16的附近區域接觸(積層)有剝離膜15之狀態，但亦有於前述區域未接觸有剝離膜15之情況。 另外，亦有無法明確區別治具用接著劑層16的第1面16a及側面16c之邊界之情形。這些於具備治具用接著劑層之其他實施形態的保護膜形成用複合片中亦相同。In the composite sheet 101 for forming a protective film, a part of a gap may be formed between the release film 15 and the layer directly in contact with the release film 15. For example, here is shown a state where the release film 15 is in contact (laminated) on the side surface 16c of the adhesive layer 16 for jigs, but there may be a case where the release film 15 is not in contact with the side surface 16c. In addition, here is shown a state where the peeling film 15 is in contact (laminated) in the vicinity of the jig adhesive layer 16 on the first surface 13a of the protective film forming film 13, but there is also a peeling off in the aforementioned area. The case of film 15. In addition, there are cases where the boundary between the first surface 16a and the side surface 16c of the adhesive layer 16 for jigs cannot be clearly distinguished. These are the same also in the composite sheet for protective film formation of another embodiment provided with the adhesive layer for jigs.

支撐片中所使用之加工前的基材中，通常該基材的單面或雙面成為具有凹凸形狀之凹凸面。原因在於，若不具有此種凹凸面，則於將基材捲取成捲筒時，基材彼此的接觸面貼附而黏連，使用變得困難。若基材彼此的接觸面中至少一面為凹凸面，則接觸面的面積變小，因此能夠抑制黏連。 因此，保護膜形成用複合片101中，基材11的第1面11a及第2面11b之任一面或兩面可為凹凸面。並且，於基材11的第1面11a及第2面11b之僅任一面為凹凸面之情形時，哪個面為凹凸面皆可。該情形時，另一面成為凹凸度低之平滑面。 此種凹凸面及平滑面的條件於具備基材11之其他保護膜形成用複合片中亦相同。In the base material before processing used in the support sheet, usually one or both sides of the base material have uneven surfaces. The reason is that if there is no such uneven surface, when the base material is wound into a roll, the contact surfaces of the base materials adhere to each other and stick, and use becomes difficult. If at least one of the contact surfaces of the substrates is a concave-convex surface, the area of the contact surface becomes small, so blocking can be suppressed. Therefore, in the composite sheet 101 for forming a protective film, either or both surfaces of the first surface 11a and the second surface 11b of the base material 11 may be uneven surfaces. In addition, when only one of the first surface 11a and the second surface 11b of the substrate 11 is an uneven surface, either surface may be an uneven surface. In this case, the other surface becomes a smooth surface with low unevenness. The conditions for such a concave-convex surface and a smooth surface are also the same in other composite sheets for forming a protective film including the base material 11.

治具用接著劑層16係用以將保護膜形成用複合片101固定於環狀框架等治具。 治具用接著劑層16例如可具有含有接著劑成分之單層結構，亦可具有於成為芯材之片的雙面積層有含有接著劑成分之層之多層結構。The adhesive layer 16 for a jig is used to fix the composite sheet 101 for forming a protective film to a jig such as a ring frame. The adhesive layer 16 for jigs may have, for example, a single-layer structure containing an adhesive component, or a multilayer structure in which a double-area layer of a sheet used as a core material has a layer containing an adhesive component.

背面抗靜電層17含有抗靜電劑。藉此，保護膜形成用複合片101的帶電壓的半衰期成為20秒以下，於將剝離膜15自保護膜形成用膜13移除時，保護膜形成用複合片101顯示剝離帶電的抑制效果。 此外，符號17a表示背面抗靜電層17中之基材11側的面(本說明書中，有時稱為「第1面」)。The back antistatic layer 17 contains an antistatic agent. Thereby, the half-life of the charging voltage of the protective film formation composite sheet 101 becomes 20 seconds or less, and when the peeling film 15 is removed from the protective film formation film 13, the protective film formation composite sheet 101 exhibits a peeling charge suppression effect. In addition, the symbol 17a indicates the surface on the side of the substrate 11 in the back antistatic layer 17 (in this specification, it may be referred to as the "first surface").

保護膜形成用複合片101係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜13的第1面13a貼附半導體晶圓(省略圖示)的內面，進而將治具用接著劑層16的第1面16a貼附於環狀框架等治具。The composite sheet 101 for forming a protective film is used in the following manner, that is, with the release film 15 removed, the inner surface of a semiconductor wafer (not shown) is attached to the first surface 13a of the film 13 for forming a protective film Then, the first surface 16a of the jig adhesive layer 16 is attached to jigs such as a ring frame.

圖2係以示意方式表示本發明的另一實施形態的保護膜形成用複合片之剖視圖。 此外，於圖2以後的圖中，對與既已說明之圖所示相同的構成要素，標附與該已說明之圖之情形相同的符號，並省略該構成要素之詳細說明。Fig. 2 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment of the present invention. In addition, in the drawings after FIG. 2, the same components as those shown in the previously described diagrams are assigned the same reference numerals as in the previously described diagrams, and detailed descriptions of the components are omitted.

此處所示之保護膜形成用複合片102除保護膜形成用膜的形狀及大小不同，且治具用接著劑層積層於黏著劑層的第1面而不積層於保護膜形成用膜的第1面之方面以外，與圖1所示之保護膜形成用複合片101相同。The protective film forming composite sheet 102 shown here differs in the shape and size of the protective film forming film, and the jig adhesive is laminated on the first side of the adhesive layer instead of being laminated on the protective film forming film Except for the first surface, it is the same as the composite sheet 101 for forming a protective film shown in FIG. 1.

更具體而言，保護膜形成用複合片102中，保護膜形成用膜23係積層於黏著劑層12的第1面12a的一部分區域、亦即黏著劑層12的寬度方向(圖2中的左右方向)的中央側的區域。進而，於黏著劑層12的第1面12a中未積層有保護膜形成用膜23之面、亦即周緣部附近的區域積層有治具用接著劑層16。並且，於保護膜形成用膜23中之與黏著劑層12側為相反側的面(本說明書中，有時稱為「第1面」)23a及治具用接著劑層16的第1面16a積層有剝離膜15。More specifically, in the protective film forming composite sheet 102, the protective film forming film 23 is laminated on a partial area of the first surface 12a of the adhesive layer 12, that is, in the width direction of the adhesive layer 12 (Fig. 2 The area on the central side of the left-right direction). Furthermore, the adhesive layer 16 for jigs is laminated|stacked on the surface where the film 23 for protective film formation is not laminated|stacked on the 1st surface 12a of the adhesive layer 12, ie, the area|region near the peripheral part. In addition, the surface of the protective film forming film 23 opposite to the adhesive layer 12 side (in this specification, sometimes referred to as the "first surface") 23a and the first surface of the jig adhesive layer 16 The release film 15 is laminated on 16a.

自上方往下俯視保護膜形成用複合片102時，保護膜形成用膜23的第1面23a的表面積小於黏著劑層12的第1面12a(亦即，合併積層有保護膜形成用膜23之區域與未積層有保護膜形成用膜23之區域所得之區域)，例如具有圓形狀等平面形狀。When the protective film forming composite sheet 102 is viewed from above, the surface area of the first surface 23a of the protective film forming film 23 is smaller than that of the first surface 12a of the adhesive layer 12 (that is, the protective film forming film 23 is laminated The region and the region where the protective film forming film 23 is not laminated) have a planar shape such as a circular shape.

保護膜形成用複合片102中，亦可於剝離膜15與和該剝離膜15直接接觸之層之間產生一部分間隙。 例如，此處表示於保護膜形成用膜23的側面23c接觸(積層)有剝離膜15之狀態，但亦有於前述側面23c未接觸有剝離膜15之情況。另外，此處表示於黏著劑層12的表面12a中未積層有保護膜形成用膜23及治具用接著劑層16之區域接觸(積層)有剝離膜15之狀態，但亦有於前述區域未接觸有剝離膜15之情況。 另外，亦有無法明確區別保護膜形成用膜23的第1面23a及側面23c之邊界之情形。這些於具備相同的形狀及大小的保護膜形成用膜之其他實施形態的保護膜形成用複合片中亦相同。In the composite sheet 102 for forming a protective film, a part of a gap may be formed between the release film 15 and the layer directly in contact with the release film 15. For example, here is shown a state where the release film 15 is in contact (laminated) on the side surface 23c of the protective film forming film 23, but there are cases where the release film 15 is not in contact with the side surface 23c. In addition, it is shown here that the area where the protective film forming film 23 and the jig adhesive layer 16 are not laminated on the surface 12a of the adhesive layer 12 is in contact (laminated) with the release film 15, but it is also in the aforementioned area The release film 15 is not in contact. In addition, there are cases where the boundary between the first surface 23a and the side surface 23c of the protective film forming film 23 cannot be clearly distinguished. These are also the same in the composite sheet for protective film formation of another embodiment which has the film for protective film formation of the same shape and size.

保護膜形成用複合片102的帶電壓的半衰期為20秒以下，於將剝離膜15自保護膜形成用膜23移除時，保護膜形成用複合片102顯示剝離帶電的抑制效果。The protective film forming composite sheet 102 has a charging voltage half-life of 20 seconds or less, and when the peeling film 15 is removed from the protective film forming film 23, the protective film forming composite sheet 102 exhibits a peeling charge suppression effect.

保護膜形成用複合片102係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜23的第1面23a貼附半導體晶圓(省略圖示)的內面，進而將治具用接著劑層16的第1面16a貼附於環狀框架等治具。The composite sheet 102 for forming a protective film is used in the following manner, that is, with the release film 15 removed, the inner surface of a semiconductor wafer (not shown) is attached to the first surface 23a of the film 23 for forming a protective film Then, the first surface 16a of the jig adhesive layer 16 is attached to jigs such as a ring frame.

圖3係以示意方式表示本發明的又一實施形態的保護膜形成用複合片之剖視圖。 此處所示之保護膜形成用複合片103除不具備治具用接著劑層16之方面以外，與圖2所示之保護膜形成用複合片102相同。Fig. 3 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment of the present invention. The composite sheet 103 for forming a protective film shown here is the same as the composite sheet 102 for forming a protective film shown in FIG. 2 except that it does not have the adhesive layer 16 for jigs.

保護膜形成用複合片103的帶電壓的半衰期為20秒以下，於將剝離膜15自保護膜形成用膜23移除時，保護膜形成用複合片103顯示剝離帶電的抑制效果。The composite sheet 103 for protective film formation has a charging voltage half-life of 20 seconds or less, and when the release film 15 is removed from the film 23 for protective film formation, the composite sheet 103 for protective film formation exhibits a peeling charge suppression effect.

保護膜形成用複合片103係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜23的第1面23a貼附半導體晶圓(省略圖示)的內面，進而將黏著劑層12的第1面12a中未積層有保護膜形成用膜23之區域貼附於環狀框架等治具。The protective film forming composite sheet 103 is used in the following manner, that is, in a state where the release film 15 is removed, the inner surface of the semiconductor wafer (not shown) is attached to the first surface 23a of the protective film forming film 23 Furthermore, the region where the protective film forming film 23 is not laminated on the first surface 12a of the adhesive layer 12 is attached to a jig such as a ring frame.

圖4係以示意方式表示本發明的又一實施形態的保護膜形成用複合片之剖視圖。 此處所示之保護膜形成用複合片104除於黏著劑層12與保護膜形成用膜23之間進而具備中間層18之方面以外，與圖3所示之保護膜形成用複合片103相同。保護膜形成用複合片104於黏著劑層12的第1面12a上具備中間層18。中間層18中之與黏著劑層12側為相反側的面(本說明書中，有時稱為「第1面」)18a係保護膜形成用膜23的積層面。Fig. 4 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment of the present invention. The composite sheet 104 for forming a protective film shown here is the same as the composite sheet 103 for forming a protective film shown in FIG. 3 except that it is provided with an intermediate layer 18 between the adhesive layer 12 and the film 23 for forming a protective film . The composite sheet 104 for forming a protective film includes an intermediate layer 18 on the first surface 12 a of the adhesive layer 12. The surface of the intermediate layer 18 opposite to the adhesive layer 12 side (in this specification, it may be referred to as the "first surface") 18a is the layered surface of the protective film forming film 23.

亦即，保護膜形成用複合片104係背面抗靜電層17、基材11、黏著劑層12、中間層18及保護膜形成用膜23依序於這些層的厚度方向上積層而構成。另外，保護膜形成用複合片104進而於保護膜形成用膜23上具備剝離膜15。That is, the composite sheet 104 for forming a protective film is constructed by stacking the back antistatic layer 17, the base material 11, the adhesive layer 12, the intermediate layer 18, and the film 23 for forming the protective film in this order in the thickness direction of these layers. In addition, the composite sheet 104 for forming a protective film further includes a release film 15 on the film 23 for forming a protective film.

保護膜形成用複合片104中，中間層18配置於保護膜形成用膜23與黏著劑層12之間，配置於不成為最表層之中間位置。 中間層18只要為於此種配置位置發揮該中間層18的功能之層，則並無特別限定。 作為中間層18，更具體而言，例如可列舉一面經剝離處理之剝離性改善層。前述剝離性改善層具有如下功能：將具備保護膜形成用膜或保護膜之半導體晶片自支撐片扯離(剝離)而進行拾取時，提高該半導體晶片自支撐片之剝離性。In the composite sheet 104 for protective film formation, the intermediate layer 18 is arrange|positioned between the film 23 for protective film formation and the adhesive layer 12, and is arrange|positioned in the middle position which does not become an outermost layer. The intermediate layer 18 is not particularly limited as long as it is a layer that performs the function of the intermediate layer 18 at such an arrangement position. As the intermediate layer 18, more specifically, for example, a releasability improvement layer having a peeling treatment on one side can be cited. The releasability improving layer has a function of improving the releasability of the semiconductor wafer from the support sheet when the semiconductor wafer provided with the protective film forming film or the protective film is pulled (peeled off) from the support sheet and picked up.

中間層18的第1面18a與保護膜形成用膜23中之黏著劑層12側的面(本說明書中，有時稱為「第2面」)23b接觸。 自上方往下俯視保護膜形成用複合片104時，中間層18的形狀(亦即，平面形狀)及大小只要中間層18能夠發揮該中間層18的功能，則並無特別限定。但為了充分地發揮中間層18的功能，較佳為中間層18的第1面18a與保護膜形成用膜23的第2面23b的整面接觸。為此，較佳為中間層18的第1面18a相對於保護膜形成用膜23的第2面23b具有同等以上的面積。另一方面，中間層18中之黏著劑層12側的面(本說明書中，有時稱為「第2面」)18b可與黏著劑層12的第1面12a的整面接觸，亦可僅與黏著劑層12的第1面12a的一部分區域接觸。但為了充分地發揮中間層18的功能，較佳為黏著劑層12的第1面12a與中間層18的第2面18b的整面接觸。 作為較佳的中間層18，例如可列舉該中間層18的第1面18a的面積及形狀與保護膜形成用膜23的第2面23b的面積及形狀同等之層。The first surface 18a of the intermediate layer 18 is in contact with the surface 23b on the side of the adhesive layer 12 in the protective film forming film 23 (in this specification, it may be referred to as the "second surface") 23b. When the composite sheet 104 for forming a protective film is viewed from above, the shape (that is, the planar shape) and the size of the intermediate layer 18 are not particularly limited as long as the intermediate layer 18 can perform the function of the intermediate layer 18. However, in order to fully exhibit the function of the intermediate layer 18, it is preferable that the first surface 18a of the intermediate layer 18 is in contact with the entire surface of the second surface 23b of the protective film forming film 23. For this reason, it is preferable that the first surface 18a of the intermediate layer 18 has an area equal to or greater than the second surface 23b of the protective film forming film 23. On the other hand, the surface 18b on the side of the adhesive layer 12 in the intermediate layer 18 (in this specification, sometimes referred to as the "second surface") 18b may be in contact with the entire surface of the first surface 12a of the adhesive layer 12, or It is in contact with only a partial area of the first surface 12a of the adhesive layer 12. However, in order to fully exhibit the function of the intermediate layer 18, it is preferable that the entire surface of the first surface 12a of the adhesive layer 12 and the second surface 18b of the intermediate layer 18 be in contact with each other. As a preferable intermediate layer 18, the area and shape of the 1st surface 18a of the intermediate layer 18 are equivalent to the area and shape of the 2nd surface 23b of the film 23 for protective film formation, for example.

保護膜形成用複合片104中，亦可於剝離膜15與和該剝離膜15直接接觸之層之間產生一部分間隙。 例如，此處表示於中間層18的側面18c接觸(積層)有剝離膜15之狀態，但亦有於前述側面18c未接觸有剝離膜15之情況。另外，此處表示於黏著劑層12的第1面12a中未積層有中間層18之區域，亦包括中間層18的附近區域在內，接觸(積層)有剝離膜15之狀態，但亦有於前述第1面12a中的中間層18的附近區域未接觸有剝離膜15之情況。 另外，亦有無法明確區別中間層18的第1面18a及側面18c之邊界之情形。In the composite sheet 104 for forming a protective film, a part of a gap may be formed between the release film 15 and the layer directly in contact with the release film 15. For example, here is shown a state where the release film 15 is in contact (laminated) on the side surface 18c of the intermediate layer 18, but there are cases where the release film 15 is not in contact with the side surface 18c. In addition, the region where the intermediate layer 18 is not laminated on the first surface 12a of the adhesive layer 12 is shown here, including the area near the intermediate layer 18, and the release film 15 is in contact (laminated), but there are also There is no case where the release film 15 is in contact with the vicinity of the intermediate layer 18 on the first surface 12a. In addition, there are cases where the boundary between the first surface 18a and the side surface 18c of the intermediate layer 18 cannot be clearly distinguished.

保護膜形成用複合片104的帶電壓的半衰期為20秒以下，於將剝離膜15自保護膜形成用膜23移除時，保護膜形成用複合片104顯示剝離帶電的抑制效果。The protective film formation composite sheet 104 has a charging voltage half-life of 20 seconds or less, and when the peeling film 15 is removed from the protective film formation film 23, the protective film formation composite sheet 104 exhibits a peeling charge suppression effect.

保護膜形成用複合片104係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜23的第1面23a貼附半導體晶圓(省略圖示)的內面，進而將黏著劑層12的第1面12a中未積層有中間層18之區域貼附於環狀框架等治具。The composite sheet 104 for forming a protective film is used in the following manner, that is, with the release film 15 removed, the inner surface of a semiconductor wafer (not shown) is attached to the first surface 23a of the film 23 for forming a protective film Then, the area where the intermediate layer 18 is not laminated on the first surface 12a of the adhesive layer 12 is attached to a jig such as a ring frame.

圖5係以示意方式表示本發明的又一實施形態的保護膜形成用複合片之剖視圖。 此處所示之保護膜形成用複合片105除不具備黏著劑層12之方面以外，與圖1所示之保護膜形成用複合片101相同。換言之，保護膜形成用複合片105除具備不具備黏著劑層12之支撐片20代替支撐片10之方面以外，與保護膜形成用複合片101相同。換言之，基材11的第1面11a係支撐片20中之保護膜形成用膜13側的面(本說明書中，有時稱為「第1面」)20a。Fig. 5 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment of the present invention. The composite sheet 105 for forming a protective film shown here is the same as the composite sheet 101 for forming a protective film shown in FIG. 1 except that it does not include the adhesive layer 12. In other words, the composite sheet 105 for protective film formation is the same as the composite sheet 101 for protective film formation except that the support sheet 20 without the adhesive layer 12 is provided instead of the support sheet 10. In other words, the first surface 11a of the base material 11 is the surface of the support sheet 20 on the side of the protective film forming film 13 (in this specification, it may be referred to as the "first surface") 20a.

保護膜形成用複合片105的帶電壓的半衰期為20秒以下，於將剝離膜15自保護膜形成用膜13移除時，保護膜形成用複合片105顯示剝離帶電的抑制效果。The composite sheet 105 for protective film formation has a charging voltage half-life of 20 seconds or less, and when the release film 15 is removed from the film 13 for protective film formation, the composite sheet 105 for protective film formation exhibits a peeling charge suppression effect.

保護膜形成用複合片105係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜13的第1面13a貼附半導體晶圓(省略圖示)的內面，進而將治具用接著劑層16的第1面16a貼附於環狀框架等治具。The composite sheet 105 for forming a protective film is used in the following manner, that is, in a state where the release film 15 is removed, the inner surface of a semiconductor wafer (not shown) is attached to the first surface 13a of the film 13 for forming a protective film Then, the first surface 16a of the jig adhesive layer 16 is attached to jigs such as a ring frame.

具備前述背面抗靜電層作為抗靜電層之保護膜形成用複合片並不限定於圖1至圖5所示之保護膜形成用複合片。例如，本實施形態的保護膜形成用複合片亦可在無損本發明的效果之範圍內，將圖1至圖5所示之保護膜形成用複合片的一部分構成變更或刪除，或者對圖1至圖5所示之保護膜形成用複合片進而追加其他構成。The composite sheet for forming a protective film provided with the aforementioned back antistatic layer as an antistatic layer is not limited to the composite sheet for forming a protective film shown in FIGS. 1 to 5. For example, the composite sheet for forming a protective film of this embodiment may be changed or deleted from a part of the composite sheet for forming a protective film shown in FIGS. To the composite sheet for forming a protective film shown in FIG. 5, other configurations are added.

圖5所示之保護膜形成用複合片不具備黏著劑層。作為不具備黏著劑層之本實施形態的保護膜形成用複合片，除此以外，例如亦可列舉於圖2至圖4所示之保護膜形成用複合片中，省略了黏著劑層之複合片。The composite sheet for forming a protective film shown in FIG. 5 does not have an adhesive layer. In addition to the composite sheet for forming a protective film of this embodiment that does not have an adhesive layer, for example, it can be exemplified in the composite sheet for forming a protective film as shown in FIGS. 2 to 4, and the adhesive layer is omitted. sheet.

另外，圖1、圖2及圖5所示之保護膜形成用複合片具備治具用接著劑層。作為具備治具用接著劑層之本實施形態的保護膜形成用複合片，除這些以外，例如亦可列舉於圖4所示之保護膜形成用複合片中，於黏著劑層的第1面新設置有治具用接著劑層之複合片。該情形時，於前述第1面上的治具用接著劑層的配置位置可與圖1、圖2及圖5所示之保護膜形成用複合片之情形相同。In addition, the composite sheet for forming a protective film shown in FIGS. 1, 2 and 5 includes an adhesive layer for a jig. As the composite sheet for forming a protective film of this embodiment provided with an adhesive layer for jigs, in addition to these, for example, the composite sheet for forming a protective film shown in FIG. 4 can be listed on the first side of the adhesive layer A new composite sheet with an adhesive layer for jigs. In this case, the arrangement position of the adhesive layer for jigs on the first surface can be the same as that of the composite sheet for forming a protective film shown in FIGS. 1, 2 and 5.

另外，圖3至圖4所示之保護膜形成用複合片不具備治具用接著劑層。作為不具備治具用接著劑層之本實施形態的保護膜形成用複合片，除這些以外，例如亦可列舉於圖1及圖5所示之保護膜形成用複合片中，省略了治具用接著劑層之複合片。In addition, the composite sheet for forming a protective film shown in FIGS. 3 to 4 does not include an adhesive layer for a jig. As the composite sheet for forming a protective film of this embodiment that does not have an adhesive layer for a jig, in addition to these, for example, the composite sheet for forming a protective film as shown in FIGS. 1 and 5 can be cited, and the jig is omitted. Composite sheet with adhesive layer.

另外，圖4所示之保護膜形成用複合片具備中間層。作為具備中間層之本實施形態的保護膜形成用複合片，除此以外，例如亦可列舉於圖1、圖2及圖5所示之保護膜形成用複合片中，於保護膜形成用膜的第2面側新設置有中間層之複合片。該情形時，於前述第2面上的中間層的配置形態可與引用圖4進行說明之情形相同。In addition, the composite sheet for forming a protective film shown in FIG. 4 includes an intermediate layer. As the composite sheet for forming a protective film of this embodiment provided with an intermediate layer, in addition to this, for example, the composite sheet for forming a protective film shown in FIG. 1, FIG. 2 and FIG. A composite sheet with an intermediate layer is newly installed on the second surface side of the. In this case, the arrangement form of the intermediate layer on the aforementioned second surface may be the same as that described with reference to FIG. 4.

另外，圖1至圖5所示之保護膜形成用複合片中，除背面抗靜電層、基材、保護膜形成用膜及剝離膜以外，不具備任何層，或僅具備黏著劑層，或者僅具備黏著劑層及中間層。作為本實施形態的保護膜形成用複合片，除這些以外，例如亦可列舉於圖1至圖5所示之保護膜形成用複合片中，具備不符合背面抗靜電層、基材、黏著劑層、中間層、保護膜形成用膜及剝離膜之任一者之其他層之複合片。In addition, the composite sheet for forming a protective film shown in FIGS. 1 to 5 does not have any layers, or only an adhesive layer, except for the back antistatic layer, the base material, the film for forming the protective film, and the release film, or Only the adhesive layer and the intermediate layer are provided. As the composite sheet for forming a protective film of this embodiment, in addition to these, for example, the composite sheet for forming a protective film shown in FIGS. 1 to 5 is provided with a non-compliant backside antistatic layer, a base material, and an adhesive. A composite sheet of any one of a layer, an intermediate layer, a protective film forming film, and a release film.

另外，本實施形態的保護膜形成用複合片中，各層的大小或形狀可根據目的任意調節。In addition, in the composite sheet for forming a protective film of this embodiment, the size or shape of each layer can be arbitrarily adjusted according to the purpose.

其次，對具備前述抗靜電性基材作為抗靜電層之保護膜形成用複合片進行說明。Next, a composite sheet for forming a protective film provided with the antistatic base material as the antistatic layer will be described.

圖6係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 此處所示之保護膜形成用複合片201具備支撐片30、及形成於支撐片30的一面(本說明書中，有時稱為「第1面」)30a上之保護膜形成用膜13。Fig. 6 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. The composite sheet 201 for forming a protective film shown here includes a supporting sheet 30 and a protective film forming film 13 formed on one surface (in this specification, sometimes referred to as "first surface") 30a of the supporting sheet 30.

支撐片30具備抗靜電性基材11'、及形成於抗靜電性基材11'的一面(本說明書中，有時稱為「第1面」)11a'上之黏著劑層12。亦即，支撐片30係抗靜電性基材11'及黏著劑層12於這些層的厚度方向上積層而構成。換言之，支撐片30的第1面30a係黏著劑層12的第1面12a。此外，符號11b'表示抗靜電性基材11'的另一面(本說明書中，有時稱為「第2面」)。The support sheet 30 includes an antistatic base material 11' and an adhesive layer 12 formed on one surface (in this specification, sometimes referred to as "first surface") 11a' of the antistatic base material 11'. That is, the support sheet 30 is formed by stacking the antistatic base material 11' and the adhesive layer 12 in the thickness direction of these layers. In other words, the first surface 30a of the support sheet 30 is the first surface 12a of the adhesive layer 12. In addition, the symbol 11b' indicates the other surface of the antistatic base material 11' (in this specification, it may be referred to as the "second surface").

亦即，保護膜形成用複合片201係抗靜電性基材11'、黏著劑層12及保護膜形成用膜13依序於這些層的厚度方向上積層而構成。另外，保護膜形成用複合片201進而於保護膜形成用膜13上具備剝離膜15。That is, the composite sheet 201 for forming a protective film is constituted by stacking the antistatic base material 11', the adhesive layer 12, and the film 13 for forming the protective film in this order in the thickness direction of these layers. In addition, the composite sheet 201 for forming a protective film further includes a release film 15 on the film 13 for forming a protective film.

保護膜形成用複合片201中，於黏著劑層12的第1面12a的整面或大致整面積層有保護膜形成用膜13，於保護膜形成用膜13的第1面13a的一部分、亦即周緣部附近的區域積層有治具用接著劑層16，於保護膜形成用膜13的第1面13a中未積層有治具用接著劑層16之面及治具用接著劑層16的第1面16a積層有剝離膜15。In the protective film forming composite sheet 201, the protective film forming film 13 is layered on the entire surface or substantially the entire area of the first surface 12a of the adhesive layer 12, and on a part of the first surface 13a of the protective film forming film 13, That is, the jig adhesive layer 16 is laminated in the area near the peripheral edge, and the jig adhesive layer 16 and the jig adhesive layer 16 are not laminated on the first surface 13a of the protective film forming film 13 The release film 15 is laminated on the first surface 16a.

保護膜形成用複合片201除具備抗靜電性基材11'代替背面抗靜電層17及基材11之積層物之方面以外，與圖1所示之保護膜形成用複合片101相同。The composite sheet 201 for forming a protective film is the same as the composite sheet 101 for forming a protective film shown in FIG. 1 except that it is provided with the antistatic base material 11' instead of the laminate of the back surface antistatic layer 17 and the base material 11.

抗靜電性基材11'含有抗靜電劑。藉此，保護膜形成用複合片201的帶電壓的半衰期成為20秒以下，於將剝離膜15自保護膜形成用膜13移除時，保護膜形成用複合片201顯示剝離帶電的抑制效果。The antistatic substrate 11' contains an antistatic agent. Thereby, the half-life of the charging voltage of the protective film formation composite sheet 201 becomes 20 seconds or less, and when the peeling film 15 is removed from the protective film formation film 13, the protective film formation composite sheet 201 exhibits a peeling charge suppression effect.

作為抗靜電性基材11'，例如可列舉除進而含有抗靜電劑之方面以外，與上述之基材11相同的基材。As the antistatic base material 11', for example, the same base material as the aforementioned base material 11 except that it further contains an antistatic agent.

保護膜形成用複合片201係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜13的第1面13a貼附半導體晶圓(省略圖示)的內面，進而將治具用接著劑層16的第1面16a貼附於環狀框架等治具。The composite sheet 201 for forming a protective film is used in the following manner, that is, with the release film 15 removed, the inner surface of a semiconductor wafer (not shown) is attached to the first surface 13a of the film 13 for forming a protective film Then, the first surface 16a of the jig adhesive layer 16 is attached to jigs such as a ring frame.

圖7係以示意方式表示本發明的另一實施形態的保護膜形成用複合片之剖視圖。 此處所示之保護膜形成用複合片202除保護膜形成用膜的形狀及大小不同，且治具用接著劑層積層於黏著劑層的第1面而不積層於保護膜形成用膜的第1面之方面以外，與圖6所示之保護膜形成用複合片201相同。 換言之，保護膜形成用複合片202除具備抗靜電性基材11'代替背面抗靜電層17及基材11之積層物之方面以外，與圖2所示之保護膜形成用複合片102相同。Fig. 7 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment of the present invention. The protective film forming composite sheet 202 shown here differs in the shape and size of the protective film forming film, and the jig adhesive is laminated on the first side of the adhesive layer instead of being laminated on the protective film forming film Except for the first surface, it is the same as the composite sheet 201 for forming a protective film shown in FIG. 6. In other words, the composite sheet 202 for forming a protective film is the same as the composite sheet 102 for forming a protective film shown in FIG. 2 except that it is provided with an antistatic base material 11' instead of the laminate of the back antistatic layer 17 and the base material 11.

亦即，保護膜形成用複合片202係抗靜電性基材11'、黏著劑層12及保護膜形成用膜23依序於這些層的厚度方向上積層而構成。另外，保護膜形成用複合片202進而於保護膜形成用膜23上具備剝離膜15。That is, the composite sheet 202 for forming a protective film is formed by stacking the antistatic base material 11', the adhesive layer 12, and the film 23 for forming a protective film in this order in the thickness direction of these layers. In addition, the composite sheet 202 for forming a protective film further includes a release film 15 on the film 23 for forming a protective film.

保護膜形成用複合片202的帶電壓的半衰期為20秒以下，於將剝離膜15自保護膜形成用膜23移除時，保護膜形成用複合片202顯示剝離帶電的抑制效果。The protective film forming composite sheet 202 has a charging voltage half-life of 20 seconds or less, and when the peeling film 15 is removed from the protective film forming film 23, the protective film forming composite sheet 202 exhibits a peeling charge suppression effect.

保護膜形成用複合片202係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜23的第1面23a貼附半導體晶圓(省略圖示)的內面，進而將治具用接著劑層16的第1面16a貼附於環狀框架等治具。The composite sheet 202 for forming a protective film is used in the following manner, that is, with the release film 15 removed, the inner surface of a semiconductor wafer (not shown) is attached to the first surface 23a of the film 23 for forming a protective film Then, the first surface 16a of the jig adhesive layer 16 is attached to jigs such as a ring frame.

圖8係以示意方式表示本發明的又一實施形態的保護膜形成用複合片之剖視圖。 此處所示之保護膜形成用複合片203除不具備治具用接著劑層16之方面以外，與圖7所示之保護膜形成用複合片202相同。 換言之，保護膜形成用複合片203除具備抗靜電性基材11'代替背面抗靜電層17及基材11之積層物之方面以外，與圖3所示之保護膜形成用複合片103相同。Fig. 8 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment of the present invention. The composite sheet 203 for forming a protective film shown here is the same as the composite sheet 202 for forming a protective film shown in FIG. 7 except that it does not include the adhesive layer 16 for jigs. In other words, the composite sheet 203 for forming a protective film is the same as the composite sheet 103 for forming a protective film shown in FIG. 3 except that it is provided with an antistatic base material 11' instead of the laminate of the back antistatic layer 17 and the base material 11.

保護膜形成用複合片203的帶電壓的半衰期為20秒以下，於將剝離膜15自保護膜形成用膜23移除時，保護膜形成用複合片203顯示剝離帶電的抑制效果。The protective film formation composite sheet 203 has a charging voltage half-life of 20 seconds or less, and when the peeling film 15 is removed from the protective film formation film 23, the protective film formation composite sheet 203 exhibits a peeling charge suppression effect.

保護膜形成用複合片203係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜23的第1面23a貼附半導體晶圓(省略圖示)的內面，進而將黏著劑層12的第1面12a中未積層有保護膜形成用膜23之區域貼附於環狀框架等治具。The protective film forming composite sheet 203 is used in the following manner, that is, with the release film 15 removed, the inner surface of the semiconductor wafer (not shown) is attached to the first surface 23a of the protective film forming film 23 Furthermore, the region where the protective film forming film 23 is not laminated on the first surface 12a of the adhesive layer 12 is attached to a jig such as a ring frame.

圖9係以示意方式表示本發明的又一實施形態的保護膜形成用複合片之剖視圖。 此處所示之保護膜形成用複合片204除於黏著劑層12與保護膜形成用膜23之間進而具備中間層18之方面以外，與圖8所示之保護膜形成用複合片203相同。Fig. 9 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment of the present invention. The composite sheet 204 for forming a protective film shown here is the same as the composite sheet 203 for forming a protective film shown in FIG. 8 except that it is provided with an intermediate layer 18 between the adhesive layer 12 and the film 23 for forming a protective film .

亦即，保護膜形成用複合片204係抗靜電性基材11'、黏著劑層12、中間層18及保護膜形成用膜23依序於這些層的厚度方向上積層而構成。另外，保護膜形成用複合片204進而於保護膜形成用膜23上具備剝離膜15。That is, the composite sheet 204 for forming a protective film is formed by stacking the antistatic base material 11', the adhesive layer 12, the intermediate layer 18, and the film 23 for forming the protective film in order in the thickness direction of these layers. In addition, the composite sheet 204 for forming a protective film further includes a release film 15 on the film 23 for forming a protective film.

進而，換言之，保護膜形成用複合片204除具備抗靜電性基材11'代替背面抗靜電層17及基材11之積層物之方面以外，與圖4所示之保護膜形成用複合片104相同。Furthermore, in other words, the composite sheet 204 for forming a protective film is similar to the composite sheet 104 for forming a protective film shown in FIG. 4, except that it is provided with an antistatic substrate 11' instead of the laminate of the back antistatic layer 17 and the substrate 11. the same.

保護膜形成用複合片204的帶電壓的半衰期為20秒以下，於將剝離膜15自保護膜形成用膜23移除時，保護膜形成用複合片204顯示剝離帶電的抑制效果。The protective film formation composite sheet 204 has a charging voltage half-life of 20 seconds or less, and when the peeling film 15 is removed from the protective film formation film 23, the protective film formation composite sheet 204 exhibits a peeling charge suppression effect.

保護膜形成用複合片204係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜23的第1面23a貼附半導體晶圓(省略圖示)的內面，進而將黏著劑層12的第1面12a中未積層有中間層18之區域貼附於環狀框架等治具。The protective film forming composite sheet 204 is used in the following manner, that is, in a state where the release film 15 is removed, the inner surface of the semiconductor wafer (not shown) is attached to the first surface 23a of the protective film forming film 23 Then, the area where the intermediate layer 18 is not laminated on the first surface 12a of the adhesive layer 12 is attached to a jig such as a ring frame.

圖10係以示意方式表示本發明的又一實施形態的保護膜形成用複合片之剖視圖。 此處所示之保護膜形成用複合片205除不具備黏著劑層12之方面以外，與圖6所示之保護膜形成用複合片201相同。換言之，保護膜形成用複合片205除具備不具備黏著劑層12之支撐片40代替支撐片30之方面以外，與保護膜形成用複合片201相同。Fig. 10 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment of the present invention. The composite sheet 205 for forming a protective film shown here is the same as the composite sheet 201 for forming a protective film shown in FIG. 6 except that it does not include the adhesive layer 12. In other words, the composite sheet 205 for forming a protective film is the same as the composite sheet 201 for forming a protective film except that it is provided with a support sheet 40 without the adhesive layer 12 instead of the support sheet 30.

支撐片40僅由抗靜電性基材11'所構成。此處，換言之，抗靜電性基材11'的第1面11a'係支撐片40中之保護膜形成用膜13側的面(本說明書中，有時稱為「第1面」)40a，且係保護膜形成用膜13的積層面。The support sheet 40 is composed of only the antistatic base material 11'. Here, in other words, the first surface 11a' of the antistatic base material 11' is the surface (in this specification, sometimes referred to as the "first surface") 40a on the side of the protective film formation film 13 in the support sheet 40, And it is the laminated surface of the film 13 for protective film formation.

亦即，保護膜形成用複合片205係抗靜電性基材11'及保護膜形成用膜13依序積層而構成。另外，保護膜形成用複合片205進而於保護膜形成用膜13上具備剝離膜15。That is, the composite sheet 205 for forming a protective film is formed by stacking the antistatic base material 11' and the film 13 for forming a protective film in this order. In addition, the composite sheet 205 for forming a protective film further includes a release film 15 on the film 13 for forming a protective film.

進而，換言之，保護膜形成用複合片205除具備抗靜電性基材11'代替背面抗靜電層17及基材11之積層物之方面以外，與圖5所示之保護膜形成用複合片105相同。Furthermore, in other words, the composite sheet 205 for forming a protective film is similar to the composite sheet 105 for forming a protective film shown in FIG. 5, except that it is provided with an antistatic base material 11' instead of the laminate of the back antistatic layer 17 and the base material 11. the same.

保護膜形成用複合片205的帶電壓的半衰期為20秒以下，於將剝離膜15自保護膜形成用膜13移除時，保護膜形成用複合片205顯示剝離帶電的抑制效果。The composite sheet 205 for protective film formation has a charging voltage half-life of 20 seconds or less, and when the release film 15 is removed from the film 13 for protective film formation, the composite sheet 205 for protective film formation exhibits a peeling charge suppression effect.

保護膜形成用複合片205係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜13的第1面13a貼附半導體晶圓(省略圖示)的內面，進而將治具用接著劑層16的第1面16a貼附於環狀框架等治具。The composite sheet 205 for forming a protective film is used in the following manner, that is, with the release film 15 removed, the inner surface of a semiconductor wafer (not shown) is attached to the first surface 13a of the film 13 for forming a protective film Then, the first surface 16a of the jig adhesive layer 16 is attached to jigs such as a ring frame.

具備前述抗靜電性基材作為抗靜電層之本實施形態的保護膜形成用複合片並不限定於圖6至圖10所示之保護膜形成用複合片。例如，本實施形態的保護膜形成用複合片亦可在無損本發明的效果之範圍內，將圖6至圖10所示之保護膜形成用複合片的一部分構成變更或刪除，或者對圖6至圖10所示之保護膜形成用複合片進而追加其他構成。The composite sheet for forming a protective film of this embodiment provided with the antistatic base material as an antistatic layer is not limited to the composite sheet for forming a protective film shown in FIGS. 6 to 10. For example, the composite sheet for forming a protective film of this embodiment may be changed or deleted from a part of the composite sheet for forming a protective film shown in FIGS. To the composite sheet for forming a protective film shown in FIG. 10, other structures are added.

圖10所示之保護膜形成用複合片不具備黏著劑層。作為不具備黏著劑層之本實施形態的保護膜形成用複合片，除此以外，例如亦可列舉於圖7至圖9所示之保護膜形成用複合片中，省略了黏著劑層之複合片。The composite sheet for forming a protective film shown in FIG. 10 does not have an adhesive layer. In addition to the composite sheet for forming a protective film of this embodiment that does not have an adhesive layer, for example, it can be exemplified in the composite sheet for forming a protective film shown in FIGS. 7 to 9, and the adhesive layer is omitted. sheet.

另外，圖6、圖7及圖10所示之保護膜形成用複合片具備治具用接著劑層。作為具備治具用接著劑層之本實施形態的保護膜形成用複合片，除這些以外，例如亦可列舉於圖9所示之保護膜形成用複合片中，於黏著劑層的第1面新設置有治具用接著劑層之複合片。該情形時，於前述第1面上的治具用接著劑層的配置位置可與圖6、圖7及圖10所示之保護膜形成用複合片之情形相同。In addition, the composite sheet for forming a protective film shown in FIGS. 6, 7 and 10 includes an adhesive layer for a jig. As the composite sheet for forming a protective film of this embodiment provided with an adhesive layer for jigs, in addition to these, for example, in the composite sheet for forming a protective film shown in FIG. 9, on the first side of the adhesive layer A new composite sheet with an adhesive layer for jigs. In this case, the arrangement position of the adhesive layer for jigs on the first surface can be the same as that of the composite sheet for forming a protective film shown in FIGS. 6, 7 and 10.

另外，圖8至圖9所示之保護膜形成用複合片不具備治具用接著劑層。作為不具備治具用接著劑層之本實施形態的保護膜形成用複合片，除這些以外，例如亦可列舉於圖6及圖10所示之保護膜形成用複合片中，省略了治具用接著劑層之複合片。In addition, the composite sheet for forming a protective film shown in FIGS. 8 to 9 does not have an adhesive layer for a jig. As the composite sheet for forming a protective film of this embodiment that does not have an adhesive layer for a jig, in addition to these, for example, the composite sheet for forming a protective film as shown in FIGS. 6 and 10 can be cited, and the jig is omitted. Composite sheet with adhesive layer.

另外，圖9所示之保護膜形成用複合片具備中間層。作為具備中間層之本實施形態的保護膜形成用複合片，除此以外，例如亦可列舉於圖6、圖7及圖10所示之保護膜形成用複合片中，於保護膜形成用膜的第2面新設置有中間層之複合片。該情形時，於前述第2面上的中間層的配置形態可與引用圖9進行說明之情形相同。In addition, the composite sheet for forming a protective film shown in FIG. 9 includes an intermediate layer. As the composite sheet for forming a protective film of this embodiment with an intermediate layer, in addition to this, for example, the composite sheet for forming a protective film shown in FIG. 6, FIG. 7 and FIG. The second side of the new composite sheet is provided with an intermediate layer. In this case, the arrangement form of the intermediate layer on the aforementioned second surface can be the same as that described with reference to FIG. 9.

另外，圖6至圖10所示之保護膜形成用複合片中，除抗靜電性基材、保護膜形成用膜及剝離膜以外，不具備任何層，或僅具備黏著劑層，或者僅具備黏著劑層及中間層。作為本實施形態的保護膜形成用複合片，除這些以外，例如亦可列舉於圖6至圖10所示之保護膜形成用複合片中，具備不符合抗靜電性基材、黏著劑層、中間層、保護膜形成用膜及剝離膜之任一者之其他層之複合片。In addition, the composite sheet for forming a protective film shown in FIGS. 6 to 10 does not have any layers, or only an adhesive layer, or only an antistatic substrate, a film for forming a protective film, and a release film. Adhesive layer and intermediate layer. As the composite sheet for forming a protective film of the present embodiment, in addition to these, for example, the composite sheet for forming a protective film shown in FIGS. 6 to 10 may include a non-compliant antistatic substrate, an adhesive layer, A composite sheet of any one of the intermediate layer, the protective film forming film, and the release film.

另外，本實施形態的保護膜形成用複合片中，亦可於剝離膜與和該剝離膜直接接觸之層之間產生一部分間隙。 另外，本實施形態的保護膜形成用複合片中，各層的大小或形狀可根據目的任意調節。In addition, in the composite sheet for forming a protective film of this embodiment, a part of a gap may be formed between the release film and the layer directly in contact with the release film. In addition, in the composite sheet for forming a protective film of this embodiment, the size or shape of each layer can be arbitrarily adjusted according to the purpose.

其次，對具備前述表面抗靜電層作為抗靜電層之保護膜形成用複合片進行說明。Next, a composite sheet for forming a protective film provided with the aforementioned surface antistatic layer as an antistatic layer will be described.

圖11係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 此處所示之保護膜形成用複合片301具備支撐片50、及形成於支撐片50的一面(本說明書中，有時稱為「第1面」)50a上之保護膜形成用膜13。Fig. 11 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. The composite sheet 301 for forming a protective film shown here includes a supporting sheet 50 and a protective film forming film 13 formed on one surface (in this specification, sometimes referred to as "first surface") 50a of the supporting sheet 50.

支撐片50具備基材11、形成於基材11的第1面11a上之表面抗靜電層19、及形成於表面抗靜電層19中之與基材11側為相反側的面(本說明書中，有時稱為「第1面」)19a上之黏著劑層12。亦即，支撐片50係基材11、表面抗靜電層19及黏著劑層12依序於這些層的厚度方向上積層而構成。換言之，支撐片50的第1面50a係黏著劑層12的第1面12a。The support sheet 50 includes a substrate 11, a surface antistatic layer 19 formed on the first surface 11a of the substrate 11, and a surface formed on the surface antistatic layer 19 opposite to the substrate 11 side (in this specification , Sometimes referred to as "the first side") the adhesive layer 12 on 19a. That is, the support sheet 50 is formed by stacking the base material 11, the surface antistatic layer 19, and the adhesive layer 12 in this order in the thickness direction of these layers. In other words, the first surface 50a of the support sheet 50 is the first surface 12a of the adhesive layer 12.

亦即，保護膜形成用複合片301係基材11、表面抗靜電層19、黏著劑層12及保護膜形成用膜13依序於這些層的厚度方向上積層而構成。另外，保護膜形成用複合片301進而於保護膜形成用膜13上具備剝離膜15。That is, the composite sheet 301 for forming a protective film is composed of a base material 11, a surface antistatic layer 19, an adhesive layer 12, and a film 13 for forming a protective film in order in the thickness direction of these layers. In addition, the composite sheet 301 for forming a protective film further includes a release film 15 on the film 13 for forming a protective film.

保護膜形成用複合片301中，於黏著劑層12的第1面12a的整面或大致整面積層有保護膜形成用膜13，於保護膜形成用膜13的第1面13a的一部分、亦即周緣部附近的區域積層有治具用接著劑層16，於保護膜形成用膜13的第1面13a中未積層有治具用接著劑層16之面及治具用接著劑層16的第1面16a積層有剝離膜15。In the protective film forming composite sheet 301, the protective film forming film 13 is layered on the entire surface or substantially the entire area of the first surface 12a of the adhesive layer 12, and on a part of the first surface 13a of the protective film forming film 13, That is, the jig adhesive layer 16 is laminated in the area near the peripheral edge, and the jig adhesive layer 16 and the jig adhesive layer 16 are not laminated on the first surface 13a of the protective film forming film 13 The release film 15 is laminated on the first surface 16a.

保護膜形成用複合片301除於基材11的第2面11b上不具備背面抗靜電層17，且於基材11的第1面11a上、更具體而言於基材11與黏著劑層12之間具備表面抗靜電層19之方面以外，與圖1所示之保護膜形成用複合片101相同。The composite sheet 301 for forming a protective film does not have the back antistatic layer 17 on the second surface 11b of the substrate 11, and is on the first surface 11a of the substrate 11, more specifically, on the substrate 11 and the adhesive layer Except that the surface antistatic layer 19 is provided between 12, it is the same as the composite sheet 101 for protective film formation shown in FIG.

表面抗靜電層19與上文說明之背面抗靜電層17相同。 亦即，保護膜形成用複合片301可謂為於保護膜形成用複合片101中，將抗靜電層的配置位置自基材11的第2面11b上變更為基材11與黏著劑層12之間之複合片。The surface antistatic layer 19 is the same as the back antistatic layer 17 described above. That is, the composite sheet for forming a protective film 301 can be said to be that in the composite sheet 101 for forming a protective film, the position of the antistatic layer is changed from the second surface 11b of the base material 11 to between the base material 11 and the adhesive layer 12 Between the composite film.

表面抗靜電層19含有抗靜電劑。藉此，保護膜形成用複合片301的帶電壓的半衰期成為20秒以下，於將剝離膜15自保護膜形成用膜13移除時，保護膜形成用複合片301顯示剝離帶電的抑制效果。 此外，符號19a表示表面抗靜電層19中之與基材11側為相反側的面(本說明書中，有時稱為「第1面」)。The surface antistatic layer 19 contains an antistatic agent. Thereby, the half-life of the charging voltage of the protective film forming composite sheet 301 becomes 20 seconds or less, and when the peeling film 15 is removed from the protective film forming film 13, the protective film forming composite sheet 301 exhibits a peeling charge suppression effect. In addition, the symbol 19a indicates the surface of the surface antistatic layer 19 on the side opposite to the substrate 11 side (in this specification, it may be referred to as the "first surface").

保護膜形成用複合片301係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜13的第1面13a貼附半導體晶圓(省略圖示)的內面，進而將治具用接著劑層16的第1面16a貼附於環狀框架等治具。The composite sheet 301 for forming a protective film is used in the following manner, that is, in a state where the release film 15 is removed, the inner surface of a semiconductor wafer (not shown) is attached to the first surface 13a of the film 13 for forming a protective film Then, the first surface 16a of the jig adhesive layer 16 is attached to jigs such as a ring frame.

具備前述表面抗靜電層作為抗靜電層之保護膜形成用複合片並不限定於圖11所示之保護膜形成用複合片。例如，作為本實施形態的保護膜形成用複合片，亦可列舉於圖2至圖5所示之保護膜形成用複合片中，以不具備背面抗靜電層、且於基材的第1面具備表面抗靜電層之方式構成之複合片(換言之，將抗靜電層的配置位置自基材的第2面變更為基材的第1面之複合片)等。The composite sheet for forming a protective film provided with the surface antistatic layer as an antistatic layer is not limited to the composite sheet for forming a protective film shown in FIG. 11. For example, as the composite sheet for forming a protective film of this embodiment, it can also be exemplified in the composite sheet for forming a protective film as shown in FIGS. 2 to 5, which does not have a back antistatic layer and is on the first surface of the substrate. A composite sheet having a surface antistatic layer (in other words, a composite sheet in which the position of the antistatic layer is changed from the second surface of the substrate to the first surface of the substrate), etc.

進而，作為具備前述表面抗靜電層作為抗靜電層之保護膜形成用複合片，並不限定於上述之保護膜形成用複合片，可列舉上文說明之具備背面抗靜電層之保護膜形成用複合片中，將抗靜電層的配置位置自基材的第2面變更為基材的第1面之複合片。Furthermore, as a composite sheet for forming a protective film provided with the aforementioned surface antistatic layer as an antistatic layer, it is not limited to the above-mentioned composite sheet for forming a protective film, and examples of the composite sheet for forming a protective film provided with a backside antistatic layer described above In the composite sheet, the position of the antistatic layer is changed from the second side of the base material to the first side of the base material.

本實施形態的保護膜形成用複合片中，各層的大小或形狀亦可根據目的任意調節。In the composite sheet for forming a protective film of this embodiment, the size or shape of each layer can be adjusted arbitrarily according to the purpose.

前文對具備選自由背面抗靜電層、抗靜電性基材及表面抗靜電層所組成之群組中的僅1種作為抗靜電層之保護膜形成用複合片進行了說明，但本發明的一實施形態的保護膜形成用複合片亦可具備選自由背面抗靜電層、抗靜電性基材及表面抗靜電層所組成之群組中的2種以上(亦即2種或3種)作為抗靜電層。此種保護膜形成用複合片的剝離帶電的抑制效果特別高，結果保護膜形成用膜與半導體晶圓之間的異物混入的抑制效果特別高。The foregoing describes the composite sheet for forming a protective film having only one selected from the group consisting of a back antistatic layer, an antistatic base material, and a surface antistatic layer as an antistatic layer, but one aspect of the present invention The composite sheet for forming a protective film of the embodiment may also have two or more types (that is, two or three types) selected from the group consisting of a back antistatic layer, an antistatic base material, and a surface antistatic layer as the antistatic layer. Electrostatic layer. Such a composite sheet for forming a protective film has a particularly high suppression effect of peeling charge, and as a result, the effect of suppressing mixing of foreign substances between the film for forming a protective film and the semiconductor wafer is particularly high.

此種保護膜形成用複合片中，作為具備前述背面抗靜電層及抗靜電性基材兩者作為抗靜電層之保護膜形成用複合片，例如可列舉於圖1至圖5所示之保護膜形成用複合片中，將基材11置換為抗靜電性基材(例如圖6至圖10所示之保護膜形成用複合片中的抗靜電性基材11')之複合片。換言之，這些保護膜形成用複合片係於圖6至圖10所示之保護膜形成用複合片中，於抗靜電性基材11'的第2面11b'進而設置有背面抗靜電層(例如圖1至圖5所示之保護膜形成用複合片中的背面抗靜電層17)之複合片。In such a composite sheet for forming a protective film, as a composite sheet for forming a protective film having both the aforementioned back antistatic layer and an antistatic substrate as an antistatic layer, for example, the protective film shown in FIGS. 1 to 5 In the composite sheet for film formation, the base material 11 is replaced with an antistatic base material (for example, the antistatic base material 11' in the composite sheet for protective film formation shown in FIGS. 6 to 10). In other words, these composite sheets for forming a protective film are in the composite sheets for forming a protective film shown in FIGS. 6 to 10, and the second surface 11b' of the antistatic base material 11' is further provided with a back antistatic layer (for example The composite sheet of the back antistatic layer 17) in the composite sheet for forming a protective film shown in FIGS. 1 to 5.

圖12所示之保護膜形成用複合片401係於圖1所示之保護膜形成用複合片101中，將基材11置換為抗靜電性基材11'之複合片。保護膜形成用複合片401除具備抗靜電性基材11'代替基材11之方面以外，與保護膜形成用複合片101相同。 保護膜形成用複合片401中的支撐片60係背面抗靜電層17、抗靜電性基材11'及黏著劑層12依序於這些層的厚度方向上積層而構成。換言之，支撐片60的一面(本說明書中，有時稱為「第1面」)60a係黏著劑層12的第1面12a。The composite sheet 401 for forming a protective film shown in FIG. 12 is a composite sheet in which the base material 11 is replaced with an antistatic base material 11' in the composite sheet 101 for forming a protective film shown in FIG. The composite sheet 401 for forming a protective film is the same as the composite sheet 101 for forming a protective film except that it has an antistatic base material 11' instead of the base material 11. The support sheet 60 in the composite sheet 401 for forming a protective film is formed by stacking the back antistatic layer 17, the antistatic base material 11', and the adhesive layer 12 in this order in the thickness direction of these layers. In other words, one side of the support sheet 60 (in this specification, sometimes referred to as the “first side”) 60 a is the first side 12 a of the adhesive layer 12.

保護膜形成用複合片401的帶電壓的半衰期為20秒以下，於將剝離膜15自保護膜形成用膜13移除時，保護膜形成用複合片401顯示剝離帶電的抑制效果。此時的抑制效果較圖1所示之保護膜形成用複合片101及圖6所示之保護膜形成用複合片201之情形大。The protective film forming composite sheet 401 has a charging voltage half-life of 20 seconds or less, and when the peeling film 15 is removed from the protective film forming film 13, the protective film forming composite sheet 401 exhibits a peeling charge suppression effect. The suppression effect at this time is larger than the case of the composite sheet 101 for protective film formation shown in FIG. 1 and the composite sheet 201 for protective film formation shown in FIG.

保護膜形成用複合片401係以與保護膜形成用複合片101及保護膜形成用複合片201之情形相同的方法使用。The composite sheet 401 for protective film formation is used by the same method as the case of the composite sheet 101 for protective film formation and the composite sheet 201 for protective film formation.

具備背面抗靜電層及抗靜電性基材兩者之本實施形態的保護膜形成用複合片中，各層的大小或形狀亦可根據目的任意調節。In the composite sheet for forming a protective film of the present embodiment that includes both a back surface antistatic layer and an antistatic base material, the size or shape of each layer can be adjusted arbitrarily according to the purpose.

另一方面，作為具備前述抗靜電性基材及表面抗靜電層兩者作為抗靜電層之保護膜形成用複合片，例如可列舉：於圖6至圖10所示之保護膜形成用複合片中，於抗靜電性基材11'與於該抗靜電性基材11'的第1面11a'側和抗靜電性基材11'相鄰之層(更具體而言，黏著劑層12或保護膜形成用膜13)之間，進而設置有表面抗靜電層(例如，圖11所示之保護膜形成用複合片301中的表面抗靜電層19)之複合片。On the other hand, as a composite sheet for forming a protective film having both the antistatic base material and the surface antistatic layer as an antistatic layer, for example, the composite sheet for forming a protective film shown in FIGS. 6 to 10 In the antistatic substrate 11' and the layer adjacent to the antistatic substrate 11' on the first surface 11a' side of the antistatic substrate 11' (more specifically, the adhesive layer 12 or Between the protective film formation films 13), a composite sheet having a surface antistatic layer (for example, the surface antistatic layer 19 in the protective film formation composite sheet 301 shown in FIG. 11) is further provided.

圖13所示之保護膜形成用複合片501係保護膜形成用複合片的一例，且係於圖11所示之保護膜形成用複合片301中，將基材11置換為抗靜電性基材11'之複合片。保護膜形成用複合片501除具備抗靜電性基材11'代替基材11之方面以外，與保護膜形成用複合片301相同。 保護膜形成用複合片501中的支撐片70係抗靜電性基材11'、表面抗靜電層19及黏著劑層12依序於這些層的厚度方向上積層而構成。換言之，支撐片70的一面(本說明書中，有時稱為「第1面」)70a係黏著劑層12的第1面12a。The composite sheet for forming a protective film 501 shown in FIG. 13 is an example of a composite sheet for forming a protective film, and is based on the composite sheet for forming a protective film 301 shown in FIG. 11 in which the base material 11 is replaced with an antistatic base material 11' composite film. The composite sheet 501 for forming a protective film is the same as the composite sheet 301 for forming a protective film, except that it is provided with an antistatic base material 11' instead of the base material 11. The support sheet 70 in the composite sheet for forming a protective film 501 is formed by stacking the antistatic base material 11', the surface antistatic layer 19, and the adhesive layer 12 sequentially in the thickness direction of these layers. In other words, one side of the support sheet 70 (in this specification, sometimes referred to as the “first side”) 70 a is the first side 12 a of the adhesive layer 12.

保護膜形成用複合片501的帶電壓的半衰期為20秒以下，於將剝離膜15自保護膜形成用膜13移除時，保護膜形成用複合片501顯示剝離帶電的抑制效果。此時的抑制效果較圖11所示之保護膜形成用複合片301及圖6所示之保護膜形成用複合片201之情形大。The protective film forming composite sheet 501 has a charging voltage half-life of 20 seconds or less. When the peeling film 15 is removed from the protective film forming film 13, the protective film forming composite sheet 501 exhibits a peeling charge suppression effect. The suppression effect at this time is larger than the case of the composite sheet 301 for protective film formation shown in FIG. 11 and the composite sheet 201 for protective film formation shown in FIG.

保護膜形成用複合片501係以與保護膜形成用複合片301及保護膜形成用複合片201之情形相同的方法使用。The composite sheet 501 for forming a protective film is used in the same way as the composite sheet 301 for forming a protective film and the composite sheet 201 for forming a protective film.

具備抗靜電性基材及表面抗靜電層兩者之本實施形態的保護膜形成用複合片中，各層的大小或形狀亦可根據目的任意調節。In the composite sheet for forming a protective film of the present embodiment including both an antistatic base material and a surface antistatic layer, the size or shape of each layer can also be adjusted arbitrarily according to the purpose.

本實施形態的保護膜形成用複合片亦可具備前述背面抗靜電層、抗靜電性基材及表面抗靜電層之全部作為抗靜電層。The composite sheet for forming a protective film of this embodiment may include all of the aforementioned back antistatic layer, antistatic base material, and surface antistatic layer as an antistatic layer.

作為具備背面抗靜電層、抗靜電性基材及表面抗靜電層之全部之保護膜形成用複合片，例如可列舉如下保護膜形成用複合片：具備支撐片、及形成於前述支撐片的一面(亦即第1面)上之保護膜形成用膜，且前述支撐片係背面抗靜電層、抗靜電性基材、表面抗靜電層及黏著劑層依序於這些層的厚度方向上積層而構成，前述黏著劑層朝向前述保護膜形成用膜側而配置。 作為此種保護膜形成用複合片，更具體而言，可列舉於圖12所示之保護膜形成用複合片401中，於抗靜電性基材11'與黏著劑層12之間進而設置有表面抗靜電層(例如圖11所示之表面抗靜電層19)之複合片。As a composite sheet for forming a protective film having all of a back antistatic layer, an antistatic base material, and a surface antistatic layer, for example, the following composite sheet for forming a protective film: provided with a support sheet and formed on one side of the aforementioned support sheet (That is, the first surface) is a protective film forming film, and the aforementioned support sheet is a back surface antistatic layer, an antistatic substrate, a surface antistatic layer, and an adhesive layer that are laminated in the thickness direction of these layers in order. In a configuration, the adhesive layer is arranged toward the film side for forming the protective film. As such a composite sheet for forming a protective film, more specifically, a composite sheet 401 for forming a protective film shown in FIG. 12 is exemplified, in which there is further provided between the antistatic base material 11' and the adhesive layer 12 A composite sheet with a surface antistatic layer (such as the surface antistatic layer 19 shown in FIG. 11).

另外，作為具備背面抗靜電層、抗靜電性基材及表面抗靜電層之全部之保護膜形成用複合片，例如可列舉如下保護膜形成用複合片：具備支撐片、及形成於前述支撐片的一面(亦即第1面)上之保護膜形成用膜，且前述支撐片係背面抗靜電層、抗靜電性基材及表面抗靜電層依序於這些層的厚度方向上積層而構成，前述表面抗靜電層朝向前述保護膜形成用膜側而配置。 作為此種保護膜形成用複合片，更具體而言，可列舉於圖12所示之保護膜形成用複合片401中，設置有表面抗靜電層(例如圖11所示之表面抗靜電層19)代替黏著劑層12之複合片。In addition, as a composite sheet for forming a protective film having all of a back antistatic layer, an antistatic base material, and a surface antistatic layer, for example, the following composite sheet for forming a protective film: provided with a support sheet and formed on the aforementioned support sheet A film for forming a protective film on one side (that is, the first side), and the aforementioned support sheet is composed of a back antistatic layer, an antistatic base material, and a surface antistatic layer in order in the thickness direction of these layers. The said surface antistatic layer is arrange|positioned toward the said film side for protective film formation. As such a composite sheet for forming a protective film, more specifically, a composite sheet 401 for forming a protective film shown in FIG. 12 is provided with a surface antistatic layer (for example, the surface antistatic layer 19 shown in FIG. 11). ) A composite sheet that replaces the adhesive layer 12.

但這些係具備背面抗靜電層、抗靜電性基材及表面抗靜電層之全部之保護膜形成用複合片的一例。However, these are an example of a composite sheet for forming a protective film having all of the back surface antistatic layer, the antistatic base material, and the surface antistatic layer.

如上所述，具備選自由背面抗靜電層、抗靜電性基材及表面抗靜電層所組成之群組中的2種以上之保護膜形成用複合片相較於具備選自由背面抗靜電層、抗靜電性基材及表面抗靜電層所組成之群組中的僅1種之保護膜形成用複合片，剝離帶電的抑制效果高，就該方面而言有利。相對於此，關於具備選自由背面抗靜電層、抗靜電性基材及表面抗靜電層所組成之群組中的僅1種之保護膜形成用複合片，就具有充分的剝離帶電的抑制效果，且此種片能夠低價且簡便地製造之方面而言亦有利。As described above, a composite sheet for forming a protective film having two or more types selected from the group consisting of a back surface antistatic layer, an antistatic base material, and a surface antistatic layer is compared with a composite sheet for forming a protective film selected from a back surface antistatic layer, The composite sheet for forming a protective film of only one type in the group consisting of an antistatic base material and a surface antistatic layer has a high peeling charge suppression effect, which is advantageous in this respect. In contrast, a composite sheet for forming a protective film having only one selected from the group consisting of a back antistatic layer, an antistatic base material, and a surface antistatic layer has a sufficient effect of suppressing peeling charge It is also advantageous in that such a sheet can be manufactured inexpensively and simply.

前文按照抗靜電層的每種配置形態，對前述保護膜形成用複合片的整體構成進行了說明，繼而對支撐片進行說明。In the foregoing, the overall configuration of the composite sheet for forming a protective film has been described for each arrangement form of the antistatic layer, and then the support sheet will be described.

[支撐片的全光線透過率] 前述保護膜形成用複合片中的支撐片的全光線透過率並無特別限定，較佳為70%以上，更佳為75%以上，尤佳為80%以上。藉由前述支撐片的全光線透過率為前述下限值以上，保護膜或保護膜形成用膜的雷射印字性及保護膜的印字視認性提高，能夠更高精度地檢查半導體晶片或保護膜的破裂或缺損。[Total light transmittance of support sheet] The total light transmittance of the supporting sheet in the aforementioned composite sheet for forming a protective film is not particularly limited, and is preferably 70% or more, more preferably 75% or more, and particularly preferably 80% or more. With the total light transmittance of the support sheet being higher than the aforementioned lower limit, the laser printability of the protective film or the protective film forming film and the visibility of the printing of the protective film are improved, and the semiconductor chip or protective film can be inspected with higher accuracy Rupture or defect.

前述保護膜形成用複合片中的支撐片的全光線透過率的上限值並無特別限定，越高越佳。若考慮支撐片的製造容易度、及支撐片的構成自由度的高度等，則支撐片的全光線透過率較佳為99%以下。The upper limit of the total light transmittance of the support sheet in the composite sheet for forming a protective film is not particularly limited, and the higher is the better. Considering the ease of manufacture of the support sheet, the height of the degree of freedom in the configuration of the support sheet, etc., the total light transmittance of the support sheet is preferably 99% or less.

支撐片的全光線透過率亦如後文實施例中所述，可依據JIS K 7375：2008而測定。The total light transmittance of the support sheet is also as described in the examples below, and can be measured in accordance with JIS K 7375:2008.

[支撐片的霧度] 前述保護膜形成用複合片中的支撐片的霧度並無特別限定，較佳為55%以下，更佳為50%以下，尤佳為45%以下。藉由前述支撐片的霧度為前述上限值以下，保護膜或保護膜形成用膜的雷射印字性、保護膜的印字視認性、半導體晶片或保護膜的破裂或缺損的檢查適性提高。[Haze of support sheet] The haze of the support sheet in the composite sheet for forming a protective film is not particularly limited, but is preferably 55% or less, more preferably 50% or less, and particularly preferably 45% or less. When the haze of the support sheet is below the upper limit, the laser printability of the protective film or the protective film forming film, the visibility of the printing of the protective film, and the inspection suitability for cracks or defects of the semiconductor wafer or the protective film are improved.

前述保護膜形成用複合片中的支撐片的霧度的下限值並無特別限定，越低越佳。若考慮支撐片的製造容易度、及支撐片的構成自由度的高度等，則支撐片的霧度亦可為40%以上。The lower limit of the haze of the support sheet in the composite sheet for forming a protective film is not particularly limited, and the lower the limit, the better. Considering the ease of manufacture of the support sheet, the height of the structural freedom of the support sheet, etc., the haze of the support sheet may be 40% or more.

支撐片的霧度可依據JIS K 7136-2000而測定。The haze of the support sheet can be measured in accordance with JIS K 7136-2000.

[抗靜電層的耐擦傷性] 前述保護膜形成用複合片中的抗靜電層的耐擦傷性會對前述複合片的保護膜形成用膜的檢查性造成影響。所謂「抗靜電層的耐擦傷性」，意指藉由其他物品摩擦抗靜電層時，抗靜電層的該摩擦面中的不易損傷之程度。 若抗靜電層的耐擦傷性高，則抗靜電層的表面遍及整面，與其他物品接觸時，不易損傷。因此，經由抗靜電層，使用感測器或藉由目視，將保護膜形成用複合片中的保護膜形成用膜進行光學檢查時，能夠抑制因檢查部位不同所致之檢查結果之偏差，且能夠高精度地檢查。相對於此，若抗靜電層的耐擦傷性低，則抗靜電層的表面的至少一部分與其他物品接觸時，容易損傷。因此，以上述方式檢查保護膜形成用複合片中的保護膜形成用膜時，產生因檢查部位不同所致之檢查結果之偏差，且檢查精度變低。[Scratch resistance of antistatic layer] The scratch resistance of the antistatic layer in the composite sheet for forming a protective film affects the inspectability of the film for forming a protective film of the composite sheet. The so-called "scratch resistance of the antistatic layer" refers to the degree to which the friction surface of the antistatic layer is not easily damaged when the antistatic layer is rubbed by other objects. If the anti-static layer has high scratch resistance, the surface of the anti-static layer is spread over the entire surface, and it is not easily damaged when it comes in contact with other objects. Therefore, when the protective film forming film in the protective film forming composite sheet is optically inspected through the antistatic layer, using a sensor or by visual inspection, it is possible to suppress the deviation of the inspection result due to the difference in the inspection site, and It can be inspected with high accuracy. On the other hand, if the scratch resistance of the antistatic layer is low, when at least a part of the surface of the antistatic layer comes into contact with other articles, it is likely to be damaged. Therefore, when the protective film formation film in the protective film formation composite sheet is inspected in the above-mentioned manner, the inspection result varies due to the difference in the inspection site, and the inspection accuracy becomes low.

抗靜電層的耐擦傷性可利用以下之方法進行評價。 亦即，首先，於用以對抗靜電層施加荷重之按壓機構的表面(以下，稱為「按壓面」)被覆法蘭絨布。此時，前述按壓機構的前述按壓面係設為面積為2cm×2cm之正方形且平面狀之面。另外，法蘭絨布的厚度並無特別限定，例如就評價結果的可靠性極高之方面而言，可為1μm至4μm。被覆於前述按壓面的可為1片法蘭絨布，亦可為2片以上之法蘭絨布於這些布的厚度方向上積層而構成之法蘭絨布之積層片。前述積層片中的各法蘭絨布的厚度可全部相同，亦可全部皆不相同，還可僅一部分相同。於使用前述積層片之情形時，前述積層片的整體的厚度、亦即前述積層片中的各法蘭絨布的厚度的合計可為1μm至4μm。The scratch resistance of the antistatic layer can be evaluated by the following method. That is, first, the surface of the pressing mechanism for applying a load to the antistatic layer (hereinafter referred to as "pressing surface") is covered with flannel cloth. At this time, the pressing surface of the pressing mechanism is a square and flat surface with an area of 2 cm×2 cm. In addition, the thickness of the flannel cloth is not particularly limited. For example, in terms of the reliability of the evaluation result, it may be 1 μm to 4 μm. The pressing surface may be covered by one piece of flannel cloth, or it may be a laminated sheet of flannel cloth formed by laminating two or more pieces of flannel cloth in the thickness direction of these cloths. The thickness of each flannel cloth in the aforementioned laminated sheet may be all the same, all may be different, or only a part may be the same. In the case of using the laminate sheet, the total thickness of the laminate sheet, that is, the total thickness of the flannel fabrics in the laminate sheet may be 1 μm to 4 μm.

繼而，將被覆有前述法蘭絨布之前述按壓機構的前述按壓面壓抵於前述抗靜電層的表面。 繼而，以如此般經由法蘭絨布將按壓機構壓抵於抗靜電層之狀態，一邊藉由按壓機構對抗靜電層施加125g/cm2 之荷重而進行按壓，一邊使按壓機構以10cm之直線距離往返運動10次。藉此，一邊經由法蘭絨布施加125g/cm2 之荷重，一邊摩擦抗靜電層。此時，抗靜電層的表面中被法蘭絨布摩擦的是寬度2cm、長度10cm之區域。Then, the pressing surface of the pressing mechanism covered with the flannel cloth is pressed against the surface of the antistatic layer. Then, in such a state that the pressing mechanism is pressed against the antistatic layer through the flannel cloth, the pressing mechanism applies a load of 125g/cm 2 to the antistatic layer to press, while making the pressing mechanism go back and forth at a linear distance of 10cm Exercise 10 times. Thereby, while applying a load of 125 g/cm 2 through the flannel cloth, rubbing the antistatic layer. At this time, the surface of the antistatic layer that is rubbed by the flannel cloth is an area with a width of 2 cm and a length of 10 cm.

繼而，藉由目視觀察抗靜電層中之該經由法蘭絨布摩擦的面中面積為2cm×2cm之區域，確認有無傷痕，可評價抗靜電層的耐擦傷性。例如，若於觀察部位存在傷痕，則確認到條紋狀的傷痕，或確認到觀察面的光反射性降低而光澤降低。若未確認到傷痕，則可判定為耐擦傷性高，若確認到傷痕，則可判定為耐擦傷性低。 抗靜電層的表面中供目視觀察之前述區域可為被法蘭絨布摩擦之寬度2cm、長度10cm之區域中的任一區域，例如可為前述區域中之長度方向上之包含中央部之區域，亦可為相同方向上之包含端部之區域。Then, by visually observing an area of 2 cm×2 cm in the surface rubbed by the flannel cloth in the antistatic layer, and confirming whether there are scratches, the scratch resistance of the antistatic layer can be evaluated. For example, if there are scars in the observation part, streak-shaped scars are confirmed, or it is confirmed that the light reflectivity of the observation surface is reduced and the gloss is reduced. If the scratch is not confirmed, it can be judged that the scratch resistance is high, and if the scratch is confirmed, it can be judged that the scratch resistance is low. The aforementioned area on the surface of the antistatic layer for visual observation can be any area of 2cm in width and 10cm in length rubbed by the flannel cloth, for example, it can be the area including the central part in the length direction of the aforementioned area, It may also be a region including the end in the same direction.

前述保護膜形成用複合片中的抗靜電層較佳為藉由上述方法評價前述抗靜電層的耐擦傷性時，未確認到傷痕。此處，所謂抗靜電層，意指上文說明之背面抗靜電層、抗靜電性基材及表面抗靜電層，作為更佳的保護膜形成用複合片，例如可列舉具備此種具有耐擦傷性之背面抗靜電層或抗靜電性基材之複合片。The antistatic layer in the composite sheet for forming a protective film is preferably such that when the scratch resistance of the antistatic layer is evaluated by the above method, no scratches are confirmed. Here, the antistatic layer means the back antistatic layer, antistatic base material, and surface antistatic layer described above. As a more preferable composite sheet for forming a protective film, for example, it has such a scratch-resistant A composite sheet with a flexible back antistatic layer or an antistatic substrate.

例如，於保護膜形成用複合片具備選自由背面抗靜電層、抗靜電性基材及表面抗靜電層所組成之群組中的2種以上作為抗靜電層之情形時，較佳為至少保護膜形成用複合片的最外層為耐擦傷性的評價對象。更具體而言，例如於保護膜形成用複合片一併具備背面抗靜電層及抗靜電性基材之情形、及一併具備背面抗靜電層及表面抗靜電層之情形時，較佳為至少背面抗靜電層為耐擦傷性的評價對象。例如於保護膜形成用複合片一併具備抗靜電性基材及表面抗靜電層之情形時，較佳為至少抗靜電性基材為耐擦傷性的評價對象。例如，於保護膜形成用複合片具備背面抗靜電層、抗靜電性基材及表面抗靜電層之全部之情形時，較佳為至少背面抗靜電層為耐擦傷性的評價對象。For example, when the composite sheet for forming a protective film has two or more selected from the group consisting of a back antistatic layer, an antistatic base material, and a surface antistatic layer as the antistatic layer, it is preferable to protect at least The outermost layer of the composite sheet for film formation is an evaluation target of scratch resistance. More specifically, for example, when the composite sheet for forming a protective film is provided with a back antistatic layer and an antistatic substrate, and when a back antistatic layer and a surface antistatic layer are provided together, it is preferably at least The back antistatic layer is an evaluation target for scratch resistance. For example, when the composite sheet for forming a protective film includes an antistatic base material and a surface antistatic layer together, it is preferable that at least the antistatic base material is an evaluation target for scratch resistance. For example, when the composite sheet for forming a protective film is provided with all of the back surface antistatic layer, the antistatic base material, and the surface antistatic layer, it is preferable that at least the back surface antistatic layer is an evaluation target of scratch resistance.

其次，對構成支撐片之各層更詳細地進行說明。Next, each layer constituting the support sheet will be described in more detail.

○基材 以下，對抗靜電性基材以外的基材進行說明。本說明書中，只要無特別說明，則單純的「基材」意指「抗靜電性基材以外的基材」。○Substrate Hereinafter, substrates other than the antistatic substrate will be described. In this specification, unless otherwise specified, the simple "base material" means "base material other than antistatic base material".

前述基材為片狀或膜狀，作為前述基材的構成材料，例如可列舉各種樹脂。 作為前述樹脂，例如可列舉：低密度聚乙烯(LDPE；Low Density Polyethylene)、直鏈低密度聚乙烯(LLDPE；Linear Low Density Polyethylene)、高密度聚乙烯(HDPE；High Density Polyethylene)等聚乙烯；聚丙烯、聚丁烯、聚丁二烯、聚甲基戊烯、降冰片烯樹脂等聚乙烯以外的聚烯烴；乙烯-乙酸乙烯酯共聚物、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物、乙烯-降冰片烯共聚物等乙烯系共聚物(使用乙烯作為單體而獲得之共聚物)；聚氯乙烯、氯乙烯共聚物等氯乙烯系樹脂(使用氯乙烯作為單體而獲得之樹脂)；聚苯乙烯；聚環烯烴；聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯、聚間苯二甲酸乙二酯、聚-2,6-萘二甲酸乙二酯、全部結構單元具有芳香族環式基之全芳香族聚酯等聚酯；2種以上之前述聚酯之共聚物；聚(甲基)丙烯酸酯；聚胺基甲酸酯；聚丙烯酸胺基甲酸酯；聚醯亞胺；聚醯胺；聚碳酸酯；氟樹脂；聚縮醛；改質聚苯醚；聚苯硫醚；聚碸；聚醚酮等。 另外，作為前述樹脂，例如亦可列舉前述聚酯與前述聚酯以外的樹脂之混合物等聚合物合金。前述聚酯與前述聚酯以外的樹脂之聚合物合金較佳為聚酯以外的樹脂的量為相對較少量。 另外，作為前述樹脂，例如亦可列舉：前文例示之前述樹脂中的1種或2種以上交聯而成之交聯樹脂；使用前文例示之前述樹脂中的1種或2種以上之離子聚合物等改質樹脂。The substrate is in a sheet shape or a film shape, and as a constituent material of the substrate, various resins can be cited, for example. Examples of the aforementioned resin include polyethylenes such as low density polyethylene (LDPE; Low Density Polyethylene), linear low density polyethylene (LLDPE; Linear Low Density Polyethylene), and high density polyethylene (HDPE; High Density Polyethylene); Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene- (Meth) acrylate copolymers, ethylene-norbornene copolymers and other vinyl copolymers (copolymers obtained by using ethylene as a monomer); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (using chlorine Resin obtained from ethylene as a monomer); polystyrene; polycyclic olefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate Diesters, poly(ethylene-2,6-naphthalate), wholly aromatic polyesters with aromatic cyclic groups in all structural units; copolymers of two or more of the aforementioned polyesters; poly(methyl) ) Acrylic ester; polyurethane; polyacrylic urethane; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; Polyetherketone; Polyetherketone etc. Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and resin other than the said polyester, can also be mentioned, for example. The polymer alloy of the polyester and the resin other than the polyester preferably has a relatively small amount of the resin other than the polyester. In addition, as the aforementioned resin, for example, a cross-linked resin obtained by cross-linking one or more of the aforementioned resins exemplified above; ionic polymerization using one or more of the aforementioned resins exemplified above Modified resin such as materials.

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

基材可由1層(單層)所構成，亦可由2層以上之多層所構成，於由多層所構成之情形時，這些多層相互可相同亦可不同，這些多層的組合並無特別限定。The substrate may be composed of one layer (single layer) or two or more layers. In the case of multiple layers, these layers may be the same or different from each other, and the combination of these layers is not particularly limited.

基材的厚度較佳為30μm至300μm，更佳為50μm至140μm。藉由基材的厚度為此種範圍，前述保護膜形成用複合片的可撓性、及朝半導體晶圓或半導體晶片之貼附性進一步提高。 此處，所謂「基材的厚度」，意指基材整體的厚度，例如所謂由多層所構成之基材的厚度，意指構成基材之全部層的合計厚度。The thickness of the substrate is preferably 30 μm to 300 μm, more preferably 50 μm to 140 μm. When the thickness of the base material is in this range, the flexibility of the composite sheet for forming a protective film and the adhesion to a semiconductor wafer or a semiconductor wafer are further improved. Here, the "thickness of the base material" means the thickness of the entire base material. For example, the thickness of the base material composed of multiple layers means the total thickness of all layers constituting the base material.

基材較佳為厚度精度高之基材，亦即較佳為無論部位如何厚度不均皆得到抑制之基材。作為上述之構成材料中可用於構成此種厚度精度高之基材之材料，例如可列舉：聚乙烯、聚乙烯以外的聚烯烴、聚對苯二甲酸乙二酯、乙烯-乙酸乙烯酯共聚物等。The substrate is preferably a substrate with high thickness accuracy, that is, a substrate in which thickness unevenness is suppressed regardless of the location. Among the above-mentioned constituent materials, materials that can be used to form such a substrate with high thickness accuracy include, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymers. Wait.

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

基材可為透明，亦可為不透明，還可根據目的而著色，還可蒸鍍其他層。 例如，於保護膜形成用膜具有能量線硬化性之情形時，基材較佳為使能量線透過。 例如，為了經由基材將保護膜形成用複合片中的保護膜形成用膜進行光學檢查，基材較佳為透明。The substrate may be transparent or opaque, and may be colored according to the purpose, and other layers may be vapor-deposited. For example, when the film for forming a protective film has energy ray curability, it is preferable that the base material transmits energy ray. For example, in order to optically inspect the protective film formation film in the protective film formation composite sheet via the base material, the base material is preferably transparent.

為了提高基材與設置於該基材上之層(例如黏著劑層、中間層或保護膜形成用膜)之接著性，亦可對基材表面實施利用噴砂處理、溶劑處理等之凹凸化處理；電暈放電處理、電子束照射處理、電漿處理、臭氧／紫外線照射處理、火焰處理、鉻酸處理、熱風處理等氧化處理等。另外，亦可對基材表面進行底塗處理。In order to improve the adhesion between the substrate and the layer provided on the substrate (such as adhesive layer, intermediate layer or protective film formation film), the surface of the substrate can also be subjected to roughening treatments such as sandblasting, solvent treatment, etc. ;Corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments. In addition, the surface of the substrate can also be primed.

基材可利用公知的方法製造。例如，含有樹脂之基材可藉由將含有前述樹脂之樹脂組成物成形而製造。The substrate can be manufactured by a known method. For example, a resin-containing substrate can be manufactured by molding a resin composition containing the aforementioned resin.

○黏著劑層 前述黏著劑層為片狀或膜狀，且含有黏著劑。 作為前述黏著劑，例如可列舉：丙烯酸系樹脂、胺基甲酸酯系樹脂、橡膠系樹脂、聚矽氧系樹脂、環氧系樹脂、聚乙烯醚、聚碳酸酯、酯系樹脂等黏著性樹脂，較佳為丙烯酸系樹脂。○Adhesive layer The aforementioned adhesive layer is in the form of a sheet or film and contains an adhesive. Examples of the aforementioned adhesives include: acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ether, polycarbonate, ester resins, etc. The resin is preferably an acrylic resin.

此外，本說明書中，「黏著性樹脂」包括具有黏著性之樹脂及具有接著性之樹脂兩者。例如，前述黏著性樹脂不僅包括樹脂本身具有黏著性之樹脂，亦包括藉由與添加劑等其他成分併用而顯示黏著性之樹脂、以及藉由存在熱或水等觸發(trigger)而顯示接著性之樹脂等。In addition, in this specification, "adhesive resin" includes both adhesive resin and adhesive resin. For example, the aforementioned adhesive resins include not only resins that have adhesive properties, but also resins that exhibit adhesiveness when used in combination with additives and other components, and those that exhibit adhesiveness by the presence of heat or water as a trigger. Resin etc.

黏著劑層可由1層(單層)所構成，亦可由2層以上之多層所構成，於由多層所構成之情形時，這些多層相互可相同亦可不同，這些多層的組合並無特別限定。The adhesive layer may be composed of one layer (single layer) or two or more layers. In the case of being composed of multiple layers, these layers may be the same or different from each other, and the combination of these layers is not particularly limited.

黏著劑層的厚度較佳為1μm至100μm，更佳為1μm至60μm，尤佳為1μm至30μm。 此處，所謂「黏著劑層的厚度」，意指黏著劑層整體的厚度，例如所謂由多層所構成之黏著劑層的厚度，意指構成黏著劑層之全部層的合計厚度。The thickness of the adhesive layer is preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, particularly preferably 1 μm to 30 μm. Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer. For example, the thickness of the adhesive layer composed of multiple layers means the total thickness of all layers constituting the adhesive layer.

黏著劑層可為透明，亦可為不透明，還可根據目的而著色。 例如，於保護膜形成用膜具有能量線硬化性之情形時，黏著劑層較佳為使能量線透過。 例如，為了經由黏著劑層將保護膜形成用複合片中的保護膜形成用膜進行光學檢查，黏著劑層較佳為透明。The adhesive layer may be transparent or opaque, and may be colored according to the purpose. For example, when the film for forming a protective film has energy ray curability, the adhesive layer preferably allows the energy ray to pass through. For example, in order to optically inspect the protective film formation film in the composite sheet for protective film formation via the adhesive layer, the adhesive layer is preferably transparent.

黏著劑層可使用能量線硬化性黏著劑而形成，亦可使用非能量線硬化性黏著劑而形成。亦即，黏著劑層可為能量線硬化性及非能量線硬化性之任一種。能量線硬化性的黏著劑層能夠容易地調節硬化前及硬化後的物性。The adhesive layer can be formed using an energy ray-curable adhesive or a non-energy ray-curing adhesive. That is, the adhesive layer may be either energy ray curable or non-energy ray curable. The energy-ray curable adhesive layer can easily adjust the physical properties before and after curing.

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

利用公知的方法塗敷黏著劑組成物即可，例如可列舉使用以下各種塗佈機之方法：氣刀塗佈機、刮刀塗佈機、棒式塗佈機、凹版塗佈機、輥式塗佈機、輥刀塗佈機、簾幕式塗佈機、模具塗佈機、刀式塗佈機、絲網塗佈機、Meyer棒式塗佈機、輕觸式塗佈機等。The adhesive composition can be applied by a known method. For example, the following methods can be cited: 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, touch coater, etc.

於基材上設置黏著劑層之情形時，例如只要於基材上塗敷黏著劑組成物，視需要使之乾燥，藉此於基材上積層黏著劑層即可。另外，於基材上設置黏著劑層之情形時，例如亦可於剝離膜上塗敷黏著劑組成物，視需要使之乾燥，藉此於剝離膜上預先形成黏著劑層，使該黏著劑層的露出面與基材的一表面貼合，藉此於基材上積層黏著劑層。該情形時的剝離膜在保護膜形成用複合片的製造過程或使用過程中的任意時間點移除即可。When the adhesive layer is provided on the substrate, for example, the adhesive composition may be coated on the substrate and dried as necessary, thereby laminating the adhesive layer on the substrate. In addition, when the adhesive layer is provided on the substrate, for example, the adhesive composition may be coated on the release film and dried if necessary, so that an adhesive layer is formed on the release film in advance to make the adhesive layer The exposed surface of the substrate is attached to a surface of the substrate, thereby depositing an adhesive layer on the substrate. The release film in this case may be removed at any point in the manufacturing process or the use process of the composite sheet for protective film formation.

黏著劑組成物的乾燥條件並無特別限定，於黏著劑組成物含有後述溶劑之情形時，較佳為進行加熱乾燥。並且，含有溶劑之黏著劑組成物例如較佳為於70℃至130℃且10秒至5分鐘之條件進行乾燥。The drying conditions of the adhesive composition are not particularly limited, and when the adhesive composition contains a solvent described later, it is preferable to heat and dry. In addition, the solvent-containing adhesive composition is preferably dried at 70°C to 130°C for 10 seconds to 5 minutes, for example.

於黏著劑層為能量線硬化性之情形時，作為含有能量線硬化性黏著劑之黏著劑組成物、亦即能量線硬化性的黏著劑組成物，例如可列舉以下之黏著劑組成物等：黏著劑組成物(I-1)，含有非能量線硬化性的黏著性樹脂(I-1a)(以下，有時簡稱為「黏著性樹脂(I-1a)」)、及能量線硬化性化合物；黏著劑組成物(I-2)，含有於非能量線硬化性的黏著性樹脂(I-1a)的側鏈導入有不飽和基之能量線硬化性的黏著性樹脂(I-2a)(以下，有時簡稱為「黏著性樹脂(I-2a)」)；黏著劑組成物(I-3)，含有前述黏著性樹脂(I-2a)及能量線硬化性化合物。When the adhesive layer is energy ray curable, as an adhesive composition containing an energy ray curable adhesive, that is, an energy ray curable adhesive composition, for example, the following adhesive compositions can be cited: The adhesive composition (I-1) contains a non-energy-ray-curable adhesive resin (I-1a) (hereinafter, sometimes referred to as "adhesive resin (I-1a)"), and an energy-ray-curable compound ; Adhesive composition (I-2), contained in the side chain of non-energy-ray-curable adhesive resin (I-1a), the side chain of the energy-ray-curable adhesive resin (I-2a) ( Hereinafter, it may be simply referred to as "adhesive resin (I-2a)"); the adhesive composition (I-3) contains the aforementioned adhesive resin (I-2a) and an energy ray curable compound.

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

[黏著性樹脂(I-1a)] 前述黏著性樹脂(I-1a)較佳為丙烯酸系樹脂。 作為前述丙烯酸系樹脂，例如可列舉至少具有源自(甲基)丙烯酸烷基酯之結構單元之丙烯酸系聚合物。 前述丙烯酸系樹脂所具有之結構單元可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。[Adhesive resin (I-1a)] The aforementioned adhesive resin (I-1a) is preferably an acrylic resin. As said acrylic resin, the acrylic polymer which has at least the structural unit derived from the alkyl (meth)acrylate is mentioned, for example. The structural unit possessed by the aforementioned acrylic resin may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

作為前述(甲基)丙烯酸烷基酯，例如可列舉構成烷基酯之烷基的碳數為1至20之(甲基)丙烯酸烷基酯，前述烷基較佳為直鏈狀或支鏈狀。 作為(甲基)丙烯酸烷基酯，更具體而言，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯((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((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)、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯等。Examples of the aforementioned alkyl (meth)acrylate include alkyl (meth)acrylates having 1 to 20 carbon atoms in the alkyl group constituting the alkyl ester, and the aforementioned alkyl group is preferably linear or branched. shape. As the alkyl (meth)acrylate, more specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate Base) hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-octyl (meth)acrylate Nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate) , Tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, ten (meth)acrylate Hexaalkyl ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), (meth) Nonadecyl acrylate, eicosyl (meth)acrylate, etc.

就黏著劑層的黏著力提高之方面而言，前述丙烯酸系聚合物較佳為具有源自前述烷基的碳數為4以上之(甲基)丙烯酸烷基酯之結構單元。並且，就黏著劑層的黏著力進一步提高之方面而言，前述烷基的碳數較佳為4至12，更佳為4至8。另外，前述烷基的碳數為4以上之(甲基)丙烯酸烷基酯較佳為丙烯酸烷基酯。In terms of improving the adhesive force of the adhesive layer, the acrylic polymer preferably has a structural unit derived from the alkyl (meth)acrylate alkyl ester having a carbon number of 4 or more. In addition, in terms of further improving the adhesive force of the adhesive layer, the carbon number of the aforementioned alkyl group is preferably 4-12, more preferably 4-8. In addition, the alkyl (meth)acrylate whose alkyl group has 4 or more carbon atoms is preferably an alkyl acrylate.

前述丙烯酸系聚合物較佳為除源自(甲基)丙烯酸烷基酯之結構單元以外，進而具有源自含官能基之單體之結構單元。 作為前述含官能基之單體，例如可列舉以下單體：藉由前述官能基與後述交聯劑反應而成為交聯的起點，或者藉由前述官能基與後述含不飽和基之化合物中的不飽和基反應，能夠於丙烯酸系聚合物的側鏈導入不飽和基。The aforementioned acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate. As the aforementioned functional group-containing monomer, for example, the following monomers can be exemplified by reacting the aforementioned functional group with the crosslinking agent described later to form the starting point of crosslinking, or by reacting the aforementioned functional group with the unsaturated group-containing compound described later The unsaturated group reacts to introduce an unsaturated group into the side chain of the acrylic polymer.

作為含官能基之單體中的前述官能基，例如可列舉：羥基、羧基、胺基、環氧基等。 亦即，作為含官能基之單體，例如可列舉：含羥基之單體、含羧基之單體、含胺基之單體、含環氧基之單體等。Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxyl group, an amino group, and an epoxy group. That is, as a monomer containing a functional group, for example, a monomer containing a hydroxyl group, a monomer containing a carboxyl group, a monomer containing an amine group, a monomer containing an epoxy group, and the like can be cited.

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 aforementioned hydroxyl-containing monomer include: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols such as allyl alcohol (unsaturated alcohols without (meth)acrylic acid skeleton), etc.

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 aforementioned carboxyl group-containing monomer include: ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, Maleic acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids (dicarboxylic acids with ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. (form Group) carboxyalkyl acrylate and the like.

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

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

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

前述丙烯酸系聚合物亦可除源自(甲基)丙烯酸烷基酯之結構單元、及源自含官能基之單體之結構單元以外，進而具有源自其他單體之結構單元。 前述其他單體只要能夠與(甲基)丙烯酸烷基酯等共聚，則並無特別限定。 作為前述其他單體，例如可列舉：苯乙烯、α-甲基苯乙烯、乙烯基甲苯、甲酸乙烯酯、乙酸乙烯酯、丙烯腈、丙烯醯胺等。The aforementioned acrylic polymer may have structural units derived from other monomers in addition to structural units derived from alkyl (meth)acrylates and functional group-containing monomers. The aforementioned other monomers are not particularly limited as long as they can be copolymerized with alkyl (meth)acrylate and the like. Examples of the aforementioned other monomers include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.

構成前述丙烯酸系聚合物之前述其他單體可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The aforementioned other monomers constituting the aforementioned acrylic polymer may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

前述丙烯酸系聚合物可用作上述之非能量線硬化性的黏著性樹脂(I-1a)。 另一方面，使前述丙烯酸系聚合物中的官能基與具有能量線聚合性不飽和基(能量線聚合性基)之含不飽和基之化合物反應而成之化合物可用作上述之能量線硬化性的黏著性樹脂(I-2a)。The aforementioned acrylic polymer can be used as the aforementioned non-energy-ray-curable adhesive resin (I-1a). On the other hand, a compound obtained by reacting a functional group in the aforementioned acrylic polymer with an unsaturated group-containing compound having an energy-ray polymerizable unsaturated group (energy-ray polymerizable group) can be used as the aforementioned energy-ray curing Adhesive resin (I-2a).

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

黏著劑組成物(I-1)中，黏著性樹脂(I-1a)的含量相對於黏著劑組成物(I-1)的總質量之比例較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為15質量%至90質量%。In the adhesive composition (I-1), the ratio of the content of the adhesive resin (I-1a) to the total mass of the adhesive composition (I-1) is preferably 5 to 99% by mass, more preferably It is 10% by mass to 95% by mass, and more preferably 15% by mass to 90% by mass.

[能量線硬化性化合物] 作為黏著劑組成物(I-1)所含有之前述能量線硬化性化合物，可列舉具有能量線聚合性不飽和基、且能夠藉由照射能量線而硬化之單體或低聚物。 能量線硬化性化合物中，作為單體，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇(甲基)丙烯酸酯等多元(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲酸酯；聚酯(甲基)丙烯酸酯；聚醚(甲基)丙烯酸酯；環氧(甲基)丙烯酸酯等。 能量線硬化性化合物中，作為低聚物，例如可列舉上述例示之單體聚合而成之低聚物等。 就分子量相對較大，不易使黏著劑層的儲存彈性模數降低之方面而言，能量線硬化性化合物較佳為(甲基)丙烯酸胺基甲酸酯、(甲基)丙烯酸胺基甲酸酯低聚物。[Energy ray hardening compound] Examples of the aforementioned energy ray curable compound contained in the adhesive composition (I-1) include monomers or oligomers that have an energy ray polymerizable unsaturated group and can be cured by energy ray irradiation. Among the energy ray curable compounds, examples of monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, (Meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate and other poly(meth)acrylates; (meth)acrylate amino Acid ester; polyester (meth)acrylate; polyether (meth)acrylate; epoxy (meth)acrylate, etc. Among the energy ray curable compounds, examples of the oligomer include oligomers obtained by polymerizing the monomers exemplified above. In terms of relatively large molecular weight and not easy to reduce the storage elastic modulus of the adhesive layer, the energy ray curable compound is preferably (meth)acrylate urethane, (meth)acrylate urethane formic acid Ester oligomer.

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

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

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

前述交聯劑例如與前述官能基反應而使黏著性樹脂(I-1a)彼此交聯。 作為交聯劑，例如可列舉：甲苯二異氰酸酯、六亞甲基二異氰酸酯、苯二甲基二異氰酸酯、這些二異氰酸酯之加合物等異氰酸酯系交聯劑(具有異氰酸酯基之交聯劑)；乙二醇縮水甘油醚等環氧系交聯劑(具有縮水甘油基之交聯劑)；六[1-(2-甲基)-氮丙啶基]三磷醯基三嗪等氮丙啶系交聯劑(具有氮丙啶基之交聯劑)；鋁螯合物等金屬螯合物系交聯劑(具有金屬螯合物結構之交聯劑)；異氰脲酸酯系交聯劑(具有異氰脲酸骨架之交聯劑)等。 就提高黏著劑的凝聚力而提高黏著劑層的黏著力之方面、及容易獲取等方面而言，交聯劑較佳為異氰酸酯系交聯劑。The aforementioned crosslinking agent reacts with the aforementioned functional group to crosslink the adhesive resins (I-1a), for example. Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; Epoxy crosslinking agents such as ethylene glycol glycidyl ether (crosslinking agents with glycidyl groups); aziridines such as hexa[1-(2-methyl)-aziridinyl] triphosphoryl triazine Crosslinking agent (crosslinking agent with aziridin group); metal chelate crosslinking agent such as aluminum chelate (crosslinking agent with metal chelate structure); isocyanurate crosslinking agent Agent (crosslinking agent with isocyanuric acid skeleton), etc. The crosslinking agent is preferably an isocyanate-based crosslinking agent in terms of enhancing the cohesive force of the adhesive and enhancing the adhesive force of the adhesive layer, and easy availability.

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

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

[光聚合起始劑] 黏著劑組成物(I-1)亦可進而含有光聚合起始劑。含有光聚合起始劑之黏著劑組成物(I-1)即便照射紫外線等相對較低能量的能量線，亦充分地進行硬化反應。[Photopolymerization initiator] The adhesive composition (I-1) may further contain a photopolymerization initiator. The adhesive composition (I-1) containing a photopolymerization initiator sufficiently undergoes a curing reaction even if it is irradiated with relatively low-energy energy rays such as ultraviolet rays.

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

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

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

[其他添加劑] 黏著劑組成物(I-1)亦可在無損本發明的效果之範圍內，含有不符合上述任一種成分之其他添加劑。 作為前述其他添加劑，例如可列舉：抗靜電劑、抗氧化劑、軟化劑(塑化劑)、填充材料(填料)、防銹劑、著色劑(顏料、染料)、增感劑、黏著賦予劑、反應延遲劑、交聯促進劑(觸媒)、層間轉移抑制劑等公知的添加劑。[Other additives] The adhesive composition (I-1) may also contain other additives that do not meet any of the above-mentioned components within a range that does not impair the effects of the present invention. As the aforementioned other additives, for example, antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, adhesion-imparting agents, Known additives such as reaction delay agents, crosslinking accelerators (catalysts), and interlayer transfer inhibitors.

此外，所謂反應延遲劑，例如係指用以抑制因混入至黏著劑組成物(I-1)中的觸媒的作用，而使保存中的黏著劑組成物(I-1)中進行目標外的交聯反應之成分。作為反應延遲劑，例如可列舉藉由針對觸媒之螯合物而形成螯合錯合物之化合物，更具體而言，可列舉1分子中具有2個以上之羰基(-C(=O)-)之化合物。 另外，所謂層間轉移抑制劑，例如係指用以抑制保護膜形成用膜等與黏著劑層相鄰之層中所含有之成分朝黏著劑層轉移之成分。作為層間轉移抑制劑，可列舉與轉移抑制對象相同的成分，例如於轉移抑制對象為保護膜形成用膜中的環氧樹脂之情形時，可使用同種的環氧樹脂。In addition, the so-called reaction delay agent means, for example, to suppress the effect of the catalyst mixed in the adhesive composition (I-1), causing the adhesive composition (I-1) in storage to carry out target removal. The component of the crosslinking reaction. As the reaction delay agent, for example, a compound that forms a chelate complex by a chelate against a catalyst can be cited. More specifically, it can include two or more carbonyl groups (-C(=O) per molecule). -) The compound. In addition, the term "interlayer transfer inhibitor" refers to, for example, a component for suppressing the transfer of a component contained in a layer adjacent to the adhesive layer such as a protective film forming film to the adhesive layer. As the interlayer transfer inhibitor, the same component as the target of the transfer suppression can be cited. For example, when the target of the transfer suppression is the epoxy resin in the film for forming a protective film, the same epoxy resin can be used.

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

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

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

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

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

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

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

[黏著劑組成物(I-2)] 如上所述，前述黏著劑組成物(I-2)含有於非能量線硬化性的黏著性樹脂(I-1a)的側鏈導入有不飽和基之能量線硬化性的黏著性樹脂(I-2a)。[Adhesive composition (I-2)] As described above, the aforementioned adhesive composition (I-2) is contained in the non-energy-ray-curable adhesive resin (I-1a) in the side chain of the energy-ray-curable adhesive resin (I- 2a).

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

前述含不飽和基之化合物係除前述能量線聚合性不飽和基以外，進而具有藉由與黏著性樹脂(I-1a)中的官能基反應而能夠與黏著性樹脂(I-1a)鍵結之基之化合物。 作為前述能量線聚合性不飽和基，例如可列舉(甲基)丙烯醯基、乙烯基(次乙基)、烯丙基(2-丙烯基)等，較佳為(甲基)丙烯醯基。 作為能夠與黏著性樹脂(I-1a)中的官能基鍵結之基，例如可列舉：能夠與羥基或胺基鍵結之異氰酸酯基及縮水甘油基、以及能夠與羧基或環氧基鍵結之羥基及胺基等。The aforementioned unsaturated group-containing compound is in addition to the aforementioned energy-ray polymerizable unsaturated group, and further has the ability to bond with the adhesive resin (I-1a) by reacting with the functional group in the adhesive resin (I-1a) The base compound. Examples of the energy ray polymerizable unsaturated group include (meth)acryloyl, vinyl (ethylene), allyl (2-propenyl), etc., preferably (meth)acryloyl . Examples of groups capable of bonding to functional groups in the adhesive resin (I-1a) include isocyanate groups and glycidyl groups capable of bonding to hydroxyl groups or amino groups, and groups capable of bonding to carboxyl groups or epoxy groups. The hydroxyl and amino groups, etc.

作為前述含不飽和基之化合物，例如可列舉：異氰酸(甲基)丙烯醯氧基乙酯、(甲基)丙烯醯基異氰酸酯、(甲基)丙烯酸縮水甘油酯等。Examples of the aforementioned unsaturated group-containing compound include (meth)acryloxyethyl isocyanate, (meth)acryloyl isocyanate, glycidyl (meth)acrylate, and the like.

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

黏著劑組成物(I-2)中，黏著性樹脂(I-2a)的含量相對於黏著劑組成物(I-2)的總質量之比例較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為10質量%至90質量%。In the adhesive composition (I-2), the ratio of the content of the adhesive resin (I-2a) to the total mass of the adhesive composition (I-2) is preferably from 5 to 99% by mass, more preferably It is 10% by mass to 95% by mass, particularly preferably 10% by mass to 90% by mass.

[交聯劑] 例如於使用與黏著性樹脂(I-1a)中的丙烯酸系聚合物相同的具有源自含官能基之單體之結構單元之前述丙烯酸系聚合物作為黏著性樹脂(I-2a)之情形時，黏著劑組成物(I-2)亦可進而含有交聯劑。[Crosslinking agent] For example, when the aforementioned acrylic polymer having the same structural unit derived from a functional group-containing monomer as the acrylic polymer in the adhesive resin (I-1a) is used as the adhesive resin (I-2a) The adhesive composition (I-2) may further contain a crosslinking agent.

作為黏著劑組成物(I-2)中的前述交聯劑，可列舉與黏著劑組成物(I-1)中的交聯劑相同的化合物。 黏著劑組成物(I-2)所含有之交聯劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。Examples of the crosslinking agent in the adhesive composition (I-2) include the same compounds as the crosslinking agent in the adhesive composition (I-1). The crosslinking agent contained in the adhesive composition (I-2) may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

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

[光聚合起始劑] 黏著劑組成物(I-2)亦可進而含有光聚合起始劑。含有光聚合起始劑之黏著劑組成物(I-2)即便照射紫外線等相對較低能量的能量線，硬化反應亦充分地進行。[Photopolymerization initiator] The adhesive composition (I-2) may further contain a photopolymerization initiator. Even if the adhesive composition (I-2) containing a photopolymerization initiator is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction proceeds sufficiently.

作為黏著劑組成物(I-2)中的前述光聚合起始劑，可列舉與黏著劑組成物(I-1)中的光聚合起始劑相同的化合物。 黏著劑組成物(I-2)所含有之光聚合起始劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。Examples of the photopolymerization initiator in the adhesive composition (I-2) include the same compounds as the photopolymerization initiator in the adhesive composition (I-1). The photopolymerization initiator contained in the adhesive composition (I-2) may be only one type, or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected.

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

[其他添加劑、溶劑] 黏著劑組成物(I-2)亦可在無損本發明的效果之範圍內含有不符合上述任一種成分之其他添加劑。 另外，黏著劑組成物(I-2)亦可以與黏著劑組成物(I-1)之情形相同的目的含有溶劑。 作為黏著劑組成物(I-2)中的前述其他添加劑及溶劑，可列舉分別與黏著劑組成物(I-1)中的其他添加劑及溶劑相同的化合物。 黏著劑組成物(I-2)所含有之其他添加劑及溶劑分別可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。 黏著劑組成物(I-2)中的其他添加劑及溶劑的含量分別無特別限定，根據該其他添加劑及溶劑的種類適宜選擇即可。[Other additives, solvents] The adhesive composition (I-2) may also contain other additives that do not meet any of the above-mentioned components within a range that does not impair the effects of the present invention. In addition, the adhesive composition (I-2) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1). Examples of the aforementioned other additives and solvents in the adhesive composition (I-2) include the same compounds as the other additives and solvents in the adhesive composition (I-1). The other additives and solvents contained in the adhesive composition (I-2) may be only one type, or two or more types, respectively. In the case of two or more types, the combination and ratio of these can be arbitrarily selected. The content of other additives and solvents in the adhesive composition (I-2) is not particularly limited, and may be appropriately selected according to the types of the other additives and solvents.

[黏著劑組成物(I-3)] 如上所述，前述黏著劑組成物(I-3)含有前述黏著性樹脂(I-2a)、及能量線硬化性化合物。[Adhesive composition (I-3)] As described above, the adhesive composition (I-3) contains the adhesive resin (I-2a) and an energy ray curable compound.

黏著劑組成物(I-3)中，黏著性樹脂(I-2a)的含量相對於黏著劑組成物(I-3)的總質量之比例較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為15質量%至90質量%。In the adhesive composition (I-3), the ratio of the content of the adhesive resin (I-2a) to the total mass of the adhesive composition (I-3) is preferably 5 to 99% by mass, and more preferably It is 10% by mass to 95% by mass, and more preferably 15% by mass to 90% by mass.

[能量線硬化性化合物] 作為黏著劑組成物(I-3)所含有之前述能量線硬化性化合物，可列舉具有能量線聚合性不飽和基，且能夠藉由照射能量線而硬化之單體及低聚物，可列舉與黏著劑組成物(I-1)所含有之能量線硬化性化合物相同的化合物。 黏著劑組成物(I-3)所含有之前述能量線硬化性化合物可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。[Energy ray hardening compound] Examples of the aforementioned energy-ray curable compound contained in the adhesive composition (I-3) include monomers and oligomers that have an energy-ray polymerizable unsaturated group and can be cured by irradiation of energy rays, including The same compound as the energy ray curable compound contained in the adhesive composition (I-1). The aforementioned energy ray curable compound contained in the adhesive composition (I-3) may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

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

[光聚合起始劑] 黏著劑組成物(I-3)亦可進而含有光聚合起始劑。含有光聚合起始劑之黏著劑組成物(I-3)即便照射紫外線等相對較低能量的能量線，硬化反應亦充分地進行。[Photopolymerization initiator] The adhesive composition (I-3) may further contain a photopolymerization initiator. Even if the adhesive composition (I-3) containing a photopolymerization initiator is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction proceeds sufficiently.

作為黏著劑組成物(I-3)中的前述光聚合起始劑，可列舉與黏著劑組成物(I-1)中的光聚合起始劑相同的化合物。 黏著劑組成物(I-3)所含有之光聚合起始劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。Examples of the aforementioned photopolymerization initiator in the adhesive composition (I-3) include the same compounds as the photopolymerization initiator in the adhesive composition (I-1). The photopolymerization initiator contained in the adhesive composition (I-3) may be only one type, or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected.

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

[其他添加劑、溶劑] 黏著劑組成物(I-3)亦可在無損本發明的效果之範圍內含有不符合上述任一種成分之其他添加劑。 另外，黏著劑組成物(I-3)亦可以與黏著劑組成物(I-1)之情形相同的目的含有溶劑。 作為黏著劑組成物(I-3)中的前述其他添加劑及溶劑，可列舉分別與黏著劑組成物(I-1)中的其他添加劑及溶劑相同的化合物。 黏著劑組成物(I-3)所含有之其他添加劑及溶劑分別可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。 黏著劑組成物(I-3)中的其他添加劑及溶劑的含量分別無特別限定，根據該其他添加劑及溶劑的種類適宜選擇即可。[Other additives, solvents] The adhesive composition (I-3) may also contain other additives that do not meet any of the above-mentioned components within a range that does not impair the effects of the present invention. In addition, the adhesive composition (I-3) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1). Examples of the aforementioned other additives and solvents in the adhesive composition (I-3) include the same compounds as the other additives and solvents in the adhesive composition (I-1). The other additives and solvents contained in the adhesive composition (I-3) may be only one type, or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected. The content of other additives and solvents in the adhesive composition (I-3) is not particularly limited, and may be appropriately selected according to the types of the other additives and solvents.

[黏著劑組成物(I-1)至黏著劑組成物(I-3)以外的黏著劑組成物] 前文主要對黏著劑組成物(I-1)、黏著劑組成物(I-2)及黏著劑組成物(I-3)進行了說明，但作為這些黏著劑組成物的含有成分所說明之化合物亦可同樣地用於這些3種黏著劑組成物以外的所有的黏著劑組成物(本說明書中，稱為「黏著劑組成物(I-1)至黏著劑組成物(I-3)以外的黏著劑組成物」)。[Adhesive composition (I-1) to adhesive composition other than adhesive composition (I-3)] In the foregoing, the adhesive composition (I-1), the adhesive composition (I-2), and the adhesive composition (I-3) were mainly described, but the compounds described as the components of the adhesive composition It can also be used in the same way for all adhesive compositions other than these three types of adhesive compositions (in this specification, referred to as "adhesive composition (I-1) to adhesive composition (I-3) other than Adhesive composition").

作為黏著劑組成物(I-1)至黏著劑組成物(I-3)以外的黏著劑組成物，除能量線硬化性的黏著劑組成物以外，亦可列舉非能量線硬化性的黏著劑組成物。 作為非能量線硬化性的黏著劑組成物，例如可列舉含有丙烯酸系樹脂、胺基甲酸酯系樹脂、橡膠系樹脂、聚矽氧系樹脂、環氧系樹脂、聚乙烯醚、聚碳酸酯、酯系樹脂等非能量線硬化性的黏著性樹脂(I-1a)之黏著劑組成物(I-4)，較佳為含有丙烯酸系樹脂之黏著劑組成物。As the adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3), in addition to the energy-ray curable adhesive composition, non-energy-ray curable adhesives can also be cited Composition. Examples of non-energy-ray-curable adhesive compositions include acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, and polycarbonates. Adhesive composition (I-4) of non-energy-ray curable adhesive resin (I-1a) such as ester resin, preferably an adhesive composition containing acrylic resin.

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

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

[黏著性樹脂(I-1a)] 作為黏著劑組成物(I-4)中的黏著性樹脂(I-1a)，可列舉與黏著劑組成物(I-1)中的黏著性樹脂(I-1a)相同的化合物。 黏著劑組成物(I-4)所含有之黏著性樹脂(I-1a)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。[Adhesive resin (I-1a)] Examples of the adhesive resin (I-1a) in the adhesive composition (I-4) include the same compounds as the adhesive resin (I-1a) in the adhesive composition (I-1). Adhesive resin (I-1a) contained in the adhesive composition (I-4) may be only one type or two or more types. In the case of two or more types, the combination and ratio of these can be arbitrarily selected .

黏著劑組成物(I-4)中，黏著性樹脂(I-1a)的含量相對於黏著劑組成物(I-4)的總質量之比例較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為15質量%至90質量%。In the adhesive composition (I-4), the ratio of the content of the adhesive resin (I-1a) to the total mass of the adhesive composition (I-4) is preferably from 5 to 99% by mass, more preferably It is 10% by mass to 95% by mass, and more preferably 15% by mass to 90% by mass.

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

作為黏著劑組成物(I-4)中的交聯劑，可列舉與黏著劑組成物(I-1)中的交聯劑相同的化合物。 黏著劑組成物(I-4)所含有之交聯劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。As the crosslinking agent in the adhesive composition (I-4), the same compounds as the crosslinking agent in the adhesive composition (I-1) can be cited. The crosslinking agent contained in the adhesive composition (I-4) may be only one type, or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

前述黏著劑組成物(I-4)中，交聯劑的含量相對於黏著性樹脂(I-1a)的含量100質量份，較佳為0.01質量份至50質量份，更佳為0.1質量份至47質量份，尤佳為0.3質量份至44質量份。In the aforementioned adhesive composition (I-4), the content of the crosslinking agent relative to the content of the adhesive resin (I-1a) is 100 parts by mass, preferably 0.01 to 50 parts by mass, more preferably 0.1 part by mass To 47 parts by mass, particularly preferably 0.3 to 44 parts by mass.

[其他添加劑、溶劑] 黏著劑組成物(I-4)亦可在無損本發明的效果之範圍內含有不符合上述任一種成分之其他添加劑。 另外，黏著劑組成物(I-4)亦可以與黏著劑組成物(I-1)之情形相同的目的含有溶劑。 作為黏著劑組成物(I-4)中的前述其他添加劑及溶劑，可列舉分別與黏著劑組成物(I-1)中的其他添加劑及溶劑相同的化合物。 黏著劑組成物(I-4)所含有之其他添加劑及溶劑分別可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。 黏著劑組成物(I-4)中的其他添加劑及溶劑的含量分別無特別限定，根據該其他添加劑及溶劑的種類適宜選擇即可。[Other additives, solvents] The adhesive composition (I-4) may also contain other additives that do not meet any of the above-mentioned components within a range that does not impair the effects of the present invention. In addition, the adhesive composition (I-4) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1). Examples of the aforementioned other additives and solvents in the adhesive composition (I-4) include the same compounds as the other additives and solvents in the adhesive composition (I-1). The other additives and solvents contained in the adhesive composition (I-4) may be only one type, or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected. The content of other additives and solvents in the adhesive composition (I-4) is not particularly limited, and may be appropriately selected according to the types of the other additives and solvents.

於後述之保護膜形成用膜為能量線硬化性之情形時，黏著劑層較佳為非能量線硬化性。原因在於，若黏著劑層為能量線硬化性，則有時無法抑制於藉由照射能量線使保護膜形成用膜硬化時，黏著劑層亦同時硬化。若黏著劑層與保護膜形成用膜同時硬化，則有時保護膜形成用膜之硬化物及黏著劑層於這些層的界面會貼附至無法剝離之程度。該情形時，難以將內面具備保護膜形成用膜之硬化物、亦即內面具備保護膜之半導體晶片(亦即附保護膜之半導體晶片)自具備黏著劑層之硬化物的支撐片剝離，而無法正常地拾取附保護膜之半導體晶片。若黏著劑層為非能量線硬化性，則能夠確實地避免此種不良情況，能夠更容易地拾取附保護膜之半導體晶片。When the film for forming a protective film described later is energy ray curable, the adhesive layer is preferably non-energy ray curable. The reason is that if the adhesive layer is energy-ray curable, it may not be possible to prevent the adhesive layer from being cured at the same time when the protective film formation film is cured by irradiation of energy rays. If the adhesive layer and the film for forming a protective film are cured at the same time, the cured product of the film for forming a protective film and the adhesive layer may stick to the interface of these layers to the extent that they cannot be peeled off. In this case, it is difficult to peel a cured product with a protective film forming film on the inner surface, that is, a semiconductor wafer with a protective film on the inner surface (ie, a semiconductor wafer with a protective film) from the support sheet of the cured product with an adhesive layer , And the semiconductor chip with protective film cannot be picked up normally. If the adhesive layer is non-energy-ray curable, such a problem can be reliably avoided, and the semiconductor wafer with the protective film can be picked up more easily.

此處，對黏著劑層為非能量線硬化性之情形的效果進行了說明，但即便為支撐片中之與保護膜形成用膜直接接觸之層為黏著劑層以外的層，只要該層為非能量線硬化性，則亦發揮相同的效果。Here, the effect of the case where the adhesive layer is non-energy-ray curable is described. However, even if the layer directly in contact with the protective film forming film in the support sheet is a layer other than the adhesive layer, as long as the layer is Non-energy ray hardening also exerts the same effect.

[黏著劑組成物之製造方法] 黏著劑組成物(I-1)至黏著劑組成物(I-3)、或黏著劑組成物(I-4)等黏著劑組成物(I-1)至黏著劑組成物(I-3)以外的黏著劑組成物係藉由調配前述黏著劑及視需要的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而獲得。 調配各成分時的添加順序並無特別限定，亦可同時添加2種以上之成分。 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；或是，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。 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。 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℃。[Method for manufacturing adhesive composition] Adhesive composition (I-1) to adhesive composition (I-3), or adhesive composition (I-4) and other adhesive composition (I-1) to adhesive composition (I-3) The adhesive composition other than that is obtained by blending the aforementioned adhesive and components other than the aforementioned adhesive if necessary, etc., to constitute each component of the adhesive composition. The order of addition when formulating each component is not particularly limited, and two or more components may be added at the same time. When a solvent is used, it can be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance; or, not diluting any compounding component other than the solvent in advance. The solvent is mixed with these formulation ingredients. The method of mixing the ingredients during the preparation is not particularly limited, and can be appropriately selected from the following known methods: a method of rotating a stirrer or a stirring blade, etc. for mixing; a method of mixing using a mixer; applying ultrasonic waves for mixing The method and so on. Regarding the temperature and time when each component is added and mixed, as long as it does not deteriorate each compounding component, it is not particularly limited and may be adjusted appropriately. The temperature is preferably 15°C to 30°C.

○背面抗靜電層 前述背面抗靜電層為片狀或膜狀，含有抗靜電劑。 前述背面抗靜電層中，除前述抗靜電劑以外，亦可含有樹脂。○Back antistatic layer The aforementioned back antistatic layer is in the form of a sheet or film and contains an antistatic agent. The said back surface antistatic layer may contain resin in addition to the said antistatic agent.

背面抗靜電層可由1層(單層)所構成，亦可由2層以上之多層所構成，於由多層所構成之情形時，這些多層相互可相同亦可不同，這些多層的組合並無特別限定。The back antistatic layer can be composed of one layer (single layer) or two or more layers. In the case of multiple layers, these layers may be the same or different from each other. The combination of these layers is not particularly limited. .

背面抗靜電層的厚度較佳為200nm以下，更佳為180nm以下，例如亦可為100nm以下。厚度為200nm以下之背面抗靜電層中，能夠維持充分的抗靜電能力，並且能夠降低抗靜電劑的使用量，因此能夠降低具備此種背面抗靜電層之保護膜形成用複合片的成本。進而，於背面抗靜電層的厚度為100nm以下之情形時，除上述效果以外，亦能夠獲得如下效果：能夠將因具備背面抗靜電層所致之保護膜形成用複合片的特性的變動抑制為最小限度。作為前述特性，例如可列舉擴展性。 此處，所謂「背面抗靜電層的厚度」，意指背面抗靜電層整體的厚度，例如所謂由多層所構成之背面抗靜電層的厚度，意指構成背面抗靜電層之全部層的合計厚度。The thickness of the back antistatic layer is preferably 200 nm or less, more preferably 180 nm or less, and for example, 100 nm or less. In the back antistatic layer with a thickness of 200 nm or less, sufficient antistatic ability can be maintained, and the amount of antistatic agent used can be reduced. Therefore, the cost of the protective film forming composite sheet with such a back antistatic layer can be reduced. Furthermore, when the thickness of the back antistatic layer is 100 nm or less, in addition to the above effects, the following effect can also be obtained: the variation in the characteristics of the protective film forming composite sheet due to the presence of the back antistatic layer can be suppressed to Minimal. As the aforementioned characteristics, for example, scalability can be cited. Here, the "thickness of the back antistatic layer" means the thickness of the entire back antistatic layer. For example, the thickness of the back antistatic layer composed of multiple layers means the total thickness of all layers constituting the back antistatic layer .

背面抗靜電層的厚度較佳為30nm以上，更佳為40nm以上，例如可為65nm以上。厚度為前述下限值以上之背面抗靜電層更容易形成，且結構更穩定。The thickness of the back antistatic layer is preferably 30 nm or more, more preferably 40 nm or more, and for example, may be 65 nm or more. The back antistatic layer whose thickness is above the aforementioned lower limit is easier to form and has a more stable structure.

背面抗靜電層的厚度可適宜調節為將上述之較佳的下限值及上限值任意組合而設定之範圍內。例如，一實施形態中，背面抗靜電層的厚度較佳為30nm至200nm，更佳為40nm至180nm，例如可為65nm至100nm。但這些係背面抗靜電層的厚度的一例。The thickness of the back antistatic layer can be appropriately adjusted to be within the range set by arbitrarily combining the above-mentioned preferred lower limit and upper limit. For example, in one embodiment, the thickness of the back antistatic layer is preferably 30 nm to 200 nm, more preferably 40 nm to 180 nm, and may be 65 nm to 100 nm, for example. However, these are examples of the thickness of the back antistatic layer.

背面抗靜電層可為透明，亦可為不透明，還可根據目的而著色。 例如，於保護膜形成用膜具有能量線硬化性之情形時，背面抗靜電層較佳為使能量線透過。 例如，為了經由背面抗靜電層將保護膜形成用複合片中的保護膜形成用膜進行光學檢查，背面抗靜電層較佳為透明。The back antistatic layer can be transparent or opaque, and can be colored according to the purpose. For example, when the film for forming a protective film has energy ray curability, it is preferable that the back surface antistatic layer allows the energy ray to pass through. For example, in order to optically inspect the protective film formation film in the composite sheet for protective film formation via the back antistatic layer, the back antistatic layer is preferably transparent.

[抗靜電組成物(VI-1)] 背面抗靜電層可使用含有前述抗靜電劑之抗靜電組成物(VI-1)而形成。例如，於背面抗靜電層的形成對象面塗敷抗靜電組成物(VI-1)，並視需要使之乾燥，藉此能夠於目標部位形成背面抗靜電層。抗靜電組成物(VI-1)中的常溫下不會氣化的成分彼此的含量比率通常與背面抗靜電層中的前述成分彼此的含量比率相同。 背面抗靜電層的更具體的形成方法與其他層的形成方法一起於後文詳細地進行說明。[Antistatic composition (VI-1)] The back antistatic layer can be formed using the antistatic composition (VI-1) containing the aforementioned antistatic agent. For example, by coating the antistatic composition (VI-1) on the surface to be formed of the back antistatic layer, and drying it if necessary, the back antistatic layer can be formed on the target site. The content ratio of the components that do not vaporize at room temperature in the antistatic composition (VI-1) is usually the same as the content ratio of the aforementioned components in the back antistatic layer. A more specific method of forming the back surface antistatic layer will be described in detail later together with the method of forming other layers.

利用公知的方法塗敷抗靜電組成物(VI-1)即可，例如可為與上述之黏著劑組成物之情形相同的方法。The antistatic composition (VI-1) may be applied by a known method, and for example, it may be the same method as in the case of the adhesive composition described above.

於基材上設置背面抗靜電層之情形時，例如於基材上塗敷抗靜電組成物(VI-1)，並視需要使之乾燥，藉此於基材上積層背面抗靜電層即可。另外，於基材上設置背面抗靜電層之情形時，例如亦可於剝離膜上塗敷抗靜電組成物(VI-1)，並視需要使之乾燥，藉此於剝離膜上預先形成背面抗靜電層，將該背面抗靜電層的露出面與基材的一表面貼合，藉此於基材上積層背面抗靜電層。該情形時的剝離膜在保護膜形成用複合片的製造過程或使用過程中的任意時間點移除即可。In the case of providing the back antistatic layer on the substrate, for example, the antistatic composition (VI-1) is coated on the substrate and dried as necessary to laminate the back antistatic layer on the substrate. In addition, when the back antistatic layer is provided on the substrate, for example, the antistatic composition (VI-1) may be coated on the release film and dried if necessary, thereby forming the back antistatic layer on the release film in advance. For the electrostatic layer, the exposed surface of the back antistatic layer is attached to one surface of the substrate, thereby laminating the back antistatic layer on the substrate. The release film in this case may be removed at any point in the manufacturing process or the use process of the composite sheet for protective film formation.

抗靜電組成物(VI-1)的乾燥條件並無特別限定，於抗靜電組成物(VI-1)含有後述溶劑之情形時，較佳為進行加熱乾燥。並且，含有溶劑之抗靜電組成物(VI-1)例如較佳為於40℃至130℃且10秒至5分鐘之條件進行乾燥。The drying conditions of the antistatic composition (VI-1) are not particularly limited, but when the antistatic composition (VI-1) contains a solvent described later, it is preferable to heat and dry. In addition, the solvent-containing antistatic composition (VI-1) is preferably dried under the conditions of 40°C to 130°C and 10 seconds to 5 minutes, for example.

抗靜電組成物(VI-1)中，除前述抗靜電劑以外，亦可含有前述樹脂。The antistatic composition (VI-1) may contain the aforementioned resin in addition to the aforementioned antistatic agent.

[抗靜電劑] 前述抗靜電劑可為導電性化合物等公知的化合物，並無特別限定。前述抗靜電劑例如可為低分子化合物及高分子化合物(換言之，低聚物或聚合物)之任一種。[Antistatic Agent] The aforementioned antistatic agent may be a known compound such as a conductive compound and is not particularly limited. The aforementioned antistatic agent may be, for example, any of a low molecular compound and a high molecular compound (in other words, an oligomer or a polymer).

前述抗靜電劑中，作為低分子化合物，例如可列舉各種離子液體。 作為前述離子液體，例如可列舉：嘧啶鎓鹽、吡啶鎓鹽、哌啶鎓鹽、吡咯啶鎓鹽、咪唑鎓鹽、嗎啉鎓鹽、鋶鹽、鏻鹽、銨鹽等公知的化合物。Among the aforementioned antistatic agents, examples of low-molecular-weight compounds include various ionic liquids. Examples of the ionic liquid include well-known compounds such as pyrimidinium salts, pyridinium salts, piperidinium salts, pyrrolidinium salts, imidazolium salts, morpholinium salts, sulfonium salts, phosphonium salts, and ammonium salts.

前述抗靜電劑中，作為高分子化合物，例如可列舉：聚(3,4-乙二氧基噻吩)/聚苯乙烯磺酸鹽(本說明書中，有時稱為「PEDOT/PSS」)、聚吡咯、奈米碳管等。前述聚吡咯為具有多個(多數)吡咯骨架之低聚物或聚合物。Among the aforementioned antistatic agents, examples of polymer compounds include poly(3,4-ethylenedioxythiophene)/polystyrene sulfonate (in this specification, it may be referred to as "PEDOT/PSS"), Polypyrrole, carbon nanotubes, etc. The aforementioned polypyrrole is an oligomer or polymer having multiple (majority) pyrrole skeletons.

抗靜電組成物(VI-1)所含有之抗靜電劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The antistatic agent contained in the antistatic composition (VI-1) may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

抗靜電組成物(VI-1)中，抗靜電劑的含量相對於溶劑以外的全部成分的總含量之比例(亦即，背面抗靜電層中的抗靜電劑的含量相對於背面抗靜電層的總質量之比例)例如可為0.1質量%至30質量%、以及0.5質量%至15質量%之任一者。藉由前述比例為前述下限值以上，保護膜形成用複合片的剝離帶電的抑制效果變高，結果保護膜形成用膜與半導體晶圓之間的異物混入的抑制效果變高。藉由前述比例為前述上限值以下，背面抗靜電層的強度變得更高。In the antistatic composition (VI-1), the ratio of the content of the antistatic agent to the total content of all components other than the solvent (that is, the content of the antistatic agent in the back antistatic layer relative to that of the back antistatic layer The ratio of the total mass) may be, for example, any of 0.1% by mass to 30% by mass, and 0.5% by mass to 15% by mass. When the aforementioned ratio is greater than or equal to the aforementioned lower limit, the effect of suppressing the peeling charge of the protective film forming composite sheet becomes higher, and as a result, the effect of suppressing foreign matter mixing between the protective film forming film and the semiconductor wafer becomes higher. When the aforementioned ratio is below the aforementioned upper limit, the strength of the back antistatic layer becomes higher.

[樹脂] 抗靜電組成物(VI-1)及背面抗靜電層所含有之前述樹脂可為硬化性及非硬化性之任一種，於為硬化性之情形時，可為能量線硬化性及熱硬化性之任一種。[Resin] The aforementioned resin contained in the antistatic composition (VI-1) and the back antistatic layer may be either curable or non-curable. In the case of curable, it may be either energy-ray curable or thermosetting Any kind.

作為較佳的前述樹脂，例如可列舉作為黏合劑樹脂發揮功能之樹脂。As a preferable said resin, the resin which functions as a binder resin, for example is mentioned.

作為前述樹脂，更具體而言，例如可列舉丙烯酸系樹脂等，較佳為能量線硬化性丙烯酸系樹脂。 作為抗靜電組成物(VI-1)及背面抗靜電層中的前述丙烯酸系樹脂，例如可列舉與前述黏著劑層中的丙烯酸系樹脂相同的樹脂。作為抗靜電組成物(VI-1)及背面抗靜電層中的前述能量線硬化性丙烯酸系樹脂，例如可列舉與前述黏著劑層中的黏著性樹脂(I-2a)相同的樹脂。As said resin, more specifically, acrylic resin etc. are mentioned, for example, Preferably it is an energy-ray curable acrylic resin. Examples of the acrylic resin in the antistatic composition (VI-1) and the back antistatic layer include the same resins as the acrylic resin in the adhesive layer. Examples of the energy ray curable acrylic resin in the antistatic composition (VI-1) and the back antistatic layer include the same resins as the adhesive resin (I-2a) in the adhesive layer.

抗靜電組成物(VI-1)及背面抗靜電層所含有之前述樹脂可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The aforementioned resin contained in the antistatic composition (VI-1) and the back antistatic layer may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

抗靜電組成物(VI-1)中，前述樹脂的含量相對於溶劑以外的全部成分的總含量之比例(亦即，背面抗靜電層中的前述樹脂的含量相對於背面抗靜電層的總質量之比例)例如可為30質量%至99.9質量%、35質量%至98質量%、60質量%至98質量%、以及85質量%至98質量%之任一種。藉由前述比例為前述下限值以上，背面抗靜電層的強度變得更高。藉由前述比例為前述上限值以下，能夠使抗靜電層中的抗靜電劑的含量更多。In the antistatic composition (VI-1), the ratio of the content of the aforementioned resin to the total content of all ingredients other than the solvent (that is, the content of the aforementioned resin in the back antistatic layer relative to the total mass of the back antistatic layer The ratio) can be, for example, any of 30% to 99.9% by mass, 35% to 98% by mass, 60% to 98% by mass, and 85% to 98% by mass. When the aforementioned ratio is greater than or equal to the aforementioned lower limit, the strength of the back antistatic layer becomes higher. When the aforementioned ratio is below the aforementioned upper limit, the content of the antistatic agent in the antistatic layer can be increased.

[能量線硬化性化合物、光聚合起始劑] 於抗靜電組成物(VI-1)含有能量線硬化性的前述樹脂之情形時，亦可含有能量線硬化性化合物。 另外，於抗靜電組成物(VI-1)含有能量線硬化性的前述樹脂之情形時，為了高效率地進行前述樹脂的聚合反應，亦可含有光聚合起始劑。 作為抗靜電組成物(VI-1)所含有之前述能量線硬化性化合物及光聚合起始劑，例如可列舉分別與黏著劑組成物(I-1)所含有之能量線硬化性化合物及光聚合起始劑相同的化合物。 抗靜電組成物(VI-1)所含有之能量線硬化性化合物及光聚合起始劑分別可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。 抗靜電組成物(VI-1)中的能量線硬化性化合物及光聚合起始劑的含量分別無特別限定，根據前述樹脂、能量線硬化性化合物或光聚合起始劑的種類適宜選擇即可。[Energy ray curable compound, photopolymerization initiator] When the antistatic composition (VI-1) contains the aforementioned resin with energy ray curability, it may also contain an energy ray curable compound. In addition, when the antistatic composition (VI-1) contains the energy-ray curable resin, a photopolymerization initiator may be contained in order to efficiently perform the polymerization reaction of the resin. As the aforementioned energy ray curable compound and photopolymerization initiator contained in the antistatic composition (VI-1), for example, the energy ray curable compound and the photopolymerization initiator contained in the adhesive composition (I-1) respectively The same compound as the polymerization initiator. The energy ray curable compound and the photopolymerization initiator contained in the antistatic composition (VI-1) may each be only one type, or two or more types. In the case of two or more types, the combination of these and The ratio can be chosen arbitrarily. The content of the energy ray curable compound and photopolymerization initiator in the antistatic composition (VI-1) is not particularly limited, and may be appropriately selected according to the type of the aforementioned resin, energy ray curable compound or photopolymerization initiator .

[其他添加劑、溶劑] 抗靜電組成物(VI-1)亦可在無損本發明的效果之範圍內含有不符合上述任一種成分之其他添加劑。 另外，抗靜電組成物(VI-1)亦可以與上述之黏著劑組成物(I-1)之情形相同的目的含有溶劑。 作為抗靜電組成物(VI-1)所含有之前述其他添加劑及溶劑，可列舉分別與上述之黏著劑組成物(I-1)所含有之其他添加劑(但抗靜電劑除外)及溶劑相同的化合物。進而，作為抗靜電組成物(VI-1)所含有之前述其他添加劑，除上述化合物以外，亦可列舉乳化劑。進而，作為抗靜電組成物(VI-1)所含有之溶劑，除上述化合物以外，亦可列舉：乙醇等其他醇；2-甲氧基乙醇(乙二醇單甲醚)、2-乙氧基乙醇(乙二醇單***)、1-甲氧基-2-丙醇(丙二醇單甲醚)等烷氧基醇等。 抗靜電組成物(VI-1)所含有之其他添加劑及溶劑分別可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。 抗靜電組成物(VI-1)中的其他添加劑及溶劑的含量分別無特別限定，根據該其他添加劑及溶劑的種類適宜選擇即可。[Other additives, solvents] The antistatic composition (VI-1) may also contain other additives that do not meet any of the above-mentioned components within a range that does not impair the effects of the present invention. In addition, the antistatic composition (VI-1) may contain a solvent for the same purpose as in the case of the above-mentioned adhesive composition (I-1). As the aforementioned other additives and solvents contained in the antistatic composition (VI-1), the same as the other additives (except the antistatic agent) and solvents contained in the aforementioned adhesive composition (I-1) can be cited. Compound. Furthermore, as the aforementioned other additives contained in the antistatic composition (VI-1), in addition to the above-mentioned compounds, emulsifiers can also be cited. Furthermore, as the solvent contained in the antistatic composition (VI-1), in addition to the above-mentioned compounds, other alcohols such as ethanol; 2-methoxyethanol (ethylene glycol monomethyl ether), 2-ethoxy Alkoxy alcohols such as ethyl alcohol (ethylene glycol monoethyl ether) and 1-methoxy-2-propanol (propylene glycol monomethyl ether). The other additives and solvents contained in the antistatic composition (VI-1) may be only one type, or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected. The content of other additives and solvents in the antistatic composition (VI-1) is not particularly limited, and may be appropriately selected according to the types of the other additives and solvents.

[抗靜電組成物(VI-1)之製造方法] 抗靜電組成物(VI-1)可藉由調配前述抗靜電劑、及視需要前述抗靜電劑以外的成分等用以構成抗靜電組成物(VI-1)之各成分而獲得。 抗靜電組成物(VI-1)除調配成分不同之方面以外，可利用與上述之黏著劑組成物之情形相同的方法製造。[Manufacturing method of antistatic composition (VI-1)] The antistatic composition (VI-1) can be obtained by blending the aforementioned antistatic agent and, if necessary, components other than the aforementioned antistatic agent to form each component of the antistatic composition (VI-1). The antistatic composition (VI-1) can be manufactured by the same method as in the case of the above-mentioned adhesive composition except for the difference in compounding components.

○抗靜電性基材 前述抗靜電性基材為片狀或膜狀，具有抗靜電性，進而具有與前述基材相同的功能。 前述保護膜形成用複合片中，抗靜電性基材具有與上文說明之基材及背面抗靜電層之積層物相同的功能，可代替該積層物而配置。 抗靜電性基材含有抗靜電劑及樹脂，例如除進而含有抗靜電劑之方面以外，可與上文說明之基材相同。○Antistatic base material The aforementioned antistatic substrate is in the form of a sheet or film, has antistatic properties, and further has the same function as the aforementioned substrate. In the aforementioned composite sheet for forming a protective film, the antistatic base material has the same function as the laminate of the base material and the back surface antistatic layer described above, and may be arranged instead of the laminate. The antistatic base material contains an antistatic agent and a resin, and may be the same as the base material described above except that it further contains an antistatic agent.

抗靜電性基材可由1層(單層)所構成，亦可由2層以上之多層所構成，於由多層所構成之情形時，這些多層相互可相同亦可不同，這些多層的組合並無特別限定。The antistatic substrate can be composed of one layer (single layer) or two or more layers. When composed of multiple layers, these layers may be the same or different from each other. There is no special combination of these layers. limited.

抗靜電性基材的厚度例如可與上文說明之基材的厚度相同。藉由抗靜電性基材的厚度為此種範圍，前述保護膜形成用複合片的可撓性、及朝半導體晶圓或半導體晶片之貼附性進一步提高。 此處，所謂「抗靜電性基材的厚度」，意指抗靜電性基材整體的厚度，例如所謂由多層所構成之抗靜電性基材的厚度，意指構成抗靜電性基材之全部層的合計厚度。The thickness of the antistatic substrate may be the same as the thickness of the substrate described above, for example. When the thickness of the antistatic base material is in this range, the flexibility of the composite sheet for forming a protective film and the adhesion to the semiconductor wafer or semiconductor wafer are further improved. Here, the "thickness of the antistatic substrate" means the thickness of the entire antistatic substrate. For example, the thickness of the antistatic substrate composed of multiple layers means the entirety of the antistatic substrate The total thickness of the layer.

抗靜電性基材可為透明，亦可為不透明，還可根據目的而著色。 例如，於保護膜形成用膜具有能量線硬化性之情形時，背面抗靜電層較佳為使能量線透過。 例如，為了經由抗靜電性基材將保護膜形成用複合片中的保護膜形成用膜進行光學檢查，抗靜電性基材較佳為透明。The antistatic substrate can be transparent or opaque, and can be colored according to the purpose. For example, when the film for forming a protective film has energy ray curability, it is preferable that the back surface antistatic layer allows the energy ray to pass through. For example, in order to optically inspect the protective film formation film in the composite sheet for protective film formation via the antistatic base material, the antistatic base material is preferably transparent.

為了提高抗靜電性基材與設置於該抗靜電性基材上之層(例如黏著劑層、中間層或保護膜形成用膜)之接著性，亦可對抗靜電性基材表面實施利用噴砂處理、溶劑處理等之凹凸化處理；電暈放電處理、電子束照射處理、電漿處理、臭氧／紫外線照射處理、火焰處理、鉻酸處理、熱風處理等氧化處理等。另外，亦可對抗靜電性基材表面進行底塗處理。In order to improve the adhesion between the antistatic substrate and the layer provided on the antistatic substrate (such as an adhesive layer, an intermediate layer or a film for forming a protective film), the surface of the antistatic substrate can also be treated with sandblasting , Solvent treatment and other uneven treatment; corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments. In addition, the surface of the antistatic substrate can also be primed.

[抗靜電組成物(VI-2)] 抗靜電性基材例如可藉由將含有前述抗靜電劑及樹脂之抗靜電組成物(VI-2)成形而製造。抗靜電組成物(VI-2)中的常溫下不會氣化的成分彼此的含量比率通常與抗靜電性基材中的前述成分彼此的含量比率相同。[Antistatic composition (VI-2)] The antistatic base material can be produced, for example, by molding the antistatic composition (VI-2) containing the antistatic agent and resin. The content ratio of the components that do not vaporize at room temperature in the antistatic composition (VI-2) is usually the same as the content ratio of the aforementioned components in the antistatic base material.

利用公知的方法將抗靜電組成物(VI-2)成形即可，例如可利用與製造前述基材時，將前述樹脂組成物成形之情形相同的方法進行。The antistatic composition (VI-2) may be molded by a known method. For example, it can be performed by the same method as when the resin composition is molded when the substrate is manufactured.

[抗靜電劑] 作為抗靜電組成物(VI-2)所含有之抗靜電劑，可列舉與前述背面抗靜電層所含有之抗靜電劑相同的化合物。 抗靜電組成物(VI-2)所含有之抗靜電劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。[Antistatic Agent] Examples of the antistatic agent contained in the antistatic composition (VI-2) include the same compounds as the antistatic agent contained in the aforementioned back antistatic layer. The antistatic agent contained in the antistatic composition (VI-2) may be only one type or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected.

抗靜電組成物(VI-2)及抗靜電性基材中，前述抗靜電劑的含量相對於前述抗靜電劑及樹脂的合計含量之比例較佳為7.5質量%以上，更佳為8.5質量%以上。藉由前述比例為前述下限值以上，保護膜形成用複合片的剝離帶電的抑制效果變高，結果保護膜形成用膜與半導體晶圓之間的異物混入的抑制效果變高。In the antistatic composition (VI-2) and the antistatic base material, the ratio of the content of the antistatic agent to the total content of the antistatic agent and the resin is preferably 7.5% by mass or more, more preferably 8.5% by mass the above. When the aforementioned ratio is greater than or equal to the aforementioned lower limit, the effect of suppressing the peeling charge of the protective film forming composite sheet becomes higher, and as a result, the effect of suppressing foreign matter mixing between the protective film forming film and the semiconductor wafer becomes higher.

抗靜電組成物(VI-2)及抗靜電性基材中，前述抗靜電劑的含量相對於前述抗靜電劑及樹脂的合計含量之比例的上限值並無特別限定。例如，就抗靜電劑的相容性變得更良好之方面而言，前述比例較佳為20質量%以下。In the antistatic composition (VI-2) and the antistatic substrate, the upper limit of the ratio of the content of the antistatic agent to the total content of the antistatic agent and the resin is not particularly limited. For example, in terms of the compatibility of the antistatic agent becoming better, the aforementioned ratio is preferably 20% by mass or less.

前述抗靜電劑的含量的比例可適宜調節為將上述之較佳的下限值及上限值任意組合而設定之範圍內。例如，一實施形態中，前述比例較佳為7.5質量%至20質量%，更佳為8.5質量%至20質量%。但這些為前述比例的一例。The ratio of the content of the aforementioned antistatic agent can be appropriately adjusted to be within a range set by arbitrarily combining the above-mentioned preferable lower limit and upper limit. For example, in one embodiment, the aforementioned ratio is preferably 7.5% by mass to 20% by mass, more preferably 8.5% by mass to 20% by mass. However, these are examples of the aforementioned ratios.

[樹脂] 作為抗靜電組成物(VI-2)及抗靜電性基材所含有之樹脂，可列舉與前述基材所含有之樹脂相同的樹脂。 抗靜電組成物(VI-2)及抗靜電性基材所含有之前述樹脂可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。[Resin] Examples of the resin contained in the antistatic composition (VI-2) and the antistatic base material include the same resins as the resin contained in the aforementioned base material. The aforementioned resin contained in the antistatic composition (VI-2) and the antistatic substrate 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 .

抗靜電組成物(VI-2)中，前述樹脂的含量相對於溶劑以外的全部成分的總含量之比例(亦即，抗靜電性基材中的前述樹脂的含量相對於抗靜電性基材的總質量之比例)較佳為30質量%至99.9質量%，更佳為35質量%至98質量%，進而較佳為60質量%至98質量%，尤佳為85質量%至98質量%。藉由前述比例為前述下限值以上，抗靜電性基材的強度變得更高。藉由前述比例為前述上限值以下，能夠使抗靜電性基材的抗靜電劑的含量更多。In the antistatic composition (VI-2), the ratio of the content of the aforementioned resin to the total content of all ingredients other than the solvent (that is, the content of the aforementioned resin in the antistatic base material relative to the amount of the antistatic base material The ratio of the total mass) is preferably 30% to 99.9% by mass, more preferably 35% to 98% by mass, still more preferably 60% to 98% by mass, and particularly preferably 85% to 98% by mass. When the aforementioned ratio is greater than or equal to the aforementioned lower limit, the strength of the antistatic substrate becomes higher. When the aforementioned ratio is not more than the aforementioned upper limit, the content of the antistatic agent of the antistatic base material can be increased.

[光聚合起始劑] 於抗靜電組成物(VI-2)含有能量線硬化性的前述樹脂之情形時，為了高效率地進行前述樹脂的聚合反應，亦可含有光聚合起始劑。 作為抗靜電組成物(VI-2)所含有之前述光聚合起始劑，例如可列舉與黏著劑組成物(I-1)所含有之光聚合起始劑相同的化合物。 抗靜電組成物(VI-2)所含有之光聚合起始劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。 抗靜電組成物(VI-2)中的光聚合起始劑的含量並無特別限定，根據前述樹脂或光聚合起始劑的種類適宜選擇即可。[Photopolymerization initiator] When the antistatic composition (VI-2) contains the energy ray-curable resin, in order to efficiently perform the polymerization reaction of the resin, a photopolymerization initiator may be contained. Examples of the photopolymerization initiator contained in the antistatic composition (VI-2) include the same compounds as the photopolymerization initiator contained in the adhesive composition (I-1). The photopolymerization initiator contained in the antistatic composition (VI-2) may be only one type or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected. The content of the photopolymerization initiator in the antistatic composition (VI-2) is not particularly limited, and may be appropriately selected according to the type of the aforementioned resin or photopolymerization initiator.

[添加劑、溶劑] 抗靜電組成物(VI-2)中，除前述抗靜電劑、樹脂及光聚合起始劑以外，亦可含有不符合這些任一種成分之填充材料、著色劑、抗氧化劑、有機潤滑劑、觸媒、軟化劑(塑化劑)等公知的各種添加劑。 作為抗靜電組成物(VI-2)所含有之前述添加劑，可列舉與上述之黏著劑組成物(I-1)所含有之其他添加劑(但抗靜電劑除外)相同的化合物。 另外，為了提高抗靜電組成物(VI-2)的流動性，亦可含有溶劑。 作為抗靜電組成物(VI-2)所含有之前述溶劑，可列舉與上述之黏著劑組成物(I-1)所含有之溶劑相同的化合物。 抗靜電組成物(VI-2)所含有之抗靜電劑及樹脂分別可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。 抗靜電組成物(VI-2)中的添加劑及溶劑的含量分別無特別限定，根據該添加劑及溶劑的種類適宜選擇即可。[Additives, solvents] In addition to the aforementioned antistatic agent, resin and photopolymerization initiator, the antistatic composition (VI-2) may also contain fillers, colorants, antioxidants, organic lubricants, and contact agents that do not meet any of these components. Various well-known additives such as medium and softener (plasticizer). Examples of the aforementioned additives contained in the antistatic composition (VI-2) include the same compounds as the other additives (except the antistatic agent) contained in the above-mentioned adhesive composition (I-1). In addition, in order to improve the fluidity of the antistatic composition (VI-2), a solvent may be contained. As the aforementioned solvent contained in the antistatic composition (VI-2), the same compounds as the solvent contained in the aforementioned adhesive composition (I-1) can be cited. The antistatic agent and resin contained in the antistatic composition (VI-2) may each be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected. The content of the additive and the solvent in the antistatic composition (VI-2) is not particularly limited, and may be appropriately selected according to the type of the additive and the solvent.

[抗靜電組成物(VI-2)之製造方法] 抗靜電組成物(VI-2)藉由調配前述抗靜電劑、前述樹脂、及視需要這些以外的成分等用以構成抗靜電組成物(VI-2)之各成分而獲得。 抗靜電組成物(VI-2)除調配成分不同之方面以外，可利用與上述之黏著劑組成物之情形相同的方法製造。[Manufacturing method of antistatic composition (VI-2)] The antistatic composition (VI-2) is obtained by blending the antistatic agent, the resin, and components other than these as necessary to form each component of the antistatic composition (VI-2). The antistatic composition (VI-2) can be manufactured by the same method as in the case of the adhesive composition described above, except for the difference in compounding components.

○表面抗靜電層 保護膜形成用複合片中的前述表面抗靜電層的配置位置與前述背面抗靜電層不同，但前述表面抗靜電層的構成本身與前述背面抗靜電層相同。例如，表面抗靜電層可使用抗靜電組成物(VI-1)，利用與上文說明之背面抗靜電層之形成方法相同的方法形成。因此，表面抗靜電層的詳細說明省略。 於保護膜形成用複合片一併具備表面抗靜電層及背面抗靜電層之情形時，這些表面抗靜電層及背面抗靜電層相互可相同亦可不同。○Surface antistatic layer The arrangement position of the surface antistatic layer in the composite sheet for forming a protective film is different from the back surface antistatic layer, but the structure itself of the surface antistatic layer is the same as the back surface antistatic layer. For example, the surface antistatic layer can be formed using the antistatic composition (VI-1), which is the same as the method for forming the back antistatic layer described above. Therefore, the detailed description of the surface antistatic layer is omitted. When the composite sheet for forming a protective film is provided with a surface antistatic layer and a back antistatic layer, the surface antistatic layer and the back antistatic layer may be the same or different from each other.

◎中間層 前述中間層為片狀或膜狀。 如上文所說明，作為較佳的中間層，可列舉一面經剝離處理之剝離性改善層。作為前述剝離性改善層，例如可列舉具備樹脂層、及形成於前述樹脂層上之剝離處理層而構成之由多層所構成之層。保護膜形成用複合片中，剝離性改善層係使該剝離性改善層的剝離處理層朝向保護膜形成用膜側而配置。◎Middle layer The aforementioned intermediate layer has a sheet shape or a film shape. As explained above, as a preferable intermediate layer, a releasability improving layer having a peeling treatment on one side can be cited. As the releasability improving layer, for example, a layer composed of multiple layers provided with a resin layer and a releasable treatment layer formed on the resin layer can be cited. In the composite sheet for forming a protective film, the releasability improvement layer is arranged such that the releasability improvement layer of the releasability improvement layer faces the film side of the protective film formation.

剝離性改善層中的前述樹脂層可藉由將含有樹脂之樹脂組成物成形而製作。 並且，剝離性改善層可藉由將前述樹脂層的一面進行剝離處理而製造。The aforementioned resin layer in the releasability improvement layer can be produced by molding a resin composition containing resin. In addition, the releasability improvement layer can be manufactured by subjecting one side of the resin layer to a peeling treatment.

前述樹脂層的剝離處理例如可藉由以下之公知的各種剝離劑進行：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、聚矽氧系或氟系之剝離劑。The peeling treatment of the aforementioned resin layer can be performed by, for example, various known release agents such as alkyd, silicone, fluorine, unsaturated polyester, polyolefin, wax, and the like. In terms of heat resistance, the aforementioned release agent is preferably an alkyd, silicone, or fluorine release agent.

作為前述樹脂層的構成材料之樹脂根據目的適宜選擇即可，並無特別限定。 作為較佳的前述樹脂，例如可列舉：聚對苯二甲酸乙二酯(PET；polyethylene terephthalate)、聚萘二甲酸乙二酯(PEN；polyethylene naphthalate)、聚對苯二甲酸丁二酯(PBT；polybutylene terephthalate)、聚乙烯(PE；polyethylene)、聚丙烯(PP；polypropylene)等。The resin as the constituent material of the resin layer may be appropriately selected according to the purpose, and is not particularly limited. As preferred aforementioned resins, for example, polyethylene terephthalate (PET; polyethylene terephthalate), polyethylene naphthalate (PEN; polyethylene naphthalate), polybutylene terephthalate (PBT ; Polybutylene terephthalate), polyethylene (PE; polyethylene), polypropylene (PP; polypropylene), etc.

前述中間層無論是否為剝離性改善層，均可由1層(單層)所構成，亦可由2層以上之多層所構成，於由多層所構成之情形時，這些多層相互可相同亦可不同，這些多層的組合並無特別限定。例如，於中間層為剝離性改善層之情形時，前述樹脂層與前述剝離處理層均可由1層(單層)所構成，亦可由2層以上之多層所構成。The aforementioned intermediate layer can be composed of one layer (single layer), whether it is a releasability improving layer or not, or can be composed of two or more layers. When composed of multiple layers, these layers may be the same or different from each other. The combination of these multiple layers is not particularly limited. For example, when the intermediate layer is a releasability improving layer, both the resin layer and the peeling treatment layer may be composed of one layer (single layer), or may be composed of multiple layers of two or more layers.

中間層的厚度根據該中間層的種類適宜調節即可，並無特別限定。 例如，剝離性改善層的厚度(樹脂層及剝離處理層的合計厚度)較佳為10nm至2000nm，更佳為25nm至1500nm，尤佳為50nm至1200nm。藉由剝離性改善層的厚度為前述下限值以上，剝離性改善層的作用變得更顯著，進而抑制剝離性改善層之切斷等破損之效果變得更高。藉由剝離性改善層的厚度為前述上限值以下，於後述拾取附保護膜之半導體晶片或附保護膜形成用膜之半導體晶片時，頂起這些晶片之力容易傳遞至這些晶片，從而能夠更容易地進行拾取。The thickness of the intermediate layer may be appropriately adjusted according to the type of the intermediate layer, and is not particularly limited. For example, the thickness of the releasability improvement layer (the total thickness of the resin layer and the peeling treatment layer) is preferably 10 nm to 2000 nm, more preferably 25 nm to 1500 nm, and particularly preferably 50 nm to 1200 nm. When the thickness of the releasability improvement layer is more than the aforementioned lower limit, the effect of the releasability improvement layer becomes more pronounced, and the effect of suppressing breakage such as breakage of the releasability improvement layer becomes higher. Since the thickness of the releasability improving layer is less than the aforementioned upper limit, when picking up a semiconductor wafer with a protective film or a semiconductor wafer with a film for forming a protective film described later, the force of pushing up these wafers can be easily transmitted to these wafers. Pick up more easily.

中間層可為透明，亦可為不透明，還可根據目的而著色。 例如，於保護膜形成用膜具有能量線硬化性之情形時，中間層較佳為使能量線透過。 例如，為了經由中間層將保護膜形成用複合片中的保護膜形成用膜進行光學檢查，中間層較佳為透明。The intermediate layer may be transparent or opaque, and may be colored according to the purpose. For example, when the film for forming a protective film has energy ray curability, the intermediate layer preferably allows energy ray to pass through. For example, in order to optically inspect the protective film forming film in the protective film forming composite sheet via the intermediate layer, the intermediate layer is preferably transparent.

◎保護膜形成用膜 前述保護膜形成用膜藉由硬化而成為保護膜。該保護膜係用以保護半導體晶圓或半導體晶片的內面(換言之，與電極形成面為相反側的面)。保護膜形成用膜為軟質，能夠容易地貼附於貼附對象物。◎Film for forming protective film The film for forming a protective film is cured to become a protective film. The protective film is used to protect the semiconductor wafer or the inner surface of the semiconductor wafer (in other words, the surface opposite to the electrode formation surface). The film for protective film formation is soft and can be easily attached to an attachment object.

本說明書中，所謂「保護膜形成用膜」，意指硬化前的膜，所謂「保護膜」，意指使保護膜形成用膜硬化而成之膜。 另外，本說明書中，即便為保護膜形成用膜硬化後，只要維持支撐片及保護膜形成用膜之硬化物(換言之，支撐片及保護膜)之積層結構，則亦將該積層結構體稱為「保護膜形成用複合片」。In this specification, the "protective film formation film" means a film before curing, and the "protective film" means a film formed by curing the protective film formation film. In addition, in this specification, even after the protective film formation film is cured, as long as the laminated structure of the support sheet and the cured product of the protective film formation film (in other words, the support sheet and the protective film) is maintained, the laminated structure is also called It is a "composite sheet for protective film formation".

前述保護膜形成用膜例如可為熱硬化性及能量線硬化性之任一種，亦可具有熱硬化性及能量線硬化性兩種特性，還可不具有熱硬化性及能量線硬化性兩種特性。The aforementioned protective film formation film may be, for example, any of thermosetting and energy ray curability, may have both thermosetting properties and energy ray curability, and may not have both thermosetting properties and energy ray curability properties. .

關於保護膜形成用膜，無論有無硬化性，並且於為硬化性之情形時無論為熱硬化性及能量線硬化性之任一種，均可由1層(單層)所構成，亦可由2層以上之多層所構成。於保護膜形成用膜由多層所構成之情形時，這些多層相互可相同亦可不同，這些多層的組合並無特別限定。Regarding the protective film formation film, whether it has curability or not, and in the case of curability, whether it is thermosetting or energy ray curability, it can be composed of one layer (single layer) or two or more layers. Consists of multiple layers. When the film for forming a protective film is composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

關於保護膜形成用膜的厚度，無論保護膜形成用膜有無硬化性，並且於為硬化性之情形時無論保護膜形成用膜為熱硬化性及能量線硬化性之任一種，均較佳為1μm至100μm，更佳為3μm至80μm，尤佳為5μm至60μm。藉由保護膜形成用膜的厚度為前述下限值以上，能夠形成保護能力更高之保護膜。另外，藉由保護膜形成用膜的厚度為前述上限值以下，能夠避免厚度過厚。 此處，所謂「保護膜形成用膜的厚度」，意指保護膜形成用膜整體的厚度，例如所謂由多層所構成之保護膜形成用膜的厚度，意指構成保護膜形成用膜之全部層的合計厚度。Regarding the thickness of the protective film formation film, regardless of whether the protective film formation film has curability, and when it is curable, regardless of whether the protective film formation film is thermosetting or energy ray curable, it is preferably 1 μm to 100 μm, more preferably 3 μm to 80 μm, particularly preferably 5 μm to 60 μm. When the thickness of the film for forming a protective film is more than the aforementioned lower limit value, a protective film with higher protective ability can be formed. In addition, since the thickness of the film for forming a protective film is not more than the aforementioned upper limit value, excessive thickness can be avoided. Here, the "thickness of the protective film formation film" means the overall thickness of the protective film formation film. For example, the thickness of the protective film formation film composed of multiple layers means the entirety of the protective film formation film The total thickness of the layer.

[保護膜形成用組成物] 保護膜形成用膜可使用含有該保護膜形成用膜的構成材料之保護膜形成用組成物而形成。例如，保護膜形成用膜可藉由於該保護膜形成用膜的形成對象面塗敷保護膜形成用組成物，並視需要使之乾燥而形成。保護膜形成用組成物中的常溫下不會氣化的成分彼此的含量比率通常與保護膜形成用膜中的前述成分彼此的含量比率相同。 熱硬化性保護膜形成用膜可使用熱硬化性保護膜形成用組成物而形成，能量線硬化性保護膜形成用膜可使用能量線硬化性保護膜形成用組成物而形成。此外，本說明書中，於保護膜形成用膜具有熱硬化性及能量線硬化性兩種特性之情形時，對於形成保護膜而言，保護膜形成用膜的熱硬化的貢獻大於能量線硬化的貢獻時，將保護膜形成用膜視作熱硬化性。相反地，對於形成保護膜而言，保護膜形成用膜的能量線硬化的貢獻大於熱硬化的貢獻時，將保護膜形成用膜視作能量線硬化性。[Composition for forming protective film] The film for protective film formation can be formed using the composition for protective film formation containing the constituent material of the film for protective film formation. For example, the protective film formation film can be formed by coating the protective film formation composition on the surface to be formed of the protective film formation film, and drying it if necessary. The content ratio of the components that do not vaporize at room temperature in the protective film formation composition is usually the same as the content ratio of the aforementioned components in the protective film formation film. The film for forming a thermosetting protective film can be formed using the composition for forming a thermosetting protective film, and the film for forming an energy ray curable protective film can be formed using the composition for forming an energy ray curable protective film. In addition, in this specification, when the protective film forming film has both thermosetting properties and energy ray curable properties, the contribution of the thermal curing of the protective film forming film to the formation of the protective film is greater than that of the energy ray curing. When contributing, the film for forming a protective film is regarded as thermosetting. On the contrary, when the contribution of the energy ray hardening of the protective film formation film is greater than the contribution of thermal hardening to the formation of the protective film, the protective film formation film is regarded as energy ray hardening property.

例如可利用與上述塗敷黏著劑組成物之情形相同的方法塗敷保護膜形成用組成物。For example, the composition for forming a protective film can be applied by the same method as in the case of applying the adhesive composition described above.

無論保護膜形成用組成物為熱硬化性及能量線硬化性之任一種，保護膜形成用組成物的乾燥條件均無特別限定。但於保護膜形成用組成物含有後述溶劑之情形時，較佳為進行加熱乾燥。並且，含有溶劑之保護膜形成用組成物例如較佳為於70℃至130℃且10秒至5分鐘之條件下進行加熱乾燥。但熱硬化性保護膜形成用組成物較佳為以該組成物本身及由該組成物所形成之熱硬化性保護膜形成用膜不熱硬化之方式進行加熱乾燥。The drying conditions of the protective film formation composition are not particularly limited regardless of whether the protective film formation composition is thermosetting or energy ray curable. However, when the composition for forming a protective film contains a solvent described later, it is preferable to heat and dry. In addition, the composition for forming a protective film containing a solvent is preferably heated and dried under the conditions of 70°C to 130°C for 10 seconds to 5 minutes, for example. However, the composition for forming a thermosetting protective film is preferably heated and dried so that the composition itself and the film for forming a thermosetting protective film formed from the composition are not thermally cured.

以下，對熱硬化性保護膜形成用膜及能量線硬化性保護膜形成用膜依序進行說明。Hereinafter, the film for forming a thermosetting protective film and the film for forming an energy ray curable protective film will be described in order.

○熱硬化性保護膜形成用膜 關於將熱硬化性保護膜形成用膜貼附於半導體晶圓的內面並使之熱硬化而形成保護膜時的硬化條件，只要保護膜成為充分地發揮該保護膜的功能之程度的硬化度，則並無特別限定，根據熱硬化性保護膜形成用膜的種類適宜選擇即可。 例如，熱硬化性保護膜形成用膜之熱硬化時的加熱溫度較佳為100℃至200℃，更佳為110℃至180℃，尤佳為120℃至170℃。並且，前述熱硬化時的加熱時間較佳為0.5小時至5小時，更佳為0.5小時至3小時，尤佳為1小時至2小時。○Film for forming thermosetting protective film Regarding the curing conditions when a film for forming a thermosetting protective film is attached to the inner surface of a semiconductor wafer and thermally cured to form a protective film, as long as the protective film has a degree of curing that can fully perform the function of the protective film , It is not particularly limited, and may be appropriately selected according to the type of the thermosetting protective film forming film. For example, the heating temperature during thermal curing of the film for forming a thermosetting protective film is preferably 100°C to 200°C, more preferably 110°C to 180°C, and particularly preferably 120°C to 170°C. In addition, the heating time during thermal hardening is preferably 0.5 hour to 5 hours, more preferably 0.5 hour to 3 hours, and particularly preferably 1 hour to 2 hours.

作為較佳的熱硬化性保護膜形成用膜，例如可列舉含有聚合物成分(A)及熱硬化性成分(B)之膜。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而進行硬化(聚合)反應之成分。此外，本說明書中，聚合反應亦包括縮聚反應。As a preferable film for forming a thermosetting protective film, for example, a film containing a polymer component (A) and a thermosetting component (B) can be cited. The polymer component (A) is regarded as a component formed by the polymerization reaction of a polymerizable compound. In addition, the thermosetting component (B) is a component that can undergo a hardening (polymerization) reaction using heat as a trigger of the reaction. In addition, in this specification, polymerization reaction also includes polycondensation reaction.

[熱硬化性保護膜形成用組成物(III-1)] 作為較佳的熱硬化性保護膜形成用組成物，例如可列舉含有前述聚合物成分(A)及熱硬化性成分(B)之熱硬化性保護膜形成用組成物(III-1)(本說明書中，有時僅簡稱為「組成物(III-1)」)等。[Composition for forming thermosetting protective film (III-1)] As a preferable composition for forming a thermosetting protective film, for example, a composition for forming a thermosetting protective film (III-1) containing the aforementioned polymer component (A) and thermosetting component (B) (this In the specification, it may be simply referred to as "composition (III-1)").

[聚合物成分(A)] 聚合物成分(A)係用以對熱硬化性保護膜形成用膜賦予造膜性以及／或者可撓性等之成分。 組成物(III-1)及熱硬化性保護膜形成用膜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，這些的組合及比率可任意選擇。[Polymer component (A)] The polymer component (A) is a component for imparting film forming properties and/or flexibility to the film for forming a thermosetting protective film. The polymer component (A) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, a combination of these And the ratio can be chosen arbitrarily.

作為聚合物成分(A)，例如可列舉：丙烯酸系樹脂、聚酯、胺基甲酸酯系樹脂、丙烯酸胺基甲酸酯樹脂、聚矽氧系樹脂、橡膠系樹脂、苯氧基樹脂、熱硬化性聚醯亞胺等，較佳為丙烯酸系樹脂。As the polymer component (A), for example, acrylic resin, polyester, urethane resin, acrylic urethane resin, silicone resin, rubber resin, phenoxy resin, The thermosetting polyimide or the like is preferably an acrylic resin.

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聚合物。 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用膜的形狀穩定性(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用膜變得易於追隨於被接著體的凹凸面，能夠進一步抑制於被接著體與熱硬化性保護膜形成用膜之間產生空隙(void)等。 此外，本說明書中，所謂重量平均分子量，只要無特別說明，則係指藉由凝膠滲透層析(GPC；Gel Permeation Chromatography)法所測定之聚苯乙烯換算值。As the aforementioned acrylic resin in the polymer component (A), a known acrylic polymer can be cited. The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is equal to or higher than the aforementioned lower limit, the shape stability of the film for forming a thermosetting protective film (stability with time during storage) improves. In addition, since the weight average molecular weight of the acrylic resin is less than the aforementioned upper limit, the film for forming a thermosetting protective film can easily follow the uneven surface of the adherend, which can further suppress the adherence and the thermosetting protection Voids and the like are generated between the films for film formation. In addition, in this specification, the weight average molecular weight means a polystyrene conversion value measured by a gel permeation chromatography (GPC; Gel Permeation Chromatography) method unless otherwise specified.

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，例如保護膜形成用膜之硬化物與支撐片之接著力受到抑制，支撐片的剝離性適度提高。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用膜及其硬化物與被接著體之接著力提高。The glass transition temperature (Tg) of the acrylic resin is preferably -60°C to 70°C, more preferably -30°C to 50°C. When the Tg of the acrylic resin is more than the aforementioned lower limit, for example, the adhesive force of the cured product of the protective film forming film and the support sheet is suppressed, and the releasability of the support sheet is appropriately improved. In addition, when the Tg of the acrylic resin is equal to or lower than the aforementioned upper limit, the adhesive force of the film for forming a thermosetting protective film and its cured product and the adherend is improved.

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2種以上之單體之共聚物等。As acrylic resins, for example, one or two or more (meth)acrylate polymers; selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N- Copolymers of two or more monomers in methylol acrylamide, etc.

此外，本說明書中，「(甲基)丙烯酸」的概念包括「丙烯酸」及「甲基丙烯酸」兩者。關於與(甲基)丙烯酸類似之用語亦相同，例如「(甲基)丙烯醯基」的概念包括「丙烯醯基」及「甲基丙烯醯基」兩者，「(甲基)丙烯酸酯」的概念包括「丙烯酸酯」及「甲基丙烯酸酯」兩者。In addition, in this specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The terms similar to (meth)acrylic acid are also the same. For example, the concept of “(meth)acrylic acid group” includes both “acrylic acid group” and “methacrylic acid group”, and “(meth)acrylate” The concept includes both "acrylate" and "methacrylate".

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((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((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」，意指胺基的1個或2個氫原子被氫原子以外的基取代而成之基。Examples of the (meth)acrylate constituting the acrylic resin include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate Base) hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-octyl (meth)acrylate Nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate) , Tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, ten (meth)acrylate Hexaalkyl ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. constitute alkyl esters The alkyl group is alkyl (meth)acrylate with a chain structure of carbon number 1 to 18; (meth)acrylic acid cycloalkane such as isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, etc. Base ester; (meth)acrylic acid benzyl ester and other (meth)acrylic acid aralkyl esters; (meth)acrylic acid dicyclopentenyl ester and other (meth)acrylic acid cycloalkenes; (meth)acrylic acid dicyclopentene Cycloalkenyloxyalkyl (meth)acrylates such as oxyethyl; (meth)acrylimines; glycidyl (meth)acrylates and other (meth)acrylates containing glycidyl groups; Base) hydroxymethyl acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate , 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyl-containing (meth)acrylates; (meth)acrylate N-methylaminoethyl and other substituted amines Base (meth)acrylate, etc. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms.

丙烯酸系樹脂例如除前述(甲基)丙烯酸酯以外，亦可為使選自(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而成之丙烯酸系樹脂。The acrylic resin may be selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, etc., in addition to the aforementioned (meth)acrylate. Acrylic resin made by copolymerization of one or more monomers.

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，這些的組合及比率可任意選擇。The monomer constituting the acrylic resin may be only one type or two or more types, and when it is two or more types, the combination and ratio of these can 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、異氰酸酯基等能夠與其他化合物鍵結之官能基。丙烯酸系樹脂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)而與其他化合物直接鍵結。藉由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複合片所獲得之封裝體的可靠性提高之傾向。The acrylic resin may also have functional groups capable of bonding to other compounds, such as vinyl groups, (meth)acrylic groups, amino groups, hydroxyl groups, carboxyl groups, and isocyanate groups. The aforementioned functional group of 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). When the acrylic resin is bonded to another compound via the aforementioned functional group, the reliability of the package obtained using the composite sheet for forming a protective film tends to be improved.

本發明中，作為聚合物成分(A)，可不使用丙烯酸系樹脂而單獨使用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」)，亦可與丙烯酸系樹脂併用。藉由使用前述熱塑性樹脂，有時樹脂膜自支撐片之剝離性提高，或熱硬化性保護膜形成用膜變得易於追隨於被接著體的凹凸面，能夠進一步抑制於被接著體與熱硬化性保護膜形成用膜之間產生空隙等。In the present invention, as the polymer component (A), a thermoplastic resin other than an acrylic resin (hereinafter, simply referred to as "thermoplastic resin" in some cases) may be used alone instead of an acrylic resin, or may be used in combination with an acrylic resin. By using the aforementioned thermoplastic resin, the peelability of the resin film from the supporting sheet may be improved, or the thermosetting protective film forming film may easily follow the uneven surface of the adherend, which can further suppress the adherence and heat curing There are voids between the films for forming a protective film.

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 to 150°C, more preferably -20 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, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, etc. are mentioned, for example.

組成物(III-1)及熱硬化性保護膜形成用膜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，這些熱塑性樹脂的組合及比率可任意選擇。The aforementioned thermoplastic resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or two or more types. In the case of two or more types, the combination of these thermoplastic resins and The ratio can be chosen arbitrarily.

組成物(III-1)中，無論聚合物成分(A)的種類如何，聚合物成分(A)的含量相對於溶劑以外的全部成分的總含量之比例(亦即，熱硬化性保護膜形成用膜中的聚合物成分(A)的含量相對於熱硬化性保護膜形成用膜的總質量之比例)均較佳為5質量%至85質量%，更佳為5質量%至80質量%，例如可為5質量%至65質量%、5質量%至50質量%、以及5質量%至35質量%之任一者。In the composition (III-1), regardless of the type of the polymer component (A), the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (that is, the formation of a thermosetting protective film The ratio of the content of the polymer component (A) in the film to the total mass of the film for forming a thermosetting protective film) is preferably 5 to 85% by mass, more preferably 5 to 80% by mass For example, it may be any of 5 mass% to 65% by mass, 5 mass% to 50% by mass, and 5 mass% to 35% by mass.

聚合物成分(A)有時亦符合熱硬化性成分(B)。本發明中，於組成物(III-1)含有此種符合聚合物成分(A)及熱硬化性成分(B)兩者之成分之情形時，組成物(III-1)視為含有聚合物成分(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) contains such components that meet both the polymer component (A) and the thermosetting component (B), the composition (III-1) is regarded as containing the polymer Component (A) and thermosetting component (B).

[熱硬化性成分(B)] 熱硬化性成分(B)係用以使熱硬化性保護膜形成用膜硬化之成分。 組成物(III-1)及熱硬化性保護膜形成用膜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，這些的組合及比率可任意選擇。[Thermosetting component (B)] The thermosetting component (B) is a component for curing the film for forming a thermosetting protective film. The composition (III-1) and the thermosetting component (B) contained in the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, these The combination and ratio can be selected arbitrarily.

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。Examples of the thermosetting component (B) include epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, etc., and preferred are Epoxy-based thermosetting resin.

(環氧系熱硬化性樹脂) 環氧系熱硬化性樹脂由環氧樹脂(B1)及熱硬化劑(B2)所構成。 組成物(III-1)及熱硬化性保護膜形成用膜所含有之環氧系熱硬化性樹脂可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。(Epoxy-based thermosetting resin) The epoxy-based thermosetting resin is composed of epoxy resin (B1) and thermosetting agent (B2). The epoxy-based thermosetting resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, these The combination and ratio can be selected arbitrarily.

・環氧樹脂(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。・Epoxy resin (B1) Examples of the epoxy resin (B1) include known epoxy resins, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, ortho-cresol novolac epoxy Resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, etc. Compound.

作為環氧樹脂(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，與丙烯酸系樹脂之相容性較高。因此，藉由使用具有不飽和烴基之環氧樹脂，使用保護膜形成用複合片所獲得之附樹脂膜之半導體晶片的可靠性提高。As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can also be used. Epoxy resins with unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of a semiconductor wafer with a resin film obtained using a composite sheet for forming a protective film is improved.

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變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。 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。 不飽和烴基為具有聚合性之不飽和基，作為該不飽和烴基的具體例，可列舉：次乙基(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。As an epoxy resin which has an unsaturated hydrocarbon group, the compound which converted a part of epoxy group of a polyfunctional epoxy resin into the group which has an unsaturated hydrocarbon group, for example is mentioned. Such a compound is obtained, for example, by performing an addition reaction of (meth)acrylic acid or a derivative thereof with an epoxy group. In addition, as an epoxy resin having an unsaturated hydrocarbon group, for example, a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring constituting the epoxy resin or the like can be cited. The unsaturated hydrocarbon group is a polymerizable unsaturated group. Specific examples of the unsaturated hydrocarbon group include ethylene (vinyl), 2-propenyl (allyl), (meth)acrylic, The (meth)acrylamido group, etc., is preferably an acrylamido 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用膜的硬化性、以及硬化後的樹脂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。 環氧樹脂(B1)的環氧當量較佳為100g/eq至1000g/eq，更佳為150g/eq至950g/eq。The number average molecular weight of the epoxy resin (B1) is not particularly limited, but it is preferably 300 to 30,000 in terms of the curability of the film for forming a thermosetting protective film, and the strength and heat resistance of the resin film after curing. , More preferably 300 to 10,000, particularly preferably 300 to 3000. The epoxy equivalent of the epoxy resin (B1) is preferably 100 g/eq to 1000 g/eq, more preferably 150 g/eq to 950 g/eq.

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，這些的組合及比率可任意選擇。The epoxy resin (B1) may be used individually by 1 type, and may use 2 or more types together, and when using 2 or more types together, these combination and ratio can be selected arbitrarily.

・熱硬化劑(B2) 熱硬化劑(B2)發揮針對環氧樹脂(B1)之硬化劑的功能。 作為熱硬化劑(B2)，例如可列舉：1分子中具有2個以上之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。・Thermal hardener (B2) The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1). As a thermosetting agent (B2), the compound which has 2 or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. As the aforementioned functional group, for example, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, a group formed by an anhydride of an acid group, etc. are mentioned, and a phenolic hydroxyl group, an amino group, or an acid group is preferably anhydride The formed group is more preferably a phenolic hydroxyl group or an amino 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、芳烷基型酚樹脂等。 熱硬化劑(B2)中，作為具有胺基之胺系硬化劑，例如可列舉：二氰二胺等。Among the thermosetting agents (B2), as phenolic curing agents having phenolic hydroxyl groups, for example, polyfunctional phenol resins, biphenols, novolac type phenol resins, dicyclopentadiene phenol resins, and aralkyl type Phenolic resin, etc. In the thermosetting agent (B2), examples of the amine-based curing agent having an amine group include dicyandiamine.

熱硬化劑(B2)亦可具有不飽和烴基。 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。 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 thermosetting agent (B2) may have an unsaturated hydrocarbon group. As the thermosetting agent (B2) having an unsaturated hydrocarbon group, for example, a compound in which a part of the hydroxyl group of a phenol resin is substituted by 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 and so on. The aforementioned unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the aforementioned 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，就保護膜自支撐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。When using a phenolic hardener as the thermosetting agent (B2), in terms of improving the peelability of the protective film self-supporting sheet, the thermosetting agent (B2) is preferably a phenol with a high softening point or glass transition temperature. Department of hardener.

熱硬化劑(B2)中，例如多官能酚樹脂、酚醛清漆型酚樹脂、二環戊二烯型酚樹脂、芳烷基型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。 熱硬化劑(B2)中，例如聯苯酚、雙氰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 number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, and aralkyl type phenol resin is preferably 300 to 30,000, and more It is preferably 400 to 10,000, particularly preferably 500 to 3,000. In the thermosetting agent (B2), the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited. For example, it is preferably 60 to 500.

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，這些的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, and when using 2 or more types together, these combination and ratio can be selected arbitrarily.

組成物(III-1)及熱硬化性保護膜形成用膜中，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，例如可為1質量份至100質量份、1質量份至50質量份、1質量份至25質量份、以及1質量份至10質量份之任一者。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用膜變得更容易進行硬化。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用膜的吸濕率降低，使用保護膜形成用複合片所獲得之封裝體的可靠性進一步提高。In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting agent (B2) is preferably 0.1 to 500 parts by mass relative to 100 parts by mass of the epoxy resin (B1) , More preferably 1 part by mass to 200 parts by mass, for example, can be any of 1 part by mass to 100 parts by mass, 1 part by mass to 50 parts by mass, 1 part by mass to 25 parts by mass, and 1 part by mass to 10 parts by mass By. When the said content of a thermosetting agent (B2) is more than the said lower limit, the film for thermosetting protective film formation becomes easy to harden. When the aforementioned content of the thermosetting agent (B2) is below the aforementioned upper limit, the moisture absorption rate of the thermosetting protective film formation film decreases, and the reliability of the package obtained using the protective film formation composite sheet is further improved.

組成物(III-1)及熱硬化性保護膜形成用膜中，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20質量份至500質量份，更佳為25質量份至300質量份，進而較佳為30質量份至150質量份，例如可為35質量份至100質量份、以及40質量份至80質量份之任一者。藉由熱硬化性成分(B)的前述含量為此種範圍，例如保護膜形成用膜之硬化物與支撐片之接著力受到抑制，支撐片的剝離性提高。In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) relative to the polymer The content of ingredient (A) is 100 parts by mass, preferably 20 parts by mass to 500 parts by mass, more preferably 25 parts by mass to 300 parts by mass, still more preferably 30 parts by mass to 150 parts by mass, for example, 35 parts by mass To 100 parts by mass and any one of 40 parts by mass to 80 parts by mass. When the aforementioned content of the thermosetting component (B) is in this range, for example, the adhesive force of the cured product of the protective film forming film and the support sheet is suppressed, and the releasability of the support sheet is improved.

[硬化促進劑(C)] 組成物(III-1)及熱硬化性保護膜形成用膜亦可含有硬化促進劑(C)。硬化促進劑(C)係用以調整組成物(III-1)的硬化速度之成分。 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(1個以上之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(1個以上之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。[Hardening accelerator (C)] The composition (III-1) and the film for forming a thermosetting protective film may contain a hardening accelerator (C). The hardening accelerator (C) is a component used to adjust the hardening speed of the composition (III-1). As a preferable hardening accelerator (C), for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol can be cited; 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 one or more hydrogen atoms are replaced by groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (more than one Phosphine in which hydrogen atoms are replaced by organic groups); tetraphenyl boron salts such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, etc.

組成物(III-1)及熱硬化性保護膜形成用膜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，這些的組合及比率可任意選擇。The composition (III-1) and the curing accelerator (C) contained in the film for forming a thermosetting protective film may be one type or two or more types. In the case of two or more types, a combination of these And the ratio can be chosen arbitrarily.

於使用硬化促進劑(C)之情形時，組成物(III-1)及熱硬化性保護膜形成用膜中，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7質量份。藉由硬化促進劑(C)的前述含量為前述下限值以上，能夠獲得更顯著的由使用硬化促進劑(C)所帶來之效果。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用膜中朝與被接著體之接著界面側移動而偏析之效果變高。結果為，使用保護膜形成用複合片所獲得之附保護膜之半導體晶片的可靠性進一步提高。In the case of using a curing accelerator (C), the content of the curing accelerator (C) in the composition (III-1) and the film for forming a thermosetting protective film is relative to the content of the thermosetting component (B) 100 Parts by mass, preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 7 parts by mass. When the aforementioned content of the hardening accelerator (C) is equal to or higher than the aforementioned lower limit, it is possible to obtain a more remarkable effect by using the hardening accelerator (C). Since the content of the hardening accelerator (C) is below the aforementioned upper limit, for example, the hardening accelerator (C) with high polarity is prevented from being in contact with the adherend in the film for forming a thermosetting protective film under high temperature and high humidity conditions. Then the interface side moves and the effect of segregation becomes higher. As a result, the reliability of the semiconductor wafer with a protective film obtained by using the composite sheet for forming a protective film is further improved.

[填充材料(D)] 組成物(III-1)及熱硬化性保護膜形成用膜亦可含有填充材料(D)。藉由熱硬化性保護膜形成用膜含有填充材料(D)，使熱硬化性保護膜形成用膜硬化而獲得之保護膜容易調整熱膨脹係數，藉由使該熱膨脹係數對於保護膜之形成對象物而言最佳化，使用保護膜形成用複合片所獲得之附保護膜之半導體晶片的可靠性進一步提高。另外，藉由熱硬化性保護膜形成用膜含有填充材料(D)，亦能夠降低保護膜的吸濕率，或提高散熱性。[Filling material (D)] The composition (III-1) and the film for forming a thermosetting protective film may contain a filler (D). When the thermosetting protective film forming film contains the filler (D), the protective film obtained by curing the thermosetting protective film forming film is easy to adjust the thermal expansion coefficient, and the thermal expansion coefficient is relative to the object forming the protective film In terms of optimization, the reliability of a semiconductor wafer with a protective film obtained by using a composite sheet for forming a protective film is further improved. In addition, when the film for forming a thermosetting protective film contains the filler (D), the moisture absorption rate of the protective film can also be reduced or the heat dissipation can 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。 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。 這些之中，無機填充材料較佳為二氧化矽或氧化鋁，更佳為二氧化矽。The filling material (D) may be any one of an organic filling material and an inorganic filling material, preferably an inorganic filling material. As a preferable inorganic filler, for example, powders such as silica, alumina, talc, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, boron nitride, etc. can be cited; these inorganic fillers are made by sphericalization Beads; surface modification products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. Among these, the inorganic filler material is preferably silica or alumina, more preferably silica.

組成物(III-1)及熱硬化性保護膜形成用膜所含有之填充材料(D)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The filler (D) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or two or more types. In the case of two or more types, the combination of these and The ratio can be chosen arbitrarily.

組成物(III-1)中，填充材料(D)的含量相對於溶劑以外的全部成分的總含量之比例(亦即，熱硬化性保護膜形成用膜中的填充材料(D)的含量相對於熱硬化性保護膜形成用膜的總質量之比例)較佳為5質量%至80質量%，更佳為10質量%至70質量%，例如可為20質量%至65質量%、30質量%至65質量%、以及40質量%至65質量%之任一者。藉由前述比例為此種範圍，上述之保護膜的熱膨脹係數之調整變得更容易。In composition (III-1), the ratio of the content of the filler (D) to the total content of all components other than the solvent (that is, the content of the filler (D) in the film for forming a thermosetting protective film is relative to The ratio of the total mass of the film for forming a thermosetting protective film) is preferably 5 mass% to 80 mass%, more preferably 10 mass% to 70 mass%, for example, 20 mass% to 65% by mass, 30 mass% Any one of% to 65% by mass, and 40% to 65% by mass. When the aforementioned ratio is in this range, the adjustment of the thermal expansion coefficient of the aforementioned protective film becomes easier.

[偶合劑(E)] 組成物(III-1)及熱硬化性保護膜形成用膜亦可含有偶合劑(E)。藉由使用具有能夠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)，能夠提高熱硬化性保護膜形成用膜對被接著體之接著性及密接性。另外，藉由使用偶合劑(E)，熱硬化性保護膜形成用膜之硬化物不損害耐熱性而耐水性提高。[Coupling agent (E)] The composition (III-1) and the film for forming a thermosetting protective film may contain a coupling agent (E). By using a compound having a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (E), the adhesiveness and adhesion of the film for forming a thermosetting protective film to the adherend can be improved. In addition, by using the coupling agent (E), the cured product of the film for forming a thermosetting protective film does not impair heat resistance and improves water resistance.

偶合劑(E)較佳為具有能夠與聚合物成分(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。 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。The coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional group possessed by the polymer component (A) and the thermosetting component (B), and more preferably a silane coupling agent. As a preferred silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethyl Oxyoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl Diethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethyl Oxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, ethylene Trimethoxysilane, vinyl triethoxysilane, imidazole silane, etc.

組成物(III-1)及熱硬化性保護膜形成用膜所含有之偶合劑(E)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The coupling agent (E) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, the combination of these and The ratio can be chosen arbitrarily.

於使用偶合劑(E)之情形時，組成物(III-1)及熱硬化性保護膜形成用膜中，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，填充材料(D)於樹脂中之分散性提高，以及／或者熱硬化性保護膜形成用膜與被接著體之接著性提高等，能夠獲得更顯著的由使用偶合劑(E)所帶來之效果。另外，藉由偶合劑(E)的前述含量為前述上限值以下，能夠進一步抑制產生逸氣。When the coupling agent (E) is used, the content of the coupling agent (E) in the composition (III-1) and the thermosetting protective film formation film is relative to the polymer component (A) and the thermosetting component ( The total content of B) is 100 parts by mass, preferably 0.03 parts by mass to 20 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass, and particularly preferably 0.1 parts by mass to 5 parts by mass. When the aforementioned content of the coupling agent (E) is more than the aforementioned lower limit, the dispersibility of the filler (D) in the resin is improved, and/or the adhesion between the thermosetting protective film forming film and the adherend is improved, etc. , Can obtain more significant effects brought by the use of coupling agent (E). In addition, when the aforementioned content of the coupling agent (E) is not more than the aforementioned upper limit, the generation of outgassing can be further suppressed.

[交聯劑(F)] 作為聚合物成分(A)若使用上述丙烯酸系樹脂等具有能夠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之情形時，組成物(III-1)及熱硬化性保護膜形成用膜亦可含有交聯劑(F)。交聯劑(F)係用以使聚合物成分(A)中的前述官能基與其他化合物鍵結而進行交聯之成分，藉由如此進行交聯，能夠調節熱硬化性保護膜形成用膜的初始接著力及凝聚力。[Crosslinking agent (F)] As the polymer component (A), if the above-mentioned acrylic resin or the like has a functional group capable of bonding with other compounds, such as vinyl, (meth)acryloyl, amino, hydroxyl, carboxyl, isocyanate, etc., the aforementioned acrylic In the case of a resin or the like, the composition (III-1) and the film for forming a thermosetting protective film may contain a crosslinking agent (F). The cross-linking agent (F) is a component used to bond the aforementioned functional groups in the polymer component (A) with other compounds to perform cross-linking. By cross-linking in this way, the film for forming a thermosetting protective film can be adjusted The initial adhesion and cohesion.

作為交聯劑(F)，例如可列舉：有機多元異氰酸酯化合物、有機多元亞胺化合物、金屬螯合物系交聯劑(具有金屬螯合物結構之交聯劑)、氮丙啶系交聯劑(具有氮丙啶基之交聯劑)等。As the crosslinking agent (F), for example, organic polyisocyanate compound, organic polyimine compound, metal chelate crosslinking agent (crosslinking agent having a metal chelate structure), aziridine crosslinking Agent (crosslinking agent with aziridinyl group) and the like.

作為前述有機多元異氰酸酯化合物，例如可列舉：芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物及脂環族多元異氰酸酯化合物(以下，有時將這些化合物統一簡稱為「芳香族多元異氰酸酯化合物等」)；前述芳香族多元異氰酸酯化合物等的三聚物、異氰脲酸酯體及加合物；使前述芳香族多元異氰酸酯化合物等與多元醇化合物反應而獲得之末端異氰酸酯胺基甲酸酯預聚物等。前述「加合物」意指前述芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物或脂環族多元異氰酸酯化合物，與乙二醇、丙二醇、新戊二醇、三羥甲基丙烷或蓖麻油等含低分子活性氫化合物之反應物。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 aforementioned 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 bodies, and adducts of the aforementioned aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc. with polyol compounds, etc. . The aforementioned "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound, or alicyclic polyisocyanate compound, which contains ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, etc. The reactant of low molecular active hydrogen compounds. As an example of the said adduct, the xylylene diisocyanate adduct of trimethylolpropane etc. mentioned later can be mentioned. In addition, the term "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the end 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；於三羥甲基丙烷等多元醇的全部或一部分羥基加成了甲苯二異氰酸酯、六亞甲基二異氰酸酯及苯二甲基二異氰酸酯中的任1種或2種以上而成之化合物；離胺酸二異氰酸酯等。As the aforementioned organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate Isocyanate; Diphenylmethane-4,4'-Diisocyanate; Diphenylmethane-2,4'-Diisocyanate; 3-Methyldiphenylmethane Diisocyanate; Hexamethylene Diisocyanate; Isophorone Diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; toluene diisocyanate is added to all or part of the hydroxyl groups of polyols such as trimethylolpropane, Compounds of any one or more 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 the aforementioned organic polyimine compound, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridine methamide), trimethylolpropane-tri-β-nitrogen Propidinyl propionate, tetramethylolmethane-tris-β-aziridinyl propionate, N,N'-toluene-2,4-bis(1-aziridinylmethamine) triethylene Based on melamine and so on.

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，能夠簡便地將交聯結構導入至熱硬化性保護膜形成用膜中。When an organic polyvalent isocyanate compound is used as the crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A). When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the reaction of the crosslinking agent (F) with the polymer component (A) can easily introduce the crosslinked structure into In the film for forming a thermosetting protective film.

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

於使用交聯劑(F)之情形時，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，能夠獲得更顯著的由使用交聯劑(F)所帶來之效果。另外，藉由交聯劑(F)的前述含量為前述上限值以下，能夠抑制使用過量的交聯劑(F)。In the case of using the crosslinking agent (F), in the composition (III-1), the content of the crosslinking agent (F) relative to the content of the polymer component (A) is 100 parts by mass, preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.1 to 10 parts by mass, particularly preferably 0.5 to 5 parts by mass. When the aforementioned content of the cross-linking agent (F) is more than the aforementioned lower limit value, a more significant effect due to the use of the cross-linking agent (F) can be obtained. In addition, when the aforementioned content of the crosslinking agent (F) is not more than the aforementioned upper limit, it is possible to suppress the excessive use of the crosslinking agent (F).

[能量線硬化性樹脂(G)] 組成物(III-1)及熱硬化性保護膜形成用膜亦可含有能量線硬化性樹脂(G)。熱硬化性保護膜形成用膜藉由含有能量線硬化性樹脂(G)，能夠藉由照射能量線而改變特性。[Energy ray curable resin (G)] The composition (III-1) and the film for forming a thermosetting protective film may contain an energy ray-curable resin (G). The film for forming a thermosetting protective film contains energy-ray-curable resin (G), so that its characteristics can be changed by energy-ray irradiation.

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。 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。The energy ray curable resin (G) is obtained by polymerizing (curing) an energy ray curable compound. Examples of the aforementioned energy ray curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate-based compounds having a (meth)acryloyl group are preferred.

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；環氧改質(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。Examples of the acrylate-based compounds include: trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate Base) acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol two(meth)acrylate, 1,6-hexanediol two (Meth)acrylates and other (meth)acrylates containing chain aliphatic skeletons; (meth)acrylates such as dicyclopentyl di(meth)acrylates containing cyclic aliphatic skeletons; polyethylene glycol Polyalkylene glycol (meth)acrylate such as di(meth)acrylate; oligoester (meth)acrylate; (meth)acrylate urethane oligomer; epoxy modification (former Base) acrylate; polyether (meth)acrylate other than the aforementioned polyalkylene glycol (meth)acrylate; itaconic acid oligomer, etc.

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，這些的組合及比率可任意選擇。The aforementioned energy ray curable compound used for polymerization may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

組成物(III-1)及熱硬化性保護膜形成用膜所含有之能量線硬化性樹脂(G)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The energy ray curable resin (G) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, these The combination and ratio can be arbitrarily selected.

於使用能量線硬化性樹脂(G)之情形時，組成物(III-1)中，能量線硬化性樹脂(G)的含量相對於組成物(III-1)的總質量之比例較佳為1質量%至95質量%，更佳為5質量%至90質量%，尤佳為10質量%至85質量%。In the case of using energy ray curable resin (G), in the composition (III-1), the ratio of the content of the energy ray curable resin (G) to the total mass of the composition (III-1) is preferably 1% by mass to 95% by mass, more preferably 5% by mass to 90% by mass, and particularly preferably 10% by mass to 85% by mass.

[光聚合起始劑(H)] 於組成物(III-1)及熱硬化性保護膜形成用膜含有能量線硬化性樹脂(G)之情形時，為了高效率地進行能量線硬化性樹脂(G)的聚合反應，亦可含有光聚合起始劑(H)。[Photopolymerization initiator (H)] When the composition (III-1) and the film for forming a thermosetting protective film contain energy ray curable resin (G), in order to efficiently polymerize the energy ray curable resin (G), it may also contain Photopolymerization initiator (H).

作為組成物(III-1)中的光聚合起始劑(H)，例如可列舉：安息香、安息香甲醚、安息香***、安息香異丙醚、安息香異丁醚、安息香苯甲酸、安息香苯甲酸甲酯、安息香二甲基縮酮等安息香化合物；苯乙酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等苯乙酮化合物；雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦等醯基氧化膦化合物；苄基苯基硫醚、一硫化四甲基秋蘭姆等硫醚化合物；1-羥基環己基苯基酮等α-酮醇化合物；偶氮雙異丁腈等偶氮化合物；二茂鈦等二茂鈦化合物；噻噸酮等噻噸酮化合物；過氧化物化合物；二乙醯等二酮化合物；苯偶醯；二苯偶醯；二苯甲酮；2,4-二乙基噻噸酮；1,2-二苯基甲烷；2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮；2-氯蒽醌等。 另外，作為前述光聚合起始劑，例如亦可列舉：1-氯蒽醌等醌化合物；胺等光增感劑等。Examples of the photopolymerization initiator (H) in the composition (III-1) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, and benzoin methyl benzoate. Esters, benzoin dimethyl ketal and other benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-di Acetophenone compounds such as phenylethane-1-one; bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl Phosphine oxide compounds such as phosphine oxide; sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenyl ketone; azobisisobutyl Azo compounds such as nitriles; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzal; benzophenone; benzophenone ; 2,4-Diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2- Chloroanthraquinone and so on. In addition, examples of the photopolymerization initiator include quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines.

組成物(III-1)及熱硬化性保護膜形成用膜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，這些的組合及比率可任意選擇。The photopolymerization initiator (H) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, these The combination and ratio can be arbitrarily selected.

於使用光聚合起始劑(H)之情形時，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 case of using the photopolymerization initiator (H), in the composition (III-1), the content of the photopolymerization initiator (H) relative to 100 parts by mass of the energy ray curable resin (G) is more It is preferably from 0.1 part by mass to 20 parts by mass, more preferably from 1 part by mass to 10 parts by mass, and particularly preferably from 2 parts by mass to 5 parts by mass.

[著色劑(I)] 組成物(III-1)及熱硬化性保護膜形成用膜亦可含有著色劑(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。[Colorant (I)] The composition (III-1) and the film for forming a thermosetting protective film may contain a coloring agent (I). As the colorant (I), for example, known coloring agents such as inorganic pigments, organic pigments, and organic dyes can be cited.

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

作為前述無機系顏料，例如可列舉：碳黑、鈷系色素、鐵系色素、鉻系色素、鈦系色素、釩系色素、鋯系色素、鉬系色素、釕系色素、鉑系色素、ITO(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 aforementioned inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments, ITO (Indium Tin Oxide; Indium Tin Oxide) based pigments, ATO (Antimony Tin Oxide; Antimony Tin Oxide) based pigments, etc.

組成物(III-1)及熱硬化性保護膜形成用膜所含有之著色劑(I)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The coloring agent (I) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, the combination of these and The ratio can be chosen arbitrarily.

於使用著色劑(I)之情形時，熱硬化性保護膜形成用膜中的著色劑(I)的含量根據目的適宜調節即可。例如，藉由調節熱硬化性保護膜形成用膜中的著色劑(I)的含量，調節保護膜的透光性，能夠調節對保護膜進行雷射印字之情形時的印字視認性。另外，藉由調節熱硬化性保護膜形成用膜中的著色劑(I)的含量，亦能夠提高保護膜的設計性，或使得半導體晶圓的內面的研削痕跡不易見。若考慮這些方面，則組成物(III-1)中，著色劑(I)的含量相對於溶劑以外的全部成分的總含量之比例(亦即，熱硬化性保護膜形成用膜中的著色劑(I)的含量相對於熱硬化性保護膜形成用膜的總質量之比例)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%。藉由前述比例為前述下限值以上，能夠獲得更顯著的由使用著色劑(I)所帶來之效果。另外，藉由前述比例為前述上限值以下，能夠抑制熱硬化性保護膜形成用膜的透光性過度降低。When using the coloring agent (I), the content of the coloring agent (I) in the film for forming a thermosetting protective film may be appropriately adjusted according to the purpose. For example, by adjusting the content of the coloring agent (I) in the film for forming a thermosetting protective film, the light transmittance of the protective film can be adjusted, and the visibility of printing when the protective film is laser-printed can be adjusted. In addition, by adjusting the content of the coloring agent (I) in the film for forming a thermosetting protective film, it is also possible to improve the design of the protective film, or make it difficult to see the grinding marks on the inner surface of the semiconductor wafer. Considering these points, the ratio of the content of the colorant (I) in the composition (III-1) to the total content of all components other than the solvent (that is, the coloring agent in the film for forming a thermosetting protective film The ratio of the content of (I) to the total mass of the film for forming a thermosetting protective film) is preferably 0.1% by mass to 10% by mass, more preferably 0.1% by mass to 7.5% by mass, and particularly preferably 0.1% by mass to 5 mass%. When the aforementioned ratio is equal to or greater than the aforementioned lower limit value, a more significant effect of the use of the colorant (I) can be obtained. In addition, when the aforementioned ratio is equal to or less than the aforementioned upper limit, it is possible to suppress an excessive decrease in the light transmittance of the film for forming a thermosetting protective film.

[通用添加劑(J)] 組成物(III-1)及熱硬化性保護膜形成用膜亦可在無損本發明的效果之範圍內，含有通用添加劑(J)。 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。[General additives (J)] The composition (III-1) and the film for forming a thermosetting protective film may contain a general-purpose additive (J) within a range that does not impair the effect of the present invention. The general additives (J) can be well-known additives, and can be arbitrarily selected according to the purpose, and are not particularly limited. Preferred general additives (J) include, for example, plasticizers, antistatic agents, antioxidants, and getters. (gettering agent) and so on.

組成物(III-1)及熱硬化性保護膜形成用膜所含有之通用添加劑(J)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。 組成物(III-1)及熱硬化性保護膜形成用膜中的通用添加劑(J)的含量並無特別限定，根據目的適宜選擇即可。The general additives (J) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or two or more types. In the case of two or more types, the combination of these and The ratio can be chosen arbitrarily. The content of the general additive (J) in the composition (III-1) and the film for forming a thermosetting protective film is not particularly limited, and may be appropriately selected according to the purpose.

[溶劑] 組成物(III-1)較佳為進而含有溶劑。含有溶劑之組成物(III-1)的操作性良好。 前述溶劑並無特別限定，作為較佳的溶劑，例如可列舉：甲苯、二甲苯等烴；甲醇、乙醇、2-丙醇、異丁醇(2-甲基丙烷-1-醇)、1-丁醇等醇；乙酸乙酯等酯；丙酮、甲基乙基酮等酮；四氫呋喃等醚；二甲基甲醯胺、N-甲基吡咯啶酮等醯胺(具有醯胺鍵之化合物)等。 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，這些的組合及比率可任意選擇。[Solvent] The composition (III-1) preferably further contains a solvent. The solvent-containing composition (III-1) has good operability. The aforementioned solvent is not particularly limited, and preferred solvents include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), 1- Alcohols such as butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds with amide bonds) Wait. The solvent contained in the composition (III-1) may be only one type or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected.

就能夠使組成物(III-1)中的含有成分更均勻地混合之方面而言，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 (III-1) is preferably methyl ethyl ketone or the like in terms of enabling the components contained in the composition (III-1) to be mixed more uniformly.

組成物(III-1)的溶劑的含量並無特別限定，例如根據溶劑以外的成分的種類適宜選擇即可。The content of the solvent of the composition (III-1) is not particularly limited, and may be appropriately selected according to the types of components other than the solvent, for example.

[熱硬化性保護膜形成用組成物之製造方法] 組成物(III-1)等熱硬化性保護膜形成用組成物藉由調配用以構成該組成物之各成分而獲得。 熱硬化性保護膜形成用組成物例如除調配成分的種類不同之方面以外，可利用與上文說明之黏著劑組成物之情形相同的方法製造。[Method for manufacturing composition for forming thermosetting protective film] The composition for forming a thermosetting protective film, such as the composition (III-1), is obtained by blending each component that constitutes the composition. The composition for forming a thermosetting protective film can be produced by the same method as that of the adhesive composition described above, except for the difference in the types of compounding components.

○能量線硬化性保護膜形成用膜 關於將能量線硬化性保護膜形成用膜貼附於半導體晶圓的內面並使之進行能量線硬化而形成保護膜時的硬化條件，只要保護膜成為充分地發揮該保護膜的功能之程度的硬化度，則並無特別限定，根據能量線硬化性保護膜形成用膜的種類適宜選擇即可。 例如，能量線硬化性保護膜形成用膜之能量線硬化時的能量線的照度較佳為120mW/cm2 至280mW/cm2 。並且，前述硬化時的能量線的光量較佳為100mJ/cm2 至1000mJ/cm2 。○Film for forming energy ray curable protective film Regarding the curing conditions when the energy ray curable protective film forming film is attached to the inner surface of the semiconductor wafer and the energy ray is cured to form a protective film, as long as the protective film becomes The degree of curing to the extent that the function of the protective film is sufficiently exhibited is not particularly limited, and may be appropriately selected according to the type of the film for forming an energy ray curable protective film. For example, the illuminance of the energy ray when the energy ray of the film for forming an energy ray curable protective film is cured is preferably 120 mW/cm 2 to 280 mW/cm 2 . In addition, the amount of light of the energy ray during curing is preferably 100 mJ/cm 2 to 1000 mJ/cm 2 .

作為能量線硬化性保護膜形成用膜，可列舉含有能量線硬化性成分(a)之膜，較佳為含有能量線硬化性成分(a)及填充材料之膜。 能量線硬化性保護膜形成用膜中，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。Examples of the film for forming an energy ray curable protective film include a film containing an energy ray curable component (a), and a film containing an energy ray curable component (a) and a filler is preferred. In the film for forming an energy ray curable protective film, the energy ray curable component (a) is preferably uncured, preferably has adhesiveness, and more preferably has uncured and adhesiveness.

[能量線硬化性保護膜形成用組成物(IV-1)] 作為較佳的能量線硬化性保護膜形成用組成物，例如可列舉含有前述能量線硬化性成分(a)之能量線硬化性保護膜形成用組成物(IV-1)(本說明書中，有時僅簡稱為「組成物(IV-1)」)等。[Composition for forming energy ray curable protective film (IV-1)] As a preferable composition for forming an energy ray curable protective film, for example, a composition (IV-1) for forming an energy ray curable protective film containing the aforementioned energy ray curable component (a) (in this specification, there is Sometimes referred to simply as "Composition (IV-1)") etc.

[能量線硬化性成分(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用膜賦予造膜性或可撓性等，並且於硬化後形成硬質的樹脂膜。 作為能量線硬化性成分(a)，例如可列舉：具有能量線硬化性基且重量平均分子量為80000至2000000之聚合物(a1)、及具有能量線硬化性基且分子量為100至80000之化合物(a2)。前述聚合物(a1)可至少一部分藉由交聯劑進行交聯，亦可不進行交聯。[Energy ray hardening component (a)] The energy ray curable component (a) is a component that is cured by irradiating energy rays. This component is used to impart film forming properties or flexibility to the energy ray curable protective film forming film, and to form a hard after curing Resin film. 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). The aforementioned polymer (a1) may be crosslinked at least partially by a crosslinking agent, or 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)] 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)進行反應而成，該丙烯酸系聚合物(a11)具有能夠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。[Polymer (a1) with energy ray curable base and weight average molecular weight of 80,000 to 2,000,000] As the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000, for example, acrylic resin (a1-1) can be cited. The acrylic resin (a1-1) is an acrylic polymer ( a11) is formed by reacting with an energy ray curable compound (a12), the acrylic polymer (a11) has a functional group capable of reacting with groups possessed by other compounds, and the energy ray curable compound (a12) has Energy-ray-curable groups such as functional group reactive groups and energy-ray-curable double bonds.

作為能夠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(胺基中的1個或2個氫原子由氫原子以外的基取代而成之基)、環氧基等。但就防止半導體晶圓或半導體晶片等的電路的腐蝕之方面而言，前述官能基較佳為羧基以外的基。 這些之中，前述官能基較佳為羥基。Examples of the aforementioned functional group capable of reacting with groups possessed by other compounds include hydroxyl groups, carboxyl groups, amino groups, and substituted amino groups (one or two hydrogen atoms in the amino group are substituted with groups other than hydrogen atoms. The base), epoxy and so on. However, in terms of preventing corrosion of circuits such as semiconductor wafers and semiconductor wafers, the aforementioned functional groups are preferably groups other than carboxyl groups. 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) 作為前述具有官能基之丙烯酸系聚合物(a11)，例如可列舉：使具有前述官能基之丙烯酸系單體與不具有前述官能基之丙烯酸系單體進行共聚而成之聚合物，亦可為除這些單體以外，進而使丙烯酸系單體以外的單體(非丙烯酸系單體)進行共聚而成之聚合物。 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，關於聚合方法，亦可採用公知的方法。・Acrylic polymers with functional groups (a11) As the acrylic polymer (a11) having a functional group, for example, a polymer obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer not having the functional group may be used. In addition to these monomers, a polymer obtained by copolymerizing monomers other than acrylic monomers (non-acrylic monomers). In addition, the aforementioned acrylic polymer (a11) may be a random copolymer or a block copolymer. Regarding the polymerization method, a known method may also be adopted.

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

作為前述含羥基之單體，例如可列舉：(甲基)丙烯酸羥基甲酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等(甲基)丙烯酸羥基烷基酯；乙烯醇、烯丙醇等非(甲基)丙烯酸系不飽和醇(不具有(甲基)丙烯醯基骨架之不飽和醇)等。Examples of the aforementioned hydroxyl-containing monomer include: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols such as allyl alcohol (unsaturated alcohols without (meth)acrylic acid skeleton), etc.

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 aforementioned carboxyl group-containing monomer include: ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, Maleic acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids (dicarboxylic acids with ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. (form Group) carboxyalkyl acrylate and the like.

具有前述官能基之丙烯酸系單體較佳為含羥基之單體。The acrylic monomer having the aforementioned functional group is preferably a hydroxyl group-containing monomer.

構成前述丙烯酸系聚合物(a11)之具有前述官能基之丙烯酸系單體可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The acrylic monomer which has the said functional group which comprises the said acrylic polymer (a11) may be only 1 type, and may be 2 or more types. When it is 2 or more types, these combination and ratio can be selected arbitrarily.

作為不具有前述官能基之丙烯酸系單體，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯((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((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。Examples of acrylic monomers that do not have the aforementioned functional group include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, N-Butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth) Hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate , Isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), ( Tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate Alkyl ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. The group is an alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms.

另外，作為不具有前述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-二甲胺基丙酯等具有非交聯性三級胺基之(甲基)丙烯酸酯等。In addition, examples of acrylic monomers that do not have the aforementioned functional group include: methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxymethyl (meth)acrylate. (Meth)acrylates containing alkoxyalkyl groups such as esters, ethoxyethyl (meth)acrylate, etc.; those containing aryl (meth)acrylates such as phenyl (meth)acrylate, etc., have aromatic groups (Meth)acrylate; non-crosslinkable (meth)acrylamide and its derivatives; (meth)acrylate N,N-dimethylaminoethyl, (meth)acrylate N,N- (Meth)acrylates with non-crosslinkable tertiary amino groups such as dimethylaminopropyl.

構成前述丙烯酸系聚合物(a11)之不具有前述官能基之丙烯酸系單體可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The acrylic monomer that does not have the aforementioned functional group constituting the aforementioned 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 can be arbitrarily selected .

作為前述非丙烯酸系單體，例如可列舉：乙烯、降冰片烯等烯烴；乙酸乙烯酯；苯乙烯等。 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，這些的組合及比率可任意選擇。Examples of the aforementioned non-acrylic monomers include olefins such as ethylene and norbornene; vinyl acetate; styrene. The aforementioned non-acrylic monomer constituting the aforementioned acrylic polymer (a11) may be only one type or two or more types, and when there are two or more types, these combinations and ratios can be arbitrarily selected.

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量相對於構成該丙烯酸系聚合物(a11)之結構單元的總量之比例(含量)較佳為0.1質量%至50質量%，更佳為1質量%至40質量%，尤佳為3質量%至30質量%。藉由前述比例為此種範圍，能夠將由前述丙烯酸系聚合物(a11)與前述能量線硬化性化合物(a12)之共聚所獲得之前述丙烯酸系樹脂(a1-1)中能量線硬化性基的含量容易地調節為使保護膜的硬化程度較佳之範圍。In the aforementioned acrylic polymer (a11), the ratio (content) of the amount of structural units derived from the acrylic monomer having the aforementioned functional group relative to the total amount of structural units constituting the acrylic polymer (a11) is preferred It is 0.1% by mass to 50% by mass, more preferably 1% by mass to 40% by mass, and particularly preferably 3% by mass to 30% by mass. When the aforementioned ratio is in this range, the energy-ray-curable group in the acrylic resin (a1-1) obtained by copolymerization of the aforementioned acrylic polymer (a11) and the aforementioned energy-ray-curable compound (a12) can be The content can be easily adjusted to a range in which the degree of hardening of the protective film is preferable.

構成前述丙烯酸系樹脂(a1-1)之前述丙烯酸系聚合物(a11)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be only one type or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected.

組成物(IV-1)中，丙烯酸系樹脂(a1-1)的含量相對於溶劑以外的成分的總含量之比例(亦即，能量線硬化性保護膜形成用膜中的丙烯酸系樹脂(a1-1)的含量相對於前述膜的總質量之比例)較佳為1質量%至70質量%，更佳為5質量%至60質量%，尤佳為10質量%至50質量%。In the composition (IV-1), the ratio of the content of the acrylic resin (a1-1) to the total content of components other than the solvent (that is, the acrylic resin (a1) in the film for forming an energy-ray curable protective film The ratio of the content of -1) to the total mass of the aforementioned film) is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 60% by mass, and particularly preferably 10% by mass to 50% by mass.

・能量線硬化性化合物(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種以上作為能夠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，該異氰酸酯基與具有羥基作為前述官能基之丙烯酸系聚合物(a11)的該羥基容易反應。・Energy ray curable compound (a12) The aforementioned energy ray-curable compound (a12) preferably has one or two or more selected from the group consisting of isocyanate groups, epoxy groups, and carboxyl groups as those capable of being combined with the aforementioned acrylic polymer (a11) The functional group reaction group preferably has an isocyanate group as the aforementioned group. When the energy ray curable compound (a12) has an isocyanate group as the group, the isocyanate group and the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group easily react.

前述能量線硬化性化合物(a12)的1分子中所具有之前述能量線硬化性基的數量並無特別限定，例如可考慮對目標保護膜所要求之收縮率等物性而適宜選擇。 例如，前述能量線硬化性化合物(a12)較佳為於1分子中具有1個至5個前述能量線硬化性基，更佳為具有1個至3個。The number of the energy ray curable group contained in one molecule of the energy ray curable compound (a12) is not particularly limited. For example, it can be appropriately selected in consideration of physical properties such as shrinkage rate required for the target protective film. For example, the aforementioned energy-ray-curable compound (a12) preferably has 1 to 5 of the aforementioned energy-ray-curable group in one molecule, and more preferably has 1 to 3.

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。 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。Examples of the energy ray curable compound (a12) include: 2-methacryloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and methacrylic acid Isocyanate, allyl isocyanate, 1,1-(bisacryloxymethyl) ethyl isocyanate; by the reaction of diisocyanate compound or polyisocyanate compound and hydroxyethyl (meth)acrylate Acrylic monoisocyanate compound obtained; Acrylic monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound, polyol compound and hydroxyethyl (meth)acrylate. Among these, the aforementioned energy ray curable compound (a12) is preferably 2-methacryloxyethyl isocyanate.

構成前述丙烯酸系樹脂(a1-1)之前述能量線硬化性化合物(a12)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的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 can be arbitrarily selected .

前述丙烯酸系樹脂(a1-1)中，源自前述能量線硬化性化合物(a12)之能量線硬化性基的含量相對於源自前述丙烯酸系聚合物(a11)之前述官能基的含量之比例較佳為20莫耳%至120莫耳%，更佳為35莫耳%至100莫耳%，尤佳為50莫耳%至100莫耳%。藉由前述含量之比例為此種範圍，保護膜的接著力進一步變大。此外，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個以上之前述基)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%。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) in the acrylic resin (a1-1) It is preferably 20 mol% to 120 mol%, more preferably 35 mol% to 100 mol%, and particularly preferably 50 mol% to 100 mol%. When the aforementioned content ratio is in this range, the adhesive force of the protective film is further increased. In addition, when the aforementioned energy ray curable compound (a12) is a monofunctional (having one aforementioned group in one molecule) compound, the upper limit of the aforementioned content ratio becomes 100 mol%. When the 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。 此處，所謂「重量平均分子量」，如上文所說明。The weight average molecular weight (Mw) of the aforementioned polymer (a1) is preferably 100,000 to 2,000,000, more preferably 300,000 to 1,500,000. 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，在與前述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。In the case where at least a part of the aforementioned polymer (a1) is crosslinked by a crosslinking agent, the aforementioned polymer (a1) can be any monomer that does not conform to the above description and constitutes the aforementioned acrylic polymer (a11) and A monomer having a group that reacts with a crosslinking agent is polymerized and crosslinked in a group that reacts with the aforementioned crosslinking agent. It may also be a group derived from the aforementioned energy ray curable compound (a12) that reacts with the aforementioned functional group. Cross-linking in the middle.

組成物(IV-1)及能量線硬化性保護膜形成用膜所含有之前述聚合物(a1)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The aforementioned polymer (a1) contained in the composition (IV-1) and the film for forming an energy-ray curable protective film may be only one type or two or more types. In the case of two or more types, these The combination and ratio can be selected arbitrarily.

(具有能量線硬化性基且分子量為100至80000之化合物(a2)) 作為具有能量線硬化性基且分子量為100至80000之化合物(a2)中的前述能量線硬化性基，可列舉包含能量線硬化性雙鍵之基，作為較佳的前述能量線硬化性基，可列舉(甲基)丙烯醯基、乙烯基等。(Compound (a2) with energy ray hardening group and molecular weight of 100 to 80,000) As the aforementioned energy-ray-curable group in the compound (a2) having an energy-ray-curable group and a molecular weight of 100 to 80,000, a group containing an energy-ray-curable double bond can be cited. As a preferable energy-beam-curable group, Examples include (meth)acryloyl and vinyl.

前述化合物(a2)只要滿足上述條件，則並無特別限定，可列舉：具有能量線硬化性基之低分子量化合物、具有能量線硬化性基之環氧樹脂、具有能量線硬化性基之酚樹脂等。The aforementioned compound (a2) is not particularly limited as long as it satisfies the above conditions. Examples include low molecular weight compounds having energy ray curable groups, epoxy resins having energy ray curable groups, and phenol resins having energy ray curable groups. 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。 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、聚四亞甲基二醇二(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-己內酯改質異氰脲酸三-(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。Among the aforementioned compounds (a2), examples of the low-molecular-weight compound having an energy-ray curable group include polyfunctional monomers or oligomers, and preferably acrylate-based compounds having a (meth)acryloyl group. Examples of the aforementioned acrylate-based compounds include: 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, and propoxylated ethoxy Bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(methyl) )Acrylate, 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxy) Ethoxy) phenyl] 茀, 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, dipropylene glycol di(meth)acrylate ) Acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloxyethoxy)phenyl]propane, Neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-bis(meth)acryloyloxypropane and other bifunctional (methyl) ) Acrylate; Tris(2-(meth)acryloyloxyethyl) isocyanurate, ε-caprolactone modified isocyanurate tris-(2-(meth)acryloyloxyethyl) Base) ester, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(methyl) ) Acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. (Meth)acrylate; (meth)acrylate urethane oligomer and other polyfunctional (meth)acrylate oligomers.

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，例如可使用日本專利特開2013-194102號公報之段落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 aforementioned compounds (a2), as an epoxy resin having an energy ray curable group and a phenol resin having an energy ray curable group, for example, the resin described in paragraph 0043 of JP 2013-194102 A can be used . Such 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 100 to 30,000, more preferably 300 to 10,000.

組成物(IV-1)及能量線硬化性保護膜形成用膜所含有之前述化合物(a2)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The aforementioned compound (a2) contained in the composition (IV-1) and the film for forming an energy ray curable protective film may be only one type or two or more types. In the case of two or more types, a combination of these And the ratio can be chosen arbitrarily.

[不具有能量線硬化性基之聚合物(b)] 於組成物(IV-1)及能量線硬化性保護膜形成用膜含有前述化合物(a2)作為前述能量線硬化性成分(a)之情形時，較佳為亦進而含有不具有能量線硬化性基之聚合物(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。[Polymer without energy ray curable base (b)] When the composition (IV-1) and the film for forming an energy ray curable protective film contain the aforementioned compound (a2) as the aforementioned energy ray curable component (a), it is preferable to further contain the non-energy ray curable component Base polymer (b). The aforementioned polymer (b) may be crosslinked at least partially by a crosslinking agent, or 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。 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)」)。Examples of the polymer (b) that does not have an energy ray curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, and acrylic urethane resins. Wait. 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種以上之丙烯酸系單體的共聚物，還可為1種或2種以上之丙烯酸系單體與1種或2種以上之丙烯酸系單體以外的單體(非丙烯酸系單體)的共聚物。The acrylic polymer (b-1) may be a known polymer, for example, it may be a homopolymer of one acrylic monomer, or a copolymer of two or more acrylic monomers, or one Or a copolymer of two or more types of acrylic monomers and one or more types of monomers (non-acrylic monomers) other than acrylic monomers.

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

作為前述(甲基)丙烯酸烷基酯，例如可列舉與上文說明之構成丙烯酸系聚合物(a11)之不具有前述官能基之丙烯酸系單體(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)相同的化合物。As the aforementioned (meth)acrylic acid alkyl ester, for example, the acrylic monomer that does not have the aforementioned functional group that constitutes the acrylic polymer (a11) explained above (the alkyl group constituting the alkyl ester has a carbon number of (Meth)acrylic acid alkyl esters of 1 to 18 chain structure).

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)丙烯酸環烯酯；(甲基)丙烯酸二環戊烯氧基乙酯等(甲基)丙烯酸環烯氧基烷基酯等。Examples of (meth)acrylates having a cyclic skeleton include cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate; (meth) ) Aralkyl (meth)acrylate such as benzyl acrylate; cycloalkenyl (meth)acrylate such as dicyclopentenyl (meth)acrylate; dicyclopentenoxyethyl (meth)acrylate, etc. ( Cycloalkenyloxyalkyl meth)acrylate 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。 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。 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 glycidyl group-containing (meth)acrylate, glycidyl (meth)acrylate etc. are mentioned, for example. Examples of the hydroxyl-containing (meth)acrylates include: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (methyl) ) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Examples of the aforementioned substituted amino group-containing (meth)acrylate include N-methylaminoethyl (meth)acrylate and the like.

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。Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; styrene and the like.

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而成之聚合物。 前述反應性官能基根據交聯劑的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。但就防止半導體晶圓或半導體晶片的電路的腐蝕之方面而言，前述反應性官能基較佳為羧基以外的基。Examples of the polymer (b) that is at least partially cross-linked by a cross-linking agent and does not have the aforementioned energy ray curable group include: the reactive functional group in the aforementioned polymer (b) reacts with the cross-linking agent的polymers. The aforementioned reactive functional group may be appropriately selected according to the kind of crosslinking agent and the like, and is not particularly limited. For example, when the crosslinking agent is a polyisocyanate compound, as the aforementioned reactive functional group, a hydroxyl group, a carboxyl group, an amino group, etc. can be mentioned. 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, as the aforementioned reactive functional group, a carboxyl group, an amino group, an amide group, etc. can be cited. Among these, those having high reactivity with an epoxy group are preferred. carboxyl. However, in terms of preventing corrosion of the semiconductor wafer or the circuit of the semiconductor wafer, the reactive functional group is preferably a group other than a carboxyl group.

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：使至少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中的任一者或兩者，使用具有前述反應性官能基之單體即可。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個以上之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 curable group, the polymer obtained by polymerizing the monomer which has at least the said reactive functional group is mentioned, for example. In the case of acrylic polymer (b-1), any one or both of the aforementioned acrylic monomers and non-acrylic monomers listed as monomers constituting the acrylic polymer (b-1) Alternatively, a monomer having the aforementioned reactive functional group may be used. As the aforementioned polymer (b) having a hydroxyl group as a reactive functional group, for example, a polymer obtained by polymerizing a hydroxyl-containing (meth)acrylate may be mentioned. In addition to this, the above-mentioned A polymer obtained by polymerizing a monomer in which one or more hydrogen atoms in the aforementioned acrylic monomer or non-acrylic monomer is 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量相對於構成該聚合物(b)之結構單元的總量之比例(含量)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 reactive functional groups, the ratio (content) of the amount of structural units derived from monomers having reactive functional groups relative to the total amount of structural units constituting the polymer (b) It is preferably 1% by mass to 20% by mass, and more preferably 2% by mass to 10% by mass. When the aforementioned ratio is in this range, the degree of crosslinking in the aforementioned polymer (b) becomes a more preferable range.

就組成物(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」，如上文所說明。In terms of better film forming properties of the composition (IV-1), the weight average molecular weight (Mw) of the polymer (b) without an energy-ray curable group is preferably 10,000 to 2,000,000, more preferably 100,000 To 1500000. Here, the so-called "weight average molecular weight" is as described above.

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

作為組成物(IV-1)，可列舉含有前述聚合物(a1)及前述化合物(a2)中的任一者或兩者之組成物。並且，於組成物(IV-1)含有前述化合物(a2)之情形時，較佳為亦進而含有不具有能量線硬化性基之聚合物(b)，該情形時，亦較佳為進而含有前述(a1)。另外，組成物(IV-1)亦可不含有前述化合物(a2)，且一併含有前述聚合物(a1)及不具有能量線硬化性基之聚合物(b)。As the composition (IV-1), a composition containing either or both of the aforementioned polymer (a1) and aforementioned compound (a2) can be cited. In addition, when the composition (IV-1) contains the aforementioned compound (a2), it is preferable to further contain a polymer (b) that does not have an energy-ray curable group, and in this case, it is also preferable to further contain The foregoing (a1). In addition, the composition (IV-1) may not contain the above-mentioned compound (a2), and may also contain the above-mentioned polymer (a1) and the polymer (b) which does not have an energy-ray curable group.

於組成物(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，組成物(IV-1)中，前述化合物(a2)的含量相對於前述聚合物(a1)及不具有能量線硬化性基之聚合物(b)的總含量100質量份，較佳為10質量份至400質量份，更佳為30質量份至350質量份。When the composition (IV-1) contains the aforementioned polymer (a1), the aforementioned compound (a2), and the polymer (b) that does not have an energy-ray curable group, in the composition (IV-1), the aforementioned The content of the compound (a2) is 100 parts by mass relative to the total content of the aforementioned polymer (a1) and the polymer (b) without an energy ray curable group, preferably 10 to 400 parts by mass, more preferably 30 Parts by mass to 350 parts by mass.

組成物(IV-1)中，前述能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的合計含量相對於溶劑以外的成分的總含量之比例(亦即，能量線硬化性保護膜形成用膜中的前述能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的合計含量相對於前述膜的總質量之比例)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之前述比例為此種範圍，能量線硬化性保護膜形成用膜的能量線硬化性變得更良好。In the composition (IV-1), the ratio of the total content of the energy ray curable component (a) and the polymer (b) not having an energy ray curable group to the total content of components other than the solvent (that is, The ratio of the total content of the aforementioned energy ray curable component (a) and the polymer (b) not having an energy ray curable group to the total mass of the aforementioned film in the film for forming an energy ray curable protective film is preferably 5 mass% to 90 mass%, more preferably 10 mass% to 80 mass%, particularly preferably 20 mass% to 70 mass%. When the aforementioned ratio of the content of the energy ray curable component is in such a range, the energy ray curability of the film for forming an energy ray curable protective film becomes better.

組成物(IV-1)中，除前述能量線硬化性成分以外，亦可根據目的而含有選自由熱硬化性成分、填充材料、偶合劑、交聯劑、光聚合起始劑、著色劑及通用添加劑所組成之群組中的1種或2種以上。In the composition (IV-1), in addition to the aforementioned energy ray curable component, it may also contain a thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, coloring agent, and One or more of the group consisting of general additives.

作為組成物(IV-1)中的前述熱硬化性成分、填充材料、偶合劑、交聯劑、光聚合起始劑、著色劑及通用添加劑，可列舉分別與組成物(III-1)中的熱硬化性成分(B)、填充材料(D)、偶合劑(E)、交聯劑(F)、光聚合起始劑(H)、著色劑(I)及通用添加劑(J)相同的化合物。As the aforementioned thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants, and general additives in the composition (IV-1), they can be listed in the composition (III-1). The thermosetting component (B), filler (D), coupling agent (E), crosslinking agent (F), photopolymerization initiator (H), coloring agent (I) and general additives (J) are the same Compound.

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組成物(IV-1)，所形成之能量線硬化性保護膜形成用膜藉由加熱而對被接著體之接著力提高，由該能量線硬化性保護膜形成用膜所形成之樹脂膜的強度亦提高。 另外，藉由使用含有前述能量線硬化性成分及著色劑之組成物(IV-1)，所形成之能量線硬化性保護膜形成用膜表現與上文說明之熱硬化性保護膜形成用膜含有著色劑(I)之情形相同的效果。For example, by using the composition (IV-1) containing the aforementioned energy ray curable component and thermosetting component, the formed film for forming an energy ray curable protective film increases its adhesive force to the adherend by heating , The strength of the resin film formed from the film for forming the energy ray curable protective film is also improved. In addition, by using the composition (IV-1) containing the aforementioned energy ray curable component and coloring agent, the formed energy ray curable protective film formation film has the same performance as the above-explained thermosetting protective film formation film The same effect is obtained when the colorant (I) is included.

組成物(IV-1)中，前述熱硬化性成分、填充材料、偶合劑、交聯劑、光聚合起始劑、著色劑及通用添加劑可分別單獨使用1種，亦可併用2種以上，於併用2種以上之情形時，這些的組合及比率可任意選擇。In the composition (IV-1), the aforementioned thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants, and general additives may be used individually or in combination of two or more. When two or more types are used in combination, the combination and ratio of these can be arbitrarily selected.

組成物(IV-1)中的前述熱硬化性成分、填充材料、偶合劑、交聯劑、光聚合起始劑、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 content of the aforementioned thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, coloring agent, and general additives in the composition (IV-1) may be appropriately adjusted according to the purpose, and is not particularly limited.

就藉由稀釋而使該組成物的操作性提高而言，組成物(IV-1)較佳為進而含有溶劑。 作為組成物(IV-1)所含有之溶劑，例如可列舉與組成物(III-1)中的溶劑相同的溶劑。 組成物(IV-1)所含有之溶劑可僅為1種，亦可為2種以上。 組成物(IV-1)中的溶劑的含量並無特別限定，例如根據溶劑以外的成分的種類適宜選擇即可。In terms of improving the workability of the composition by dilution, the composition (IV-1) preferably further contains a solvent. Examples of the solvent contained in the composition (IV-1) include the same solvents as the solvent in the composition (III-1). The solvent contained in the composition (IV-1) may be only one type or two or more types. The content of the solvent in the composition (IV-1) is not particularly limited, and may be appropriately selected according to the types of components other than the solvent, for example.

[能量線硬化性保護膜形成用組成物之製造方法] 組成物(IV-1)等能量線硬化性保護膜形成用組成物可藉由調配用以構成該組成物之各成分而獲得。 能量線硬化性保護膜形成用組成物例如除調配成分的種類不同之方面以外，可利用與上文說明之黏著劑組成物之情形相同的方法進行製造。[Method for manufacturing composition for forming energy ray curable protective film] A composition for forming an energy ray curable protective film, such as composition (IV-1), can be obtained by blending each component that constitutes the composition. The composition for forming an energy ray-curable protective film can be manufactured by the same method as the adhesive composition described above, except for the difference in the types of ingredients.

◎剝離膜 前述剝離膜可作為前述保護膜形成用複合片之保護膜形成用膜側的最表層而具備之任意的構成要素。成為於保護膜形成用膜上具備剝離膜之狀態之保護膜形成用複合片中，將該剝離膜自保護膜形成用膜移除時，保護膜形成用複合片的剝離帶電得到抑制。◎Release film The peeling film may be an arbitrary component provided as the outermost layer on the protective film forming film side of the protective film forming composite sheet. In the composite sheet for protective film formation in the state provided with a peeling film on the film for protective film formation, when the peeling film is removed from the film for protective film formation, peeling charging of the composite sheet for protective film formation is suppressed.

前述剝離膜可為公知的膜，例如可列舉聚對苯二甲酸乙二酯製膜等樹脂製膜的單面經實施聚矽氧處理等剝離處理而成之膜。 前述剝離膜亦可與上述之作為中間層之剝離性改善層具有相同的構成。The said release film may be a well-known film, For example, the film which performed peeling process, such as a silicone process, on one side of resin film, such as a polyethylene terephthalate film, is mentioned. The aforementioned release film may have the same structure as the aforementioned release improving layer as the intermediate layer.

前述剝離膜的厚度並無特別限定，例如可為10μm至1000μm等。The thickness of the aforementioned release film is not particularly limited, and may be, for example, 10 μm to 1000 μm.

作為前述保護膜形成用複合片的一實施形態，可列舉以下之保護膜形成用複合片：具備支撐片、及形成於前述支撐片的一面上之保護膜形成用膜，並且前述保護膜形成用複合片的帶電壓的半衰期為20秒以下，前述支撐片具備基材、及形成於前述基材的單面或雙面上之抗靜電層，或者前述支撐片具備具有抗靜電性之基材作為抗靜電層，前述抗靜電層含有選自由嘧啶鎓鹽、吡啶鎓鹽、哌啶鎓鹽、吡咯啶鎓鹽、咪唑鎓鹽、嗎啉鎓鹽、鋶鹽、鏻鹽、銨鹽、聚(3,4-乙二氧基噻吩)/聚苯乙烯磺酸鹽、聚吡咯及奈米碳管所組成之群組中的1種或2種以上。As one embodiment of the composite sheet for forming a protective film, the following composite sheet for forming a protective film includes a supporting sheet and a protective film forming film formed on one side of the supporting sheet, and the protective film forming The charged half-life of the composite sheet is 20 seconds or less. The support sheet has a substrate and an antistatic layer formed on one or both sides of the substrate, or the support sheet has a substrate with antistatic properties. Antistatic layer, the aforementioned antistatic layer contains selected from pyrimidinium salt, pyridinium salt, piperidinium salt, pyrrolidinium salt, imidazolium salt, morpholinium salt, sulfonium salt, phosphonium salt, ammonium salt, poly(3) ,4-ethylenedioxythiophene)/polystyrene sulfonate, polypyrrole and carbon nanotubes are one or more of the group.

作為前述保護膜形成用複合片的一實施形態，可列舉以下之保護膜形成用複合片：具備支撐片、及形成於前述支撐片的一面上之保護膜形成用膜，並且前述保護膜形成用複合片的帶電壓的半衰期為20秒以下，前述支撐片具備基材、及形成於前述基材的單面或雙面上之抗靜電層，或者前述支撐片具備具有抗靜電性之基材作為抗靜電層，前述抗靜電層含有選自由嘧啶鎓鹽、吡啶鎓鹽、哌啶鎓鹽、吡咯啶鎓鹽、咪唑鎓鹽、嗎啉鎓鹽、鋶鹽、鏻鹽、銨鹽、聚(3,4-乙二氧基噻吩)/聚苯乙烯磺酸鹽、聚吡咯及奈米碳管所組成之群組中的1種或2種以上，形成於前述基材的單面或雙面上之前述抗靜電層的合計厚度為30nm至200nm。As one embodiment of the composite sheet for forming a protective film, the following composite sheet for forming a protective film includes a supporting sheet and a protective film forming film formed on one side of the supporting sheet, and the protective film forming The charged half-life of the composite sheet is 20 seconds or less. The support sheet has a substrate and an antistatic layer formed on one or both sides of the substrate, or the support sheet has a substrate with antistatic properties. Antistatic layer, the aforementioned antistatic layer contains selected from pyrimidinium salt, pyridinium salt, piperidinium salt, pyrrolidinium salt, imidazolium salt, morpholinium salt, sulfonium salt, phosphonium salt, ammonium salt, poly(3) ,4-Ethylenedioxythiophene)/polystyrene sulfonate, polypyrrole and carbon nanotubes consisting of one or two or more types, formed on one or both sides of the aforementioned substrate The total thickness of the aforementioned antistatic layer is 30nm to 200nm.

作為前述保護膜形成用複合片的一實施形態，可列舉以下之保護膜形成用複合片：具備支撐片、及形成於前述支撐片的一面上之保護膜形成用膜，並且前述保護膜形成用複合片的帶電壓的半衰期為20秒以下，前述支撐片具備基材、及形成於前述基材的單面或雙面上之抗靜電層，或者前述支撐片具備具有抗靜電性之基材作為抗靜電層，前述抗靜電層含有選自由嘧啶鎓鹽、吡啶鎓鹽、哌啶鎓鹽、吡咯啶鎓鹽、咪唑鎓鹽、嗎啉鎓鹽、鋶鹽、鏻鹽、銨鹽、聚(3,4-乙二氧基噻吩)/聚苯乙烯磺酸鹽、聚吡咯及奈米碳管所組成之群組中的1種或2種以上，前述具有抗靜電性之基材包含前述抗靜電劑及樹脂，於前述具有抗靜電性之基材中，前述抗靜電劑的含量相對於前述抗靜電劑及樹脂的合計含量之比例為7.5%質量以上。As one embodiment of the composite sheet for forming a protective film, the following composite sheet for forming a protective film includes a supporting sheet and a protective film forming film formed on one side of the supporting sheet, and the protective film forming The charged half-life of the composite sheet is 20 seconds or less. The support sheet has a substrate and an antistatic layer formed on one or both sides of the substrate, or the support sheet has a substrate with antistatic properties. Antistatic layer, the aforementioned antistatic layer contains selected from pyrimidinium salt, pyridinium salt, piperidinium salt, pyrrolidinium salt, imidazolium salt, morpholinium salt, sulfonium salt, phosphonium salt, ammonium salt, poly(3) ,4-Ethylenedioxythiophene)/polystyrene sulfonate, polypyrrole and carbon nanotubes consisting of one or more types, and the aforementioned antistatic substrate includes the aforementioned antistatic The ratio of the content of the antistatic agent to the total content of the antistatic agent and the resin in the base material having antistatic properties is 7.5% by mass or more.

◇保護膜形成用複合片之製造方法 前述保護膜形成用複合片可藉由將上述各層以成為對應的位置關係之方式進行積層而製造。各層之形成方法如上文所說明。◇Method for manufacturing composite sheet for forming protective film The said composite sheet for protective film formation can be manufactured by laminating|stacking each said layer so that it may become a corresponding positional relationship. The formation method of each layer is as described above.

例如，於製造支撐片時，於基材上或抗靜電性基材上積層黏著劑層之情形時，於基材上或抗靜電性基材上塗敷上述黏著劑組成物，並視需要使之乾燥即可。該方法可應用於在基材或抗靜電性基材的前述凹凸面上積層黏著劑層之情形、及在基材或抗靜電性基材的前述平滑面上積層黏著劑層之情形之任一情形。並且，該方法尤其適於在前述凹凸面上積層黏著劑層之情形。原因在於，於應用該方法之情形時，能夠獲得抑制於基材或抗靜電性基材的前述凹凸面與黏著劑層之間產生空隙部之高效果。For example, in the case of laminating an adhesive layer on a substrate or an antistatic substrate when manufacturing a support sheet, apply the above adhesive composition on the substrate or the antistatic substrate, and make it as necessary Just dry. This method can be applied to either the case of laminating an adhesive layer on the aforementioned uneven surface of the substrate or the antistatic substrate, and the case of laminating the adhesive layer on the aforementioned smooth surface of the substrate or the antistatic substrate situation. In addition, this method is particularly suitable for the case where an adhesive layer is laminated on the aforementioned uneven surface. The reason is that when this method is applied, it is possible to obtain a high effect of suppressing the generation of voids between the aforementioned uneven surface of the substrate or the antistatic substrate and the adhesive layer.

於製造支撐片時，於基材上或抗靜電性基材上積層背面抗靜電層或表面抗靜電層之情形亦相同。 該情形時，除使用抗靜電組成物(VI-1)代替黏著劑組成物之方面以外，可利用與上述之積層黏著劑層之方法相同的方法，於基材上或抗靜電性基材上積層背面抗靜電層或表面抗靜電層。When manufacturing the support sheet, it is the same to laminate the back antistatic layer or the surface antistatic layer on the substrate or the antistatic substrate. In this case, except for using the antistatic composition (VI-1) instead of the adhesive composition, the same method as the above-mentioned laminated adhesive layer can be used on the substrate or on the antistatic substrate Laminated back antistatic layer or surface antistatic layer.

另一方面，於基材上或抗靜電性基材上積層黏著劑層之情形時，亦可應用以下之方法代替如上所述般於基材上或抗靜電性基材上塗敷黏著劑組成物之方法。 亦即，亦可利用以下之方法於基材上或抗靜電性基材上積層黏著劑層：於剝離膜上塗敷黏著劑組成物，並視需要使之乾燥，藉此於剝離膜上預先形成黏著劑層，使該黏著劑層的露出面與基材或抗靜電性基材的一表面貼合。並且，該方法尤其適於在前述平滑面上積層黏著劑層之情形。原因在於，於應用該方法之情形時，能夠獲得抑制於基材或抗靜電性基材的前述平滑面與黏著劑層之間產生空隙部之高效果。On the other hand, when an adhesive layer is laminated on a substrate or an antistatic substrate, the following method can also be used instead of coating the adhesive composition on the substrate or the antistatic substrate as described above的方法。 The method. That is, the following method can also be used to laminate the adhesive layer on the substrate or the antistatic substrate: apply the adhesive composition on the release film, and dry it as necessary, thereby pre-forming on the release film The adhesive layer makes the exposed surface of the adhesive layer adhere to the substrate or one surface of the antistatic substrate. Moreover, this method is particularly suitable for the case where an adhesive layer is laminated on the aforementioned smooth surface. The reason is that when this method is applied, it is possible to obtain a high effect of suppressing the generation of voids between the smooth surface of the substrate or the antistatic substrate and the adhesive layer.

於製造支撐片時，使用剝離膜，於基材上或抗靜電性基材上積層背面抗靜電層或表面抗靜電層之情形亦相同。 該情形時，除使用抗靜電組成物(VI-1)代替黏著劑組成物之方面以外，可利用與上述之使用剝離膜積層黏著劑層之方法相同的方法，於基材上或抗靜電性基材上積層背面抗靜電層或表面抗靜電層。When manufacturing the support sheet, the release film is used to laminate the back antistatic layer or the surface antistatic layer on the substrate or the antistatic substrate. In this case, except that the antistatic composition (VI-1) is used instead of the adhesive composition, the same method as the above-mentioned method of using the peeling film to laminate the adhesive layer can be used on the substrate or antistatic The back antistatic layer or the surface antistatic layer is laminated on the substrate.

前文列舉了於基材上或抗靜電性基材上積層黏著劑層、背面抗靜電層或表面抗靜電層之情形作為示例，但上述方法例如亦可應用於在基材上或抗靜電性基材上積層中間層之情形等積層其他層之情形。The foregoing exemplifies the case of laminating an adhesive layer, a back antistatic layer, or a surface antistatic layer on a substrate or an antistatic substrate, but the above method can also be applied to a substrate or an antistatic substrate. The case where the middle layer is laminated on the material and other layers are laminated.

另一方面，例如於已積層於基材上或抗靜電性基材上之黏著劑層上，進而積層保護膜形成用膜之情形時，可於黏著劑層上塗敷保護膜形成用組成物，而直接形成保護膜形成用膜。保護膜形成用膜以外的層亦可使用用以形成該層之組成物，利用相同的方法，於黏著劑層上積層該層。如此，於已積層於基材上之任一層(以下，簡稱為「第1層」)上，形成新的層(以下，簡稱為「第2層」)，而形成連續的2層之積層結構(換言之，第1層及第2層之積層結構)之情形時，可應用於前述第1層上塗敷用以形成前述第2層之組成物，並視需要使之乾燥之方法。 但是，較佳為藉由下述方式形成連續的2層之積層結構：使用用以形成第2層之組成物，於剝離膜上預先形成第2層，將該已形成之第2層中之與和前述剝離膜接觸之側為相反側的露出面來與第1層的露出面貼合。此時，前述組成物較佳為塗敷於剝離膜的剝離處理面。剝離膜於形成積層結構後視需要移除即可。 此處列舉了於黏著劑層上積層保護膜形成用膜之情形作為示例，但例如於黏著劑層上積層中間層之情形、於中間層上積層保護膜形成用膜之情形、於表面抗靜電層上積層黏著劑層之情形等，成為對象之積層結構可任意選擇。On the other hand, for example, when a protective film formation film is laminated on an adhesive layer that has been laminated on a substrate or an antistatic substrate, the protective film formation composition can be coated on the adhesive layer. Instead, the protective film formation film is directly formed. Layers other than the protective film formation film can also use the composition for forming the layer, and the layer is laminated on the adhesive layer by the same method. In this way, a new layer (hereinafter referred to as the "second layer") is formed on any layer (hereinafter referred to as the "first layer") that has been laminated on the substrate to form a continuous two-layer laminated structure (In other words, in the case of a laminated structure of the first layer and the second layer), it can be applied to the method of coating the composition for forming the second layer on the first layer and drying it if necessary. However, it is preferable to form a continuous two-layer laminated structure by using a composition for forming the second layer, forming a second layer on the release film in advance, and making the second layer The side in contact with the release film is the exposed surface on the opposite side, and is bonded to the exposed surface of the first layer. In this case, the aforementioned composition is preferably applied to the release-treated surface of the release film. The peeling film can be removed as needed after forming the laminated structure. Here, as an example, the case where the protective film formation film is laminated on the adhesive layer, but for example, the case where the intermediate layer is laminated on the adhesive layer, the case where the protective film formation film is laminated on the intermediate layer, and the surface is antistatic The case where the adhesive layer is laminated on top of each other, etc., can be arbitrarily selected as the target laminated structure.

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

此外，保護膜形成用複合片通常係以於該保護膜形成用複合片中之與支撐片為相反側的最表層(例如保護膜形成用膜)的表面貼合有剝離膜之狀態保管。因此，可藉由下述方式獲得附剝離膜之保護膜形成用複合片：於該剝離膜(較佳為該剝離膜的剝離處理面)上，塗敷保護膜形成用組成物等用以形成構成最表層之層之組成物，並視需要使之乾燥，藉此於剝離膜上預先形成構成最表層之層，利用上述任一種方法於該層中之與剝離膜接觸之側為相反側的露出面上積層剩餘各層，不移除剝離膜而保持貼合狀態不變。In addition, the composite sheet for forming a protective film is usually stored in a state where a release film is attached to the surface of the outermost layer (for example, the film for forming a protective film) on the opposite side to the support sheet in the composite sheet for forming a protective film. Therefore, a composite sheet for forming a protective film with a release film can be obtained by coating the release film (preferably the release-treated surface of the release film) with a protective film forming composition, etc. to form Form the composition of the outermost layer and dry it if necessary, thereby forming the outermost layer on the release film in advance, and use any of the above methods to place the side in contact with the release film on the opposite side of the layer The remaining layers are laminated on the exposed surface, and the peeling film is not removed and the attached state is maintained.

◇半導體晶片之製造方法 前述保護膜形成用複合片可用於製造半導體晶片。 作為此時的半導體晶片之製造方法，例如可列舉具有以下步驟之方法：使用於保護膜形成用複合片中的保護膜形成用膜上具備剝離膜之保護膜形成用複合片作為前述保護膜形成用複合片，自前述保護膜形成用膜移除前述剝離膜之步驟(以下，有時簡稱為「剝離步驟」)；將移除前述剝離膜後的前述保護膜形成用複合片中的保護膜形成用膜貼附於半導體晶圓之步驟(以下，有時簡稱為「貼附步驟」)；使貼附於前述半導體晶圓後的前述保護膜形成用膜硬化而形成保護膜之步驟(以下，有時簡稱為「保護膜形成步驟」)；分割前述半導體晶圓，切斷前述保護膜或保護膜形成用膜，獲得具備切斷後的保護膜或保護膜形成用膜之多個半導體晶片之步驟(以下，有時簡稱為「分割步驟」)；以及將具備前述切斷後的保護膜或保護膜形成用膜之半導體晶片自前述支撐片扯離而進行拾取之步驟(以下，有時簡稱為「拾取步驟」)。 前述製造方法中，於前述貼附步驟後，進行前述保護膜形成步驟、分割步驟及拾取步驟。並且，雖於分割步驟後進行拾取步驟，但除該方面以外，進行保護膜形成步驟、分割步驟及拾取步驟之順序可根據目的任意設定。◇Method of manufacturing semiconductor chip The aforementioned composite sheet for forming a protective film can be used to manufacture semiconductor wafers. As a method of manufacturing a semiconductor wafer at this time, for example, a method having the following steps: a composite sheet for forming a protective film provided with a release film on the film for forming a protective film used in a composite sheet for forming a protective film is formed as the aforementioned protective film Using a composite sheet, the step of removing the release film from the film for forming a protective film (hereinafter, sometimes referred to as "peeling step"); the protective film in the composite sheet for forming a protective film after removing the release film The step of attaching the forming film to the semiconductor wafer (hereinafter sometimes referred to as the "attaching step"); the step of curing the protective film forming film attached to the semiconductor wafer to form a protective film (hereinafter , Sometimes simply referred to as "protective film formation step"); divide the semiconductor wafer, cut the protective film or protective film formation film, and obtain a plurality of semiconductor wafers with the cut protective film or protective film formation film Step (hereinafter, sometimes referred to as "dividing step"); and the step of picking up the semiconductor wafer provided with the protective film or protective film forming film after cutting from the support sheet (hereinafter, sometimes referred to as "Pickup Step"). In the aforementioned manufacturing method, after the aforementioned attaching step, the aforementioned protective film forming step, dividing step, and picking step are performed. Furthermore, although the picking step is performed after the dividing step, in addition to this aspect, the order of performing the protective film forming step, the dividing step, and the picking step can be arbitrarily set according to the purpose.

作為前述保護膜形成用複合片的使用對象之半導體晶圓的厚度並無特別限定，就後述更容易分割為半導體晶片之方面而言，較佳為30μm至1000μm，更佳為100μm至400μm。The thickness of the semiconductor wafer to be used for the composite sheet for forming a protective film is not particularly limited, but it is preferably 30 μm to 1000 μm, more preferably 100 μm to 400 μm in terms of easier division into semiconductor wafers described later.

以下，一邊參照圖式，一邊對上述製造方法進行說明。圖14係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。此處，列舉保護膜形成用複合片如圖1所示之情形的製造方法為例進行說明。Hereinafter, the above-mentioned manufacturing method will be described with reference to the drawings. FIG. 14 is a cross-sectional view for schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. Here, the manufacturing method of the case where the composite sheet for protective film formation is shown in FIG. 1 is mentioned as an example and demonstrated.

本實施形態的製造方法(本說明書中，有時稱為「製造方法(1)」)具有：使用於保護膜形成用複合片中的保護膜形成用膜上具備剝離膜之保護膜形成用複合片作為前述保護膜形成用複合片，自前述保護膜形成用膜移除前述剝離膜之步驟(剝離步驟)；將移除前述剝離膜後的前述保護膜形成用複合片中的保護膜形成用膜貼附於半導體晶圓之步驟(貼附步驟)；使貼附於前述半導體晶圓後的前述保護膜形成用膜硬化而形成保護膜之步驟(保護膜形成步驟)；分割前述半導體晶圓，切斷前述保護膜，獲得具備切斷後的保護膜之多個半導體晶片之步驟(分割步驟)；以及將具備前述切斷後的保護膜之半導體晶片自前述支撐片扯離而進行拾取之步驟(拾取步驟)。The manufacturing method of this embodiment (in this specification, sometimes referred to as "manufacturing method (1)") has: the protective film forming film used in the protective film forming composite sheet is provided with a release film on the protective film forming composite The sheet is used as the composite sheet for forming the protective film, and the step of removing the peeling film from the film for forming the protective film (peeling step); the protective film is formed in the composite sheet for forming the protective film after the peeling film is removed The step of attaching the film to the semiconductor wafer (attaching step); the step of hardening the protective film forming film attached to the semiconductor wafer to form a protective film (protecting film forming step); dividing the semiconductor wafer , The step of cutting the protective film to obtain a plurality of semiconductor wafers with the cut protective film (dividing step); and the step of separating the semiconductor wafer with the cut protective film from the support sheet and picking it up ( Picking step).

製造方法(1)的前述剝離步驟中，使用於保護膜形成用複合片中的保護膜形成用膜上具備剝離膜之保護膜形成用複合片、亦即圖1所示之保護膜形成用複合片101作為前述保護膜形成用複合片。並且，於剝離步驟中，如圖14A所示，自保護膜形成用膜101移除剝離膜15。 此外，此處為方便起見而對移除剝離膜15後的保護膜形成用複合片亦標附符號101而表示。 如上文所說明，移除剝離膜15後的保護膜形成用複合片101的剝離帶電得到抑制。In the aforementioned peeling step of the manufacturing method (1), the protective film forming film used in the protective film forming composite sheet is provided with a peeling film on the protective film forming composite sheet, that is, the protective film forming composite sheet shown in FIG. 1 The sheet 101 serves as the aforementioned composite sheet for forming a protective film. And in the peeling step, as shown in FIG. 14A, the peeling film 15 is removed from the film 101 for protective film formation. In addition, for the sake of convenience, the composite sheet for forming a protective film after the release film 15 is removed is also indicated by the reference numeral 101. As described above, the peeling charge of the composite sheet 101 for forming a protective film after the peeling film 15 is removed is suppressed.

製造方法(1)的剝離步驟後，於前述貼附步驟中，如圖14B所示，於半導體晶圓9的內面9b，貼附移除剝離膜15後的保護膜形成用複合片101中的保護膜形成用膜13。 於貼附步驟中，亦可藉由將保護膜形成用膜13進行加熱而使之軟化，並貼附於半導體晶圓9。 此外，此處省略圖示半導體晶圓9中電路面上的凸塊等。After the peeling step of the manufacturing method (1), in the foregoing attaching step, as shown in FIG. 14B, on the inner surface 9b of the semiconductor wafer 9, the protective film forming composite sheet 101 with the peeling film 15 removed is attached The film 13 for forming a protective film. In the attaching step, the protective film forming film 13 may be heated to soften it and attached to the semiconductor wafer 9. In addition, the bumps and the like on the circuit surface of the semiconductor wafer 9 are omitted here.

如前文所說明，於剝離步驟後，保護膜形成用複合片101的剝離帶電得到抑制。因此，於貼附步驟後，於保護膜形成用膜13與半導體晶圓9之間之異物之混入得到抑制。更具體而言，於保護膜形成用膜13的第1面13a與半導體晶圓9的內面9b之間未確認到異物，或者確認到之異物的數量明顯少。As described above, after the peeling step, the peeling charge of the composite sheet 101 for forming a protective film is suppressed. Therefore, after the attaching step, mixing of foreign matter between the protective film forming film 13 and the semiconductor wafer 9 is suppressed. More specifically, no foreign matter was confirmed between the first surface 13a of the protective film forming film 13 and the inner surface 9b of the semiconductor wafer 9, or the number of confirmed foreign matter was significantly small.

製造方法(1)的貼附步驟後，於前述保護膜形成步驟中，使貼附於半導體晶圓9後的保護膜形成用膜13硬化，如圖14C所示，形成保護膜13'。此時，於保護膜形成用膜13為熱硬化性之情形時，藉由將保護膜形成用膜13進行加熱，而形成保護膜13'。於保護膜形成用膜13為能量線硬化性之情形時，藉由經由支撐片10對保護膜形成用膜13照射能量線，而形成保護膜13'。 此外，此處以符號101'表示保護膜形成用膜13成為保護膜13'後的保護膜形成用複合片。該情況於以後的圖中亦相同。After the attaching step of the manufacturing method (1), in the aforementioned protective film forming step, the protective film forming film 13 attached to the semiconductor wafer 9 is cured, and as shown in FIG. 14C, a protective film 13' is formed. At this time, when the protective film formation film 13 is thermosetting, the protective film formation film 13 is heated to form the protective film 13'. When the protective film formation film 13 is energy ray curable, the protective film 13 ′ is formed by irradiating the protective film formation film 13 with energy rays through the support sheet 10. In addition, the code|symbol 101' represents the composite sheet for protective film formation after the film 13 for protective film formation becomes a protective film 13' here. This situation is also the same in subsequent figures.

保護膜形成步驟中，保護膜形成用膜13的硬化條件、亦即熱硬化時的加熱溫度及加熱時間、以及能量線硬化時的能量線的照度及光量如上文所說明。In the protective film formation step, the curing conditions of the protective film formation film 13, that is, the heating temperature and heating time during thermal curing, and the illuminance and light intensity of the energy rays during energy ray curing are as described above.

製造方法(1)的保護膜形成步驟後，於前述分割步驟中，分割半導體晶圓9，切斷保護膜13'，如圖14D所示，獲得具備切斷後的保護膜130'之多個半導體晶片9'。此時，保護膜13'係於沿著半導體晶片9'的周緣部之位置被切斷(分割)。After the protective film forming step of the manufacturing method (1), in the aforementioned dividing step, the semiconductor wafer 9 is divided, and the protective film 13' is cut, as shown in FIG. 14D, to obtain a plurality of semiconductors with the cut protective film 130' Chip 9'. At this time, the protective film 13' is cut (divided) at a position along the peripheral edge of the semiconductor wafer 9'.

前述分割步驟中，分割半導體晶圓9、切斷保護膜13'之方法可為公知的方法。 作為此種方法，例如可列舉：使用切割刀片，將半導體晶圓9連同保護膜13'一起分割(切斷)之方法；以朝設定於半導體晶圓9的內部之焦點來聚焦之方式照射雷射光，於半導體晶圓9的內部形成改質層，繼而，將形成有該改質層且於內面9b貼附有保護膜13'之半導體晶圓9與該保護膜13'一起沿保護膜13'的表面方向擴展，切斷保護膜13'，並且於改質層的部位分割半導體晶圓9之方法等。In the aforementioned dividing step, the method of dividing the semiconductor wafer 9 and cutting the protective film 13' may be a known method. As such a method, for example, a method of dividing (cutting) the semiconductor wafer 9 together with the protective film 13' using a dicing blade; and irradiating the lightning to focus on the focal point set inside the semiconductor wafer 9 The light is irradiated to form a modified layer inside the semiconductor wafer 9. Then, the semiconductor wafer 9 with the modified layer formed and the protective film 13' attached to the inner surface 9b along with the protective film 13' The surface direction of 13' is expanded, the protective film 13' is cut, and the semiconductor wafer 9 is divided at the modified layer.

製造方法(1)的分割步驟後，於前述拾取步驟中，如圖14E所示，將具備切斷後的保護膜130'之半導體晶片9'自支撐片10扯離而進行拾取。此處，以箭頭I表示拾取方向，該情況於以後的圖中亦相同。作為用以將半導體晶片9'連同保護膜130'一起自支撐片10扯離之扯離機構8，可列舉真空吸嘴等。 藉由以上步驟，獲得目標半導體晶片9'作為附保護膜之半導體晶片。 利用製造方法(1)所獲得之附保護膜之半導體晶片，於保護膜130'與半導體晶片9'之間的異物之混入得到抑制，具有優異的特性。After the dividing step of the manufacturing method (1), in the aforementioned pickup step, as shown in FIG. 14E, the semiconductor wafer 9'with the cut protective film 130' is pulled off from the support sheet 10 and picked up. Here, the arrow I indicates the pick-up direction, and this situation is the same in subsequent figures. As the pulling-off mechanism 8 for pulling the semiconductor wafer 9'together with the protective film 130' from the supporting sheet 10, a vacuum suction nozzle or the like can be cited. Through the above steps, the target semiconductor chip 9'is obtained as a semiconductor chip with protective film. In the semiconductor wafer with a protective film obtained by the manufacturing method (1), the incorporation of foreign matter between the protective film 130' and the semiconductor wafer 9'is suppressed, and it has excellent characteristics.

製造方法(1)中，於保護膜形成步驟後進行分割步驟，但於本實施形態的半導體晶片之製造方法中，亦可不進行保護膜形成步驟而進行分割步驟，於分割步驟後進行保護膜形成步驟(有時將本實施形態稱為「製造方法(2)」)。 亦即，本實施形態的製造方法(製造方法(2))具有：使用於保護膜形成用複合片中的保護膜形成用膜上具備剝離膜之保護膜形成用複合片作為前述保護膜形成用複合片，自前述保護膜形成用膜移除前述剝離膜之步驟(剝離步驟)；將移除前述剝離膜後的前述保護膜形成用複合片中的保護膜形成用膜貼附於半導體晶圓之步驟(貼附步驟)；分割前述半導體晶圓，切斷前述保護膜形成用膜，獲得具備切斷後的保護膜形成用膜之多個半導體晶片之步驟(分割步驟)；使貼附於前述半導體晶圓後的前述保護膜形成用膜(切斷後的保護膜形成用膜)硬化而形成保護膜之步驟(保護膜形成步驟)；以及將具備前述切斷後(已切斷)的保護膜之半導體晶片自前述支撐片扯離而進行拾取之步驟(拾取步驟)。 圖15係用於以示意方式說明此種半導體晶片之製造方法的一實施形態之剖視圖。In the manufacturing method (1), the dividing step is performed after the protective film forming step. However, in the semiconductor wafer manufacturing method of this embodiment, the dividing step may be performed without the protective film forming step, and the protective film forming is performed after the dividing step Step (this embodiment is sometimes referred to as "manufacturing method (2)"). That is, the manufacturing method (manufacturing method (2)) of the present embodiment has: a protective film forming composite sheet provided with a release film on the protective film forming film used in the protective film forming composite sheet as the protective film forming Composite sheet, the step of removing the peeling film from the protective film forming film (peeling step); attaching the protective film forming film in the protective film forming composite sheet after the peeling film is removed to the semiconductor wafer The step (attachment step); the step of dividing the semiconductor wafer, cutting the protective film forming film, and obtaining a plurality of semiconductor wafers with the cut protective film forming film (dividing step); attaching to the foregoing The step of curing the protective film forming film (the protective film forming film after cutting) after the semiconductor wafer to form a protective film (protective film forming step); and cutting the protective film provided with the cutting (cut) The semiconductor wafer is pulled away from the aforementioned support sheet and picked up (pickup step). FIG. 15 is a cross-sectional view for schematically explaining an embodiment of the manufacturing method of such a semiconductor wafer.

製造方法(2)的前述剝離步驟及貼附步驟分別如圖15A至圖15B所示，可利用與製造方法(1)的剝離步驟及貼附步驟相同的方法(如圖14A至圖14B所示)進行。 與製造方法(1)之情形同樣地，製造方法(2)中，於貼附步驟後，於保護膜形成用膜13與半導體晶圓9之間的異物之混入亦得到抑制。The aforementioned peeling step and attaching step of the manufacturing method (2) are shown in FIGS. 15A to 15B, respectively, and the same method as the peeling step and attaching step of the manufacturing method (1) can be used (as shown in FIGS. 14A to 14B) )get on. As in the case of the manufacturing method (1), in the manufacturing method (2), the mixing of foreign matter between the protective film forming film 13 and the semiconductor wafer 9 after the attaching step is also suppressed.

製造方法(2)的前述分割步驟中，分割半導體晶圓9，切斷保護膜形成用膜13，如圖15C所示，獲得具備切斷後的保護膜形成用膜130之多個半導體晶片9'。此時，保護膜形成用膜13係於沿著半導體晶片9'的周緣部之位置被切斷(分割)。以符號130表示該切斷後的保護膜形成用膜13。In the aforementioned dividing step of the manufacturing method (2), the semiconductor wafer 9 is divided, and the protective film forming film 13 is cut, as shown in FIG. 15C, to obtain a plurality of semiconductor wafers 9'having the cut protective film forming film 130 . At this time, the protective film forming film 13 is cut (divided) at a position along the peripheral edge of the semiconductor wafer 9'. The code|symbol 130 shows the film 13 for protective film formation after this cutting|disconnection.

製造方法(2)的前述保護膜形成步驟中，使保護膜形成用膜130硬化，如圖15D所示，於半導體晶片9'形成保護膜130'。 製造方法(2)中的保護膜形成步驟可利用與製造方法(1)中的保護膜形成步驟相同的方法進行。 藉由進行本步驟，獲得與製造方法(1)的分割步驟結束後、亦即與圖14D相同的狀態的附保護膜之半導體晶片。In the aforementioned protective film forming step of the manufacturing method (2), the protective film forming film 130 is cured, and as shown in FIG. 15D, a protective film 130' is formed on the semiconductor wafer 9'. The protective film forming step in the manufacturing method (2) can be performed by the same method as the protective film forming step in the manufacturing method (1). By performing this step, after the dividing step of the manufacturing method (1) is completed, that is, the semiconductor wafer with a protective film in the same state as in FIG. 14D is obtained.

製造方法(2)的前述拾取步驟中，如圖15E所示，將具備切斷後的保護膜130'之半導體晶片9'自支撐片10扯離而進行拾取。 製造方法(2)中的拾取步驟可利用與製造方法(1)中的拾取步驟相同的方法(如圖14E所示)進行。 藉由以上步驟，獲得目標半導體晶片9'作為附保護膜之半導體晶片。 利用製造方法(2)所獲得之附保護膜之半導體晶片，於保護膜130'與半導體晶片9'之間的異物之混入得到抑制，具有優異的特性。In the aforementioned pickup step of the manufacturing method (2), as shown in FIG. 15E, the semiconductor wafer 9'provided with the cut protective film 130' is separated from the support sheet 10 and picked up. The pick-up step in the manufacturing method (2) can be performed by the same method as the pick-up step in the manufacturing method (1) (as shown in FIG. 14E). Through the above steps, the target semiconductor chip 9'is obtained as a semiconductor chip with protective film. In the semiconductor wafer with a protective film obtained by the manufacturing method (2), the incorporation of foreign matter between the protective film 130' and the semiconductor wafer 9'is suppressed, and it has excellent characteristics.

製造方法(1)及(2)中，於保護膜形成步驟後進行拾取步驟，但於本實施形態的半導體晶片之製造方法中，亦可不進行保護膜形成步驟而進行至拾取步驟，於拾取步驟後進行保護膜形成步驟(有時將本實施形態稱為「製造方法(3)」)。 亦即，本實施形態的製造方法(製造方法(3))具有：使用於保護膜形成用複合片中的保護膜形成用膜上具備剝離膜之保護膜形成用複合片作為前述保護膜形成用複合片，自前述保護膜形成用膜移除前述剝離膜之步驟(剝離步驟)；將移除前述剝離膜後的前述保護膜形成用複合片中的保護膜形成用膜貼附於半導體晶圓之步驟(貼附步驟)；分割前述半導體晶圓，切斷前述保護膜形成用膜，獲得具備切斷後的保護膜形成用膜之多個半導體晶片之步驟(分割步驟)；將具備前述切斷後的保護膜形成用膜之半導體晶片自前述支撐片扯離而進行拾取之步驟(拾取步驟)；以及使貼附於前述半導體晶圓後的前述保護膜形成用膜(切斷及拾取後的保護膜形成用膜)硬化而形成保護膜之步驟(保護膜形成步驟)。 圖16係用於以示意方式說明此種半導體晶片之製造方法的一實施形態之剖視圖。In the manufacturing methods (1) and (2), the pick-up step is performed after the protective film formation step. However, in the semiconductor wafer manufacturing method of this embodiment, the protective film formation step may not be performed and the pick-up step is performed. Then, a protective film formation step is performed (this embodiment may be referred to as "manufacturing method (3)"). That is, the manufacturing method (manufacturing method (3)) of this embodiment has: a protective film forming composite sheet provided with a release film on the protective film forming film used in the protective film forming composite sheet as the protective film forming Composite sheet, the step of removing the peeling film from the protective film forming film (peeling step); attaching the protective film forming film in the protective film forming composite sheet after the peeling film is removed to the semiconductor wafer The step (attachment step); the step of dividing the semiconductor wafer, cutting the protective film forming film, and obtaining a plurality of semiconductor wafers with the cut protective film forming film (dividing step); The step of picking up the semiconductor wafer of the protective film forming film from the support sheet (pickup step); and making the protective film forming film attached to the semiconductor wafer (protection after cutting and picking) The step of hardening the film for film formation to form a protective film (protective film forming step). FIG. 16 is a cross-sectional view for schematically explaining an embodiment of the method of manufacturing such a semiconductor wafer.

製造方法(3)的前述剝離步驟、貼附步驟及分割步驟分別如圖16A至圖16C所示，可利用與製造方法(2)的剝離步驟、貼附步驟及分割步驟相同的方法(如圖15A至圖15C所示)進行。 與製造方法(1)之情形同樣地，製造方法(3)中，於貼附步驟後，於保護膜形成用膜13與半導體晶圓9之間的異物之混入亦得到抑制。The aforementioned peeling step, attaching step, and dividing step of the manufacturing method (3) are shown in FIGS. 16A to 16C, respectively. The same method as the peeling step, attaching step, and dividing step of the manufacturing method (2) can be used (as shown in FIG. 15A to 15C). As in the case of the manufacturing method (1), in the manufacturing method (3), after the attaching step, the incorporation of foreign matter between the protective film forming film 13 and the semiconductor wafer 9 is also suppressed.

製造方法(3)的前述拾取步驟中，如圖16D所示，將具備切斷後的保護膜形成用膜130之半導體晶片9'自支撐片10扯離而進行拾取。 製造方法(3)中的拾取步驟可利用與製造方法(1)及(2)中的拾取步驟相同的方法(如圖14E及圖15E所示)進行。In the aforementioned pickup step of the manufacturing method (3), as shown in FIG. 16D, the semiconductor wafer 9'provided with the cut protective film forming film 130 is separated from the supporting sheet 10 and picked up. The pick-up step in the manufacturing method (3) can be performed by the same method as the pick-up step in the manufacturing methods (1) and (2) (as shown in FIGS. 14E and 15E).

製造方法(3)的前述保護膜形成步驟中，使拾取後的保護膜形成用膜130硬化，如圖16E所示，於半導體晶片9'形成保護膜130'。 於保護膜形成用膜13為熱硬化性之情形時，製造方法(3)中的保護膜形成步驟可利用與製造方法(1)及(2)中的保護膜形成步驟相同的方法進行。於保護膜形成用膜13為能量線硬化性之情形時，製造方法(3)中的保護膜形成步驟無需經由支撐片10對保護膜形成用膜130照射能量線，除該方面以外，可利用與製造方法(1)及(2)中的保護膜形成步驟相同的方法進行。 藉由以上步驟，獲得目標半導體晶片9'作為附保護膜之半導體晶片。 利用製造方法(3)所獲得之附保護膜之半導體晶片，於保護膜130'與半導體晶片9'之間的異物之混入得到抑制，具有優異的特性。In the aforementioned protective film forming step of the manufacturing method (3), the picked-up protective film forming film 130 is cured, and as shown in FIG. 16E, a protective film 130' is formed on the semiconductor wafer 9'. When the protective film forming film 13 is thermosetting, the protective film forming step in the manufacturing method (3) can be performed by the same method as the protective film forming step in the manufacturing methods (1) and (2). In the case where the protective film formation film 13 is energy-ray curable, the protective film formation step in the manufacturing method (3) does not need to irradiate the protective film formation film 130 with energy rays through the support sheet 10, and can be used in addition to this aspect It is performed in the same manner as the protective film formation step in the manufacturing methods (1) and (2). Through the above steps, the target semiconductor chip 9'is obtained as a semiconductor chip with protective film. In the semiconductor wafer with a protective film obtained by the manufacturing method (3), the mixing of foreign matter between the protective film 130' and the semiconductor wafer 9'is suppressed, and it has excellent characteristics.

製造方法(1)至(3)中，如上文所說明，作為分割半導體晶圓9而獲得半導體晶片9'之方法，可應用以下之方法：不使用切割刀片，而於半導體晶圓9的內部形成改質層，於該改質層的部位分割半導體晶圓9。該情形時，前述分割步驟中，於半導體晶圓9的內部形成改質層之步驟只要為較於改質層的部位分割半導體晶圓9之步驟之前的階段，則可於任一階段進行，例如可於貼附步驟之前、貼附步驟與保護膜形成步驟之間等任一階段進行。In the manufacturing methods (1) to (3), as described above, as a method of dividing the semiconductor wafer 9 to obtain the semiconductor wafer 9', the following method can be applied: without using a dicing blade, but inside the semiconductor wafer 9 A modified layer is formed, and the semiconductor wafer 9 is divided at the portion of the modified layer. In this case, in the aforementioned dividing step, the step of forming a modified layer inside the semiconductor wafer 9 can be performed at any stage as long as it is a stage before the step of dividing the semiconductor wafer 9 at the portion of the modified layer. For example, it can be performed at any stage before the attaching step, between the attaching step and the protective film forming step.

前文對使用圖1所示之保護膜形成用複合片101之情形的半導體晶片之製造方法進行了說明，但本發明的半導體晶片之製造方法並不限定於此。 例如，本發明的半導體晶片之製造方法即便使用圖2至圖5所示之保護膜形成用複合片102至保護膜形成用複合片105、圖6至圖10所示之保護膜形成用複合片201至保護膜形成用複合片205、圖11至圖13所示之保護膜形成用複合片301、保護膜形成用複合片401及保護膜形成用複合片501等圖1所示之保護膜形成用複合片101以外的保護膜形成用複合片，亦能夠同樣地製造半導體晶片。 如此，於使用另一實施形態的保護膜形成用複合片之情形時，只要基於這些片的結構的差異，於上述製造方法中，適宜地進行步驟之追加、變更、刪除等來製造半導體晶片即可。In the foregoing, the method of manufacturing a semiconductor wafer in the case of using the composite sheet 101 for forming a protective film shown in FIG. 1 has been described, but the method of manufacturing a semiconductor wafer of the present invention is not limited to this. For example, the method of manufacturing a semiconductor wafer of the present invention uses the protective film forming composite sheet 102 to the protective film forming composite sheet 105 shown in FIGS. 2 to 5, and the protective film forming composite sheet shown in FIGS. 6 to 10 201 to the protective film forming composite sheet 205, the protective film forming composite sheet 301 shown in FIGS. 11 to 13, the protective film forming composite sheet 401, and the protective film forming composite sheet 501, etc. It is also possible to manufacture semiconductor wafers in the same way with composite sheets for forming a protective film other than composite sheet 101. In this way, in the case of using the composite sheet for forming a protective film of another embodiment, based on the difference in the structure of these sheets, in the above-mentioned manufacturing method, adding, changing, and deleting steps are appropriately performed to manufacture a semiconductor wafer. can.

◇半導體裝置之製造方法 藉由上述製造方法獲得附保護膜之半導體晶片後，藉由公知的方法將該半導體晶片倒裝晶片連接於基板的電路面，然後製成半導體封裝體，藉由使用該半導體封裝體，能夠製造目標半導體裝置(省略圖示)。 [實施例]◇Method of manufacturing semiconductor device After the semiconductor chip with protective film is obtained by the above-mentioned manufacturing method, the semiconductor chip is flip-chip connected to the circuit surface of the substrate by a known method, and then a semiconductor package is manufactured. By using the semiconductor package, it can be manufactured Target semiconductor device (not shown). [Example]

以下，藉由具體的實施例對本發明更詳細地進行說明。但是，本發明完全不受限於以下所示之實施例。Hereinafter, the present invention will be described in more detail with specific examples. However, the present invention is not limited at all to the examples shown below.

[抗靜電組成物] 以下表示實施例或比較例中所使用之抗靜電組成物。 抗靜電組成物(VI-1)-1：將聚吡咯藉由反應性乳化劑乳化，並溶解於有機溶劑而獲得之聚吡咯溶液。 抗靜電組成物(VI-1)-2：出光興產公司製造的「UVH515」[Antistatic composition] The antistatic composition used in the examples or comparative examples is shown below. Antistatic composition (VI-1)-1: A polypyrrole solution obtained by emulsifying polypyrrole with a reactive emulsifier and dissolving it in an organic solvent. Antistatic composition (VI-1)-2: "UVH515" manufactured by Idemitsu Kosan Co., Ltd.

[保護膜形成用組成物的製造原料] 以下表示用於製造保護膜形成用組成物之原料。 [聚合物成分(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)共聚而成之丙烯酸系樹脂(重量平均分子量400000、玻璃轉移溫度-1℃) [熱硬化性成分(B)] ・環氧樹脂(B1) (B1)-1：雙酚A型環氧樹脂(三菱化學公司製造的「jER1055」，環氧當量800g/eq至900g/eq) (B1)-2：雙酚A型環氧樹脂(日本觸媒公司製造的「BPA328」，環氧當量235g/eq) (B1)-3：二環戊二烯型環氧樹脂(DIC公司製造的「Epiclon HP-7200HH」，環氧當量274g/eq至286g/eq) ・熱硬化劑(B2) (B2)-1：雙氰胺(熱活性潛伏性環氧樹脂硬化劑，三菱化學公司製造的「DICY7」，活性氫量21g/eq) [硬化促進劑(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的「Curezol 2PHZ-PW」) [填充材料(D)] (D)-1：二氧化矽填料(Admatechs公司製造的「SC2050MA」，利用環氧系化合物進行了表面修飾之二氧化矽填料，平均粒徑500nm) [著色劑(I)] (I)-1：碳黑(三菱化學公司製造的「MA600B」)[Materials for the production of protective film forming compositions] The raw materials used to manufacture the protective film forming composition are shown below. [Polymer component (A)] (A)-1: Copolymerize n-butyl acrylate (10 parts by mass), methyl acrylate (70 parts by mass), glycidyl methacrylate (5 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass) Acrylic resin (weight average molecular weight 400,000, glass transition temperature -1℃) [Thermosetting component (B)] ・Epoxy resin (B1) (B1)-1: Bisphenol A epoxy resin ("jER1055" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 800g/eq to 900g/eq) (B1)-2: Bisphenol A epoxy resin ("BPA328" manufactured by Nippon Shokubai Co., Ltd., epoxy equivalent 235g/eq) (B1)-3: Dicyclopentadiene epoxy resin ("Epiclon HP-7200HH" manufactured by DIC Corporation, epoxy equivalent 274g/eq to 286g/eq) ・Thermal hardener (B2) (B2)-1: Dicyandiamide (thermally active latent epoxy resin hardener, "DICY7" manufactured by Mitsubishi Chemical Corporation, active hydrogen content 21g/eq) [Hardening accelerator (C)] (C)-1: 2-Phenyl-4,5-dihydroxymethylimidazole ("Curezol 2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd.) [Filling material (D)] (D)-1: Silica filler ("SC2050MA" manufactured by Admatechs, silica filler with surface modification with epoxy compound, average particle size 500nm) [Colorant (I)] (I)-1: Carbon black ("MA600B" manufactured by Mitsubishi Chemical Corporation)

[實施例1] [保護膜形成用複合片之製造] [熱硬化性保護膜形成用組成物(III-1)之製造] 將聚合物成分(A)-1(150質量份)、環氧樹脂(B1)-1(10質量份)、環氧樹脂(B1)-2(60質量份)、環氧樹脂(B1)-3(30質量份)、熱硬化劑(B2)-1(2.4質量份)、硬化促進劑(C)-1(2.4質量份)、填充材料(D)-1(320質量份)、及著色劑(I)-1(1.16質量份)進行混合，進而以這些成分的合計濃度成為55質量%之方式，利用甲基乙基酮進行稀釋，製備熱硬化性保護膜形成用組成物(III-1)。[Example 1] [Manufacturing of composite sheet for forming protective film] [Manufacturing of composition for forming thermosetting protective film (III-1)] The polymer component (A)-1 (150 parts by mass), epoxy resin (B1)-1 (10 parts by mass), epoxy resin (B1)-2 (60 parts by mass), epoxy resin (B1)- 3 (30 parts by mass), thermosetting agent (B2)-1 (2.4 parts by mass), hardening accelerator (C)-1 (2.4 parts by mass), filler (D)-1 (320 parts by mass), and coloring Agent (I)-1 (1.16 parts by mass) was mixed, and then diluted with methyl ethyl ketone so that the total concentration of these components became 55% by mass, to prepare a thermosetting protective film forming composition (III- 1).

[保護膜形成用膜之製造] 使用聚對苯二甲酸乙二酯製膜的單面藉由聚矽氧處理進行了剝離處理之剝離膜(琳得科公司製造的「SP-PET381031」，厚度38μm)，於該剝離膜的前述剝離處理面，塗敷上述所獲得之熱硬化性保護膜形成用組成物(III-1)，於100℃乾燥2分鐘，藉此製造厚度40μm之熱硬化性的保護膜形成用膜。[Production of protective film forming film] Use a peeling film made of polyethylene terephthalate on one side of the film that has been peeled off by silicone treatment ("SP-PET381031" made by Lindeco, thickness 38μm). The peeling treatment surface was coated with the thermosetting protective film forming composition (III-1) obtained above, and dried at 100°C for 2 minutes to produce a 40 μm thick thermosetting protective film forming film.

[抗靜電層之形成] 作為基材，準備以下之聚丙烯製基材(厚度80μm)，其中一面的表面粗糙度Ra為0.2μm，另一面的表面粗糙度Ra小於該值，如此一面為凹凸面，另一面為平滑面。 於該聚丙烯製基材的前述凹凸面，使用棒式塗佈機，塗佈前述抗靜電組成物(VI-1)-1，於100℃乾燥2分鐘，藉此於前述基材上形成厚度75nm之背面抗靜電層。[Formation of antistatic layer] As a base material, prepare the following polypropylene base material (thickness 80μm), one of which has a surface roughness Ra of 0.2μm, and the other surface has a surface roughness Ra less than this value, so that one side is uneven and the other is smooth . The antistatic composition (VI-1)-1 was coated on the uneven surface of the polypropylene substrate using a bar coater, and dried at 100°C for 2 minutes, thereby forming a thickness on the substrate 75nm back antistatic layer.

[黏著劑組成物(I-4)之製造] 製備非能量線硬化性的黏著劑組成物(I-4)，該黏著劑組成物(I-4)含有丙烯酸系聚合物(100質量份)、雙酚A型環氧樹脂(三菱化學公司製造的「JER828」)(以前述環氧樹脂的量計為30質量份)、及3官能苯二甲基二異氰酸酯系交聯劑(三井武田化學公司製造的「Takenate D110N」)(以前述交聯劑的量計為35質量份)，進而含有作為溶劑之甲基乙基酮，且前述丙烯酸系聚合物、環氧樹脂及交聯劑的合計濃度為35質量%。前述丙烯酸系聚合物係使丙烯酸-2-乙基己酯(60質量份)、甲基丙烯酸甲酯(30質量份)、及丙烯酸2-羥基乙酯(10質量份)共聚而成之重量平均分子量為600000之共聚物。[Manufacturing of adhesive composition (I-4)] A non-energy-ray-curable adhesive composition (I-4) was prepared. The adhesive composition (I-4) contained an acrylic polymer (100 parts by mass) and a bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation) "JER828") (30 parts by mass based on the amount of the aforementioned epoxy resin), and a trifunctional xylylene diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (with the aforementioned crosslinking The amount of the agent is 35 parts by mass), and methyl ethyl ketone as a solvent is further contained, and the total concentration of the aforementioned acrylic polymer, epoxy resin, and crosslinking agent is 35% by mass. The aforementioned acrylic polymer is a weight average copolymer of 2-ethylhexyl acrylate (60 parts by mass), methyl methacrylate (30 parts by mass), and 2-hydroxyethyl acrylate (10 parts by mass) A copolymer with a molecular weight of 600,000.

[支撐片之製造] 使用與上述製造保護膜形成用膜時所使用之剝離膜相同的剝離膜(琳得科公司製造的「SP-PET381031」，厚度38μm)，於該剝離膜的剝離處理面塗敷上述所獲得之黏著劑組成物(I-4)，於120℃加熱乾燥2分鐘，藉此形成厚度5μm之非能量線硬化性的黏著劑層。 繼而，將該剝離膜及黏著劑層之積層物中黏著劑層的露出面(換言之，黏著劑層中之與剝離膜側為相反側的面)、與上述所獲得之基材及背面抗靜電層之積層物中基材的露出面(換言之，基材中之與背面抗靜電層側為相反側的面)貼合。藉此，製造背面抗靜電層、基材、黏著劑層及剝離膜依序於這些層的厚度方向上積層而構成之附剝離膜之支撐片。[Manufacturing of Support Sheet] Using the same release film ("SP-PET381031" manufactured by Lindeco, thickness 38μm) as the release film used in the production of the protective film forming film described above, the release film obtained above was coated on the release treatment surface The adhesive composition (I-4) was heated and dried at 120°C for 2 minutes to form a non-energy-ray-curable adhesive layer with a thickness of 5 μm. Then, the exposed surface of the adhesive layer in the laminate of the release film and the adhesive layer (in other words, the surface of the adhesive layer opposite to the release film side), and the substrate and back surface obtained above are antistatic The exposed surface of the substrate in the layered laminate (in other words, the surface of the substrate opposite to the back antistatic layer side) is bonded. Thereby, the back surface antistatic layer, the base material, the adhesive layer, and the release film are sequentially stacked in the thickness direction of these layers to form a support sheet with release film.

[保護膜形成用複合片之製造] 於上述所獲得之支撐片中，移除剝離膜。然後，將該支撐片中新產生之黏著劑層的露出面(換言之，黏著劑層中之與基材側為相反側的面)、與上述所獲得之剝離膜及保護膜形成用膜之積層物中保護膜形成用膜的露出面(換言之，保護膜形成用膜中之與剝離膜側為相反側的面)貼合。藉此，獲得背面抗靜電層(厚度75nm)、基材(厚度80μm)、黏著劑層(厚度5μm)、保護膜形成用膜(厚度40μm)及剝離膜(厚度38μm)依序於這些層的厚度方向上積層而構成之保護膜形成用複合片。該保護膜形成用複合片中，將背面抗靜電層、基材及黏著劑層之積層體(換言之，支撐片)的平面形狀設為直徑為270mm之圓形，將保護膜形成用膜及剝離膜之積層體的平面形狀設為直徑為210mm之圓形，使這些2個圓成為同心。 繼而，移除剝離膜，於保護膜形成用膜的露出面(換言之，保護膜形成用膜中之與黏著劑層側為相反側的面、或第1面)中之保護膜形成用膜的周緣部附近的區域，設置治具用接著劑層。 繼而，於保護膜形成用膜的第1面及治具用接著劑層的第1面，貼合與之前移除之剝離膜相同的剝離膜(琳得科公司製造的「SP-PET381031」，厚度38μm)。 藉由以上步驟，製造附剝離膜之保護膜形成用複合片，該複合片為圖1所示之構成且保護膜形成用膜的大小較支撐片的大小略小。 表1中表示構成保護膜形成用複合片之各層。層一欄記載為「-」時，表示保護膜形成用複合片不具備該層。[Manufacturing of composite sheet for forming protective film] In the support sheet obtained above, the release film was removed. Then, the exposed surface of the adhesive layer newly generated in the support sheet (in other words, the surface of the adhesive layer opposite to the substrate side), and the above-obtained release film and protective film forming film are laminated The exposed surface of the protective film formation film (in other words, the surface of the protective film formation film opposite to the release film side) is bonded. Thereby, a back antistatic layer (thickness 75nm), base material (thickness 80μm), adhesive layer (thickness 5μm), protective film formation film (thickness 40μm) and release film (thickness 38μm) in this order were obtained A composite sheet for forming a protective film formed by layering in the thickness direction. In this composite sheet for forming a protective film, the planar shape of the laminate of the back antistatic layer, the base material, and the adhesive layer (in other words, the support sheet) is set to a circular shape with a diameter of 270 mm, and the protective film forming film is peeled off. The planar shape of the film laminate was set to a circle with a diameter of 210 mm, and these two circles were made concentric. Then, the release film is removed, and the protective film formation film is on the exposed surface of the protective film formation film (in other words, the surface of the protective film formation film opposite to the adhesive layer side, or the first surface) In the area near the peripheral edge, an adhesive layer for jigs is provided. Then, on the first surface of the protective film forming film and the first surface of the adhesive layer for jigs, the same release film as the previously removed release film ("SP-PET381031" manufactured by Lindek Corporation, Thickness of 38μm). Through the above steps, a composite sheet for forming a protective film with a release film is manufactured. The composite sheet has the structure shown in FIG. 1 and the size of the film for forming a protective film is slightly smaller than that of the support sheet. Table 1 shows each layer constituting the composite sheet for forming a protective film. When the column of layer is described as "-", it means that the composite sheet for forming a protective film does not have the layer.

[保護膜形成用複合片之評價] [保護膜形成用複合片的最大帶電壓及帶電壓的半衰期之測定] 自上述所獲得之保護膜形成用複合片切取大小為45mm×45mm之細片，移除剝離膜，製作試片。 作為半衰期測定機，使用Shishido Elctrostatic公司製造的「STATIC HONESTMETER Type S-5109」，使用前述試片，依據JIS L 1094：2014，連續地測定試片(保護膜形成用複合片)的帶電壓。此時，使半衰期測定機中的施加部的針電極的前端接近於作為試片中之基材側的最表層之背面抗靜電層，使試片於電暈放電場帶電後，於試片之背面抗靜電層側測定帶電壓。然後，根據此時所獲得之測定值求出試片的最大帶電壓，進而求出試片的帶電壓衰減至最大帶電壓之1/2之時間，設為試片的帶電壓的半衰期。結果示於表1。[Evaluation of composite sheet for forming protective film] [Measurement of the maximum charged voltage and the charged half-life of the composite sheet for forming a protective film] A thin piece of 45 mm×45 mm in size was cut from the composite sheet for forming a protective film obtained above, and the release film was removed to prepare a test piece. As a half-life measuring machine, "STATIC HONESTMETER Type S-5109" manufactured by Shishido Elctrostatic was used, and the aforementioned test piece was used to continuously measure the charging voltage of the test piece (composite sheet for forming a protective film) in accordance with JIS L 1094:2014. At this time, make the tip of the needle electrode of the applicator in the half-life measuring machine close to the back antistatic layer which is the outermost layer on the substrate side of the test piece, and charge the test piece in the corona discharge field. The charged voltage was measured on the side of the back antistatic layer. Then, the maximum charged voltage of the test piece was obtained from the measured value obtained at this time, and the time for the charged voltage of the test piece to decay to 1/2 of the maximum charged voltage was calculated as the half-life of the charged voltage of the test piece. The results are shown in Table 1.

[保護膜形成用膜及半導體晶圓間的異物混入的抑制效果之確認] 針對上述所獲得之附剝離膜之保護膜形成用複合片，自作為該保護膜形成用複合片之基材側的最表層之背面抗靜電層之側，藉由目視進行觀察，進而使用數位顯微鏡(KEYENCE公司製造的「VE-8000」)進行觀察。然後，於保護膜形成用膜與剝離膜之整個區域中確認於保護膜形成用膜與剝離膜之間無最大長度為0.5mm以上之異物。[Confirmation of the effect of suppressing foreign matter mixing between the protective film formation film and the semiconductor wafer] The composite sheet for forming a protective film with a release film obtained above was visually observed from the side of the back antistatic layer of the base material side of the composite sheet for forming a protective film, and then a digital microscope was used ("VE-8000" manufactured by KEYENCE) for observation. Then, it was confirmed that there was no foreign matter having a maximum length of 0.5 mm or more between the protective film formation film and the release film in the entire region of the protective film formation film and the release film.

繼而，使用貼帶機(琳得科公司製造的「RAD-2500」)，自該附剝離膜之保護膜形成用複合片剝離(移除)剝離膜，並且立即將保護膜形成用複合片中的保護膜形成用膜的露出面(換言之為第1面)貼附於8吋矽晶圓(厚度350μm)的研磨面，將治具用接著劑層的露出面(換言之為第1面)貼附於環狀框架的表面，獲得保護膜形成用複合片及矽晶圓之積層物。Then, using a tape applicator ("RAD-2500" manufactured by Lindeco), peel (remove) the peeling film from the composite sheet for forming a protective film with peeling film, and immediately put it in the composite sheet for forming a protective film The exposed surface (in other words, the first surface) of the protective film formation film of the ”is attached to the polished surface of an 8-inch silicon wafer (thickness 350μm), and the exposed surface (in other words, the first surface) of the jig adhesive layer Attach it to the surface of the ring frame to obtain a laminate of a composite sheet for forming a protective film and a silicon wafer.

繼而，針對所獲得之該積層物，自作為該積層物中之基材側的最表層之背面抗靜電層之側，藉由目視進行觀察，進而使用數位顯微鏡(KEYENCE公司製造的「VE-8000」)進行觀察，於矽晶圓的整個區域確認於保護膜形成用膜與矽晶圓之間有無異物混入。於混入異物之情形時，將保護膜形成用複合片自矽晶圓剝離，使用前述數位顯微鏡，測定該異物的最大長度。然後，依據下述評價基準，評價異物混入的抑制效果。結果示於表1。 (評價基準) A：無最大長度為0.5mm以上之異物。 B：最大長度為0.5mm以上之異物有1個至3個。 C：最大長度為0.5mm以上之異物有4個以上。Then, the obtained laminate was observed visually from the side of the back antistatic layer which is the outermost layer on the substrate side of the laminate, and then a digital microscope (“VE-8000 manufactured by KEYENCE” ") Observation is performed to confirm whether foreign matter has entered between the protective film formation film and the silicon wafer over the entire area of the silicon wafer. When foreign matter is mixed, the protective film forming composite sheet is peeled from the silicon wafer, and the maximum length of the foreign matter is measured using the aforementioned digital microscope. Then, based on the following evaluation criteria, the effect of suppressing the incorporation of foreign matter was evaluated. The results are shown in Table 1. (Evaluation criteria) A: No foreign matter with a maximum length of 0.5mm or more. B: There are 1 to 3 foreign objects with a maximum length of 0.5mm or more. C: There are more than 4 foreign objects with a maximum length of 0.5 mm or more.

此外，本評價項目中，所謂「異物的最大長度」，意指於利用數位顯微鏡所得之觀察圖像中，於異物的表面選擇任意的相互不同的2點，測定連結這些2點間之線段的長度時，該異物中成為最長之前述線段的長度。In addition, in this evaluation item, the "maximum length of the foreign body" means that in the observation image obtained with a digital microscope, two points that are different from each other are selected on the surface of the foreign body, and the line segment connecting these two points is measured. In the case of length, the foreign matter becomes the length of the longest line segment.

[支撐片的全光線透過率之測定] 針對上述所獲得之支撐片，依據JIS K 7375：2008，使用分光光度計(島津製作所公司製造的「UV-VIS-NIR SPECTROPHOTOMETER UV-3600」)，測定全光線透過率(%)。結果示於表1。[Measurement of the total light transmittance of the support sheet] For the support sheet obtained above, in accordance with JIS K 7375:2008, a spectrophotometer ("UV-VIS-NIR SPECTROPHOTOMETER UV-3600" manufactured by Shimadzu Corporation) was used to measure the total light transmittance (%). The results are shown in Table 1.

[抗靜電層的耐擦傷性之評價] 針對上述所獲得之支撐片中的背面抗靜電層，利用下述方法評價耐擦傷性。 亦即，使用大榮科學精器製作所製造的平面磨耗試驗機「PA-2A」，於該試驗機中的頭部的按壓面被覆法蘭絨布。前述按壓面係平面狀，且前述按壓面的面積為2cm×2cm。作為法蘭絨布，使用厚度處於上文說明之範圍內之法蘭絨布。將該被覆有法蘭絨布之頭部的按壓面壓抵於背面抗靜電層的表面，以該狀態，一邊藉由頭部對背面抗靜電層施加125g/cm2 之荷重而進行按壓，一邊使頭部以10cm之直線距離往返運動10次，藉此一邊經由法蘭絨布施加125g/cm2 之荷重，一邊摩擦背面抗靜電層。然後，目視觀察背面抗靜電層的該摩擦面中面積為2cm×2cm之區域，將未確認到傷痕之情形判定為「A」，將確認到傷痕之情形判定為「B」，而評價抗靜電層的耐擦傷性。 結果示於表1中的「抗靜電層或基材的耐擦傷性」一欄。[Evaluation of Scratch Resistance of Antistatic Layer] With respect to the back antistatic layer in the support sheet obtained above, the scratch resistance was evaluated by the following method. That is, the surface abrasion tester "PA-2A" manufactured by Daiei Scientific Precision Manufacturing Co., Ltd. was used, and the pressing surface of the head in the tester was covered with flannel cloth. The pressing surface is flat, and the area of the pressing surface is 2 cm×2 cm. As the flannel cloth, use a flannel cloth whose thickness is within the range described above. The pressing surface of the head covered with the flannel cloth was pressed against the surface of the back antistatic layer. In this state, the head applied a load of 125g/cm 2 to the back antistatic layer to press, while making The head moves back and forth 10 times with a linear distance of 10 cm, thereby applying a load of 125 g/cm 2 through the flannel cloth while rubbing the antistatic layer on the back. Then, visually observe the area of the rubbing surface of the back antistatic layer with an area of 2cm×2cm, and judge the case where no scratches are confirmed as "A", and the case where the scratches are confirmed as "B", and evaluate the antistatic layer The abrasion resistance. The results are shown in the column "Scratch resistance of antistatic layer or substrate" in Table 1.

[保護膜形成用複合片之製造及評價] [實施例2] 使用前述抗靜電組成物(VI-1)-2代替前述抗靜電組成物(VI-1)-1，變更前述抗靜電組成物(VI-1)-2的塗佈量，於50℃乾燥1分鐘，藉此於基材上形成厚度170nm之背面抗靜電層，除這些方面以外，利用與實施例1之情形相同的方法，製造及評價保護膜形成用複合片。本實施例中所製造之附剝離膜之保護膜形成用複合片係背面抗靜電層(厚度170nm)、基材(厚度80μm)、黏著劑層(厚度5μm)、保護膜形成用膜(厚度40μm)及剝離膜(厚度38μm)依序於這些層的厚度方向上積層而構成，並且為圖1所示之構成且保護膜形成用膜的大小較支撐片的大小略小。 結果示於表1。[Production and evaluation of composite sheet for forming protective film] [Example 2] Use the aforementioned antistatic composition (VI-1)-2 instead of the aforementioned antistatic composition (VI-1)-1, change the coating amount of the aforementioned antistatic composition (VI-1)-2, and dry at 50°C 1 Minutes, thereby forming a back antistatic layer with a thickness of 170 nm on the substrate. Except for these points, the same method as in Example 1 was used to manufacture and evaluate a composite sheet for forming a protective film. The composite sheet for forming a protective film with a release film manufactured in this example is a back antistatic layer (thickness 170nm), base material (thickness 80μm), adhesive layer (thickness 5μm), protective film formation film (thickness 40μm) ) And a release film (thickness: 38 μm) are laminated in the thickness direction of these layers in order, and have the configuration shown in FIG. 1 and the size of the protective film forming film is slightly smaller than the size of the support sheet. The results are shown in Table 1.

[實施例3] 變更前述抗靜電組成物(VI-1)-2的塗佈量，將背面抗靜電層的厚度設為50nm代替170nm，除這些方面以外，利用與實施例2之情形相同的方法，製造及評價保護膜形成用複合片。本實施例中所製造之附剝離膜之保護膜形成用複合片係背面抗靜電層(厚度50nm)、基材(厚度80μm)、黏著劑層(厚度5μm)、保護膜形成用膜(厚度40μm)及剝離膜(厚度38μm)依序於這些層的厚度方向上積層而構成，並且為圖1所示之構成且保護膜形成用膜的大小較支撐片的大小略小。 結果示於表1。[Example 3] The coating amount of the aforementioned antistatic composition (VI-1)-2 was changed, and the thickness of the back antistatic layer was set to 50nm instead of 170nm. Except for these points, the same method as in Example 2 was used to manufacture and evaluate Composite sheet for protective film formation. The composite sheet for forming a protective film with a release film manufactured in this example is a back antistatic layer (thickness 50nm), base material (thickness 80μm), adhesive layer (thickness 5μm), and protective film formation film (thickness 40μm) ) And a release film (thickness: 38 μm) are laminated in the thickness direction of these layers in order, and have the configuration shown in FIG. 1 and the size of the protective film forming film is slightly smaller than the size of the support sheet. The results are shown in Table 1.

[實施例4] [保護膜形成用複合片之製造] [抗靜電性基材之製造] 對含有丙烯酸胺基甲酸酯樹脂及光聚合起始劑、且光聚合起始劑的含量相對於丙烯酸胺基甲酸酯樹脂的含量之比例為3質量%之組成物，調配作為抗靜電劑之鏻系離子液體(由鏻鹽所構成之離子液體)，並進行攪拌，藉此獲得能量線硬化性的抗靜電組成物(VI-2)。此時，抗靜電組成物(VI-2)中，抗靜電劑的含量相對於抗靜電劑及丙烯酸胺基甲酸酯樹脂的合計含量之比例係設為9質量%。[Example 4] [Manufacturing of composite sheet for forming protective film] [Manufacture of antistatic base material] The composition containing acrylic urethane resin and photopolymerization initiator, and the ratio of the content of the photopolymerization initiator to the content of the acrylic urethane resin is 3% by mass, formulated as an antistatic agent The phosphonium-based ionic liquid (ionic liquid composed of phosphonium salt) is stirred to obtain an energy-ray curable antistatic composition (VI-2). At this time, in the antistatic composition (VI-2), the ratio of the content of the antistatic agent to the total content of the antistatic agent and the acrylic urethane resin was 9% by mass.

繼而，藉由噴注式模具(fountain die)方式，將上述所獲得之抗靜電組成物(VI-2)塗佈於聚對苯二甲酸乙二酯製之製程膜(東麗公司製造之「Lumirror T60 PET 50 T-60 Toray」，厚度50μm製品)上，形成厚度80μm之塗膜。然後，使用紫外線照射裝置(EYEGRAPHICS公司製造的「ECS-401GX」)，使用高壓水銀燈(EYEGRAPHICS公司製造的「H04-L41」)，將燈的高度設為150mm、燈輸出設為3kw(換算輸出120mW/cm)、波長365nm之光線的照度設為271mW/cm2 、光量設為175mJ/cm2 ，對該塗膜照射紫外線。 繼而，使用剝離膜(琳得科公司製造的「SP-PET3801」，厚度38μm)，將該剝離膜的剝離處理面貼合於該紫外線照射後的塗膜。 繼而，使用與上述相同的紫外線照射裝置及高壓水銀燈，將燈的高度設為150mm、波長365nm之光線的照度設為271mW/cm2 、光量設為600mJ/cm2 ，經由前述剝離膜，對前述塗膜照射紫外線2次，藉此使前述塗膜(更具體而言，前述丙烯酸胺基甲酸酯樹脂)進行紫外線硬化。 繼而，自該紫外線硬化後的塗膜，移除前述製程膜及剝離膜，獲得含有聚丙烯酸胺基甲酸酯及鏻系離子液體，且厚度為80μm之抗靜電性基材。所獲得之抗靜電性基材中，抗靜電劑的含量相對於抗靜電劑及聚丙烯酸胺基甲酸酯的合計含量之比例為9質量%。表1中的「抗靜電劑(含量之比例(質量%))」一欄中表示該數值。Then, the antistatic composition (VI-2) obtained above was coated on a process film made of polyethylene terephthalate (manufactured by Toray) by means of a fountain die. On Lumirror T60 PET 50 T-60 Toray", a product with a thickness of 50μm), a coating film with a thickness of 80μm is formed. Then, using an ultraviolet irradiation device ("ECS-401GX" manufactured by EYEGRAPHICS) and a high-pressure mercury lamp ("H04-L41" manufactured by EYEGRAPHICS), the height of the lamp was set to 150mm and the lamp output was set to 3kw (converted output 120mW) /cm), the illuminance of light with a wavelength of 365 nm was set to 271 mW/cm 2 , and the amount of light was set to 175 mJ/cm 2 , and ultraviolet rays were irradiated to the coating film. Then, using a release film ("SP-PET3801" manufactured by Lindk Co., Ltd., thickness 38 μm), the release treatment surface of the release film was bonded to the coating film after ultraviolet irradiation. Then, using the above-described ultraviolet irradiation apparatus and the same high-pressure mercury lamp to set the height of 150mm, 365nm wavelength of the illumination light to 271mW / cm 2, light quantity is set to 600mJ / cm 2, via the release film of the The coating film is irradiated with ultraviolet rays twice, whereby the coating film (more specifically, the acrylic urethane resin) is cured by ultraviolet rays. Then, from the UV-cured coating film, the aforementioned process film and release film were removed to obtain an antistatic substrate containing polyacrylate urethane and phosphonium-based ionic liquid and a thickness of 80 μm. In the obtained antistatic base material, the ratio of the content of the antistatic agent to the total content of the antistatic agent and the polyacrylate urethane was 9% by mass. The column of "antistatic agent (content ratio (mass%))" in Table 1 shows this value.

[支撐片之製造] 利用與實施例1之情形相同的方法，於剝離膜(琳得科公司製造的「SP-PET381031」，厚度38μm)的剝離處理面，形成厚度5μm之非能量線硬化性的黏著劑層。 繼而，將該剝離膜及黏著劑層之積層物中黏著劑層的露出面(換言之，黏著劑層中之與剝離膜側為相反側的面)、與上述所獲得之抗靜電性基材的一面貼合。藉此，製造抗靜電性基材、黏著劑層及剝離膜依序於這些層的厚度方向上積層而構成的附剝離膜之支撐片。[Manufacturing of Support Sheet] Using the same method as in Example 1, a non-energy-ray-curable adhesive layer with a thickness of 5 μm was formed on the release-treated surface of a release film ("SP-PET381031" manufactured by Lindeco, thickness 38 μm). Then, the exposed surface of the adhesive layer in the laminate of the release film and the adhesive layer (in other words, the surface of the adhesive layer opposite to the release film side), and the antistatic substrate obtained above Fit on one side. Thereby, a support sheet with a release film formed by sequentially stacking the antistatic base material, the adhesive layer, and the release film in the thickness direction of these layers is manufactured.

[保護膜形成用複合片之製造] 使用上述所獲得之具備抗靜電性基材之支撐片代替具備背面抗靜電層及基材之前述支撐片，除該方面以外，利用與實施例1之情形相同的方法，製造附剝離膜之保護膜形成用複合片，該附剝離膜之保護膜形成用複合片係抗靜電性基材(厚度80μm)、黏著劑層(厚度5μm)、保護膜形成用膜(厚度40μm)及剝離膜(厚度38μm)依序於這些層的厚度方向上積層而構成，且進而具備治具用接著劑層。於該附剝離膜之保護膜形成用複合片中，抗靜電性基材及黏著劑層之積層體(換言之，支撐片)的平面形狀係直徑為270mm之圓形，保護膜形成用膜及剝離膜之積層體的平面形狀係直徑為210mm之圓形，這些2個圓為同心。該附剝離膜之保護膜形成用複合片為圖6所示之構成且保護膜形成用膜的大小較支撐片的大小略小。[Manufacturing of composite sheet for forming protective film] The support sheet with the antistatic substrate obtained above was used instead of the aforementioned support sheet with the back antistatic layer and the substrate. Except for this point, the same method as in Example 1 was used to produce a protection with a release film Composite sheet for film formation, the composite sheet for forming protective film with release film is antistatic base material (thickness 80μm), adhesive layer (thickness 5μm), protective film formation film (thickness 40μm) and release film (thickness 38 μm) is formed by sequentially stacking these layers in the thickness direction, and further includes an adhesive layer for jigs. In this composite sheet for forming a protective film with a release film, the planar shape of the laminate of the antistatic substrate and the adhesive layer (in other words, the support sheet) is a circle with a diameter of 270 mm, and the film for forming a protective film and the release The planar shape of the film laminate is a circle with a diameter of 210 mm, and these two circles are concentric. This composite sheet for forming a protective film with a release film has the structure shown in FIG. 6, and the size of the film for forming a protective film is slightly smaller than the size of the support sheet.

[保護膜形成用複合片之評價] 針對上述所獲得之保護膜形成用複合片，利用與實施例1之情形相同的方法進行評價。耐擦傷性之評價係對抗靜電性基材進行。結果示於表1。[Evaluation of composite sheet for forming protective film] The composite sheet for forming a protective film obtained above was evaluated in the same manner as in the case of Example 1. The evaluation of scratch resistance is performed on antistatic substrates. The results are shown in Table 1.

[保護膜形成用複合片之製造及評價] [比較例1] 不形成背面抗靜電層，除該方面以外，利用與實施例1之情形相同的方法，製造及評價保護膜形成用複合片。本比較例中所製造之附剝離膜之保護膜形成用複合片係基材(厚度80μm)、黏著劑層(厚度5μm)、保護膜形成用膜(厚度40μm)及剝離膜(厚度38μm)依序於這些層的厚度方向上積層而構成，且進而具備治具用接著劑層，並且於圖1中不具備背面抗靜電層，且保護膜形成用膜的大小較支撐片的大小略小。此外，本比較例中，對基材進行耐擦傷性之評價。 結果示於表1。[Production and evaluation of composite sheet for forming protective film] [Comparative Example 1] Except for this point, the back antistatic layer was not formed. The same method as that of Example 1 was used to manufacture and evaluate a composite sheet for forming a protective film. The composite sheet base material (thickness 80μm), adhesive layer (thickness 5μm), protective film formation film (thickness 40μm) and release film (thickness 38μm) for forming a protective film with a release film manufactured in this comparative example These layers are sequentially stacked in the thickness direction, and further include an adhesive layer for jigs. In addition, the back antistatic layer is not provided in FIG. 1, and the size of the protective film forming film is slightly smaller than the size of the support sheet. In addition, in this comparative example, the scratch resistance of the substrate was evaluated. The results are shown in Table 1.

[比較例2] 變更前述抗靜電組成物(VI-1)-2的塗佈量，將背面抗靜電層的厚度設為15nm代替170nm，除這些方面以外，利用與實施例2之情形相同的方法，製造及評價保護膜形成用複合片。本比較例中所製造之附剝離膜之保護膜形成用複合片係背面抗靜電層(厚度15nm)、基材(厚度80μm)、黏著劑層(厚度5μm)、保護膜形成用膜(厚度40μm)及剝離膜(厚度38μm)依序於這些層的厚度方向上積層而構成，且進而具備治具用接著劑層，並且為圖1所示之構成且保護膜形成用膜的大小較支撐片的大小略小。結果示於表1。[Comparative Example 2] The coating amount of the aforementioned antistatic composition (VI-1)-2 was changed, and the thickness of the back antistatic layer was set to 15nm instead of 170nm. Except for these points, the same method as in Example 2 was used to manufacture and evaluate Composite sheet for protective film formation. The composite sheet for forming a protective film with a release film manufactured in this comparative example is a back antistatic layer (thickness 15nm), base material (thickness 80μm), adhesive layer (thickness 5μm), and protective film formation film (thickness 40μm) ) And a release film (thickness 38μm) are laminated in order in the thickness direction of these layers, and further include an adhesive layer for jigs, and have the structure shown in Figure 1 and the size of the protective film forming film is larger than that of the support sheet The size is slightly smaller. The results are shown in Table 1.

[比較例3] 使用減少了抗靜電劑的含量之基材作為抗靜電性基材，除該方面以外，利用與實施例4之情形相同的方法，製造及評價保護膜形成用複合片。於所獲得之抗靜電性基材中，抗靜電劑的含量相對於抗靜電劑及聚丙烯酸胺基甲酸酯的合計含量之比例為3質量%。表1中的「抗靜電劑的含量之比例」一欄中表示該數值。 本比較例中所製造之附剝離膜之保護膜形成用複合片係抗靜電性基材(厚度80μm)、黏著劑層(厚度5μm)、保護膜形成用膜(厚度40μm)及剝離膜(厚度38μm)依序於這些層的厚度方向上積層而構成，且進而具備治具用接著劑層，並且為圖6所示之構成且保護膜形成用膜的大小較支撐片的大小略小。 結果示於表1。[Comparative Example 3] A base material with a reduced content of the antistatic agent was used as an antistatic base material. Except for this point, the same method as in Example 4 was used to manufacture and evaluate a composite sheet for forming a protective film. In the obtained antistatic substrate, the ratio of the content of the antistatic agent to the total content of the antistatic agent and the polyacrylate urethane is 3% by mass. The column of "the ratio of the content of the antistatic agent" in Table 1 shows this value. The composite sheet for forming a protective film with a release film manufactured in this comparative example is an antistatic base material (thickness 80μm), an adhesive layer (thickness 5μm), a protective film formation film (thickness 40μm), and a release film (thickness 38 μm) is formed by sequentially stacking these layers in the thickness direction, and further includes an adhesive layer for jigs, and has the configuration shown in FIG. 6 and the size of the protective film forming film is slightly smaller than the size of the support sheet. The results are shown in Table 1.

[表1] 實施例1 實施例 2 實施例 3 實施例 4 比較例 1 比較例 2 比較例 3 保護膜形成用複合片的構成 保護膜形成用膜 硬化性 熱硬化性 厚度(μm) 40 黏著劑層 硬化性 非能量線硬化性 厚度(μm) 5 基材 主材料 聚丙烯 - 聚丙烯 - 厚度(μm) 80 - 80 -                 抗靜電層 背面抗靜電層 主材料 聚吡咯 PEDOT/PSS - - PEDOT/PSS - 厚度(μm) 75 170 50 - - 15 - 抗靜電性基材 主材料 - - - 聚丙烯酸胺基甲酸酯 - - 聚丙烯酸胺基甲酸酯 厚度(μm) - - - 80 - - 80 抗靜電劑(含量之比例(質量%)) - - - 鏻系離子液體(9) - - 鏻系離子液體(3) 評價結果 保護膜形成用複合片的帶電壓的半衰期(秒) 1 3.5 5 15 >120 22 32 保護膜形成用膜及半導體晶圓間的異物混入的抑制效果 A A B B C C C 保護膜形成用複合片的最大帶電壓(V) 10 215 370 730 1400 820 970 支撐片的全光線透過率(%) 80 91 91 91 92 92 93 抗靜電層或基材的耐擦傷性 A A A A B A A [Table 1] Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Comparative example 3 Composition of composite sheet for forming protective film Protective film formation film Hardening Thermosetting Thickness (μm) 40 Adhesive layer Hardening Non-energy ray hardening Thickness (μm) 5 Substrate Main material Polypropylene - Polypropylene - Thickness (μm) 80 - 80 - Antistatic layer Antistatic layer on the back Main material Polypyrrole PEDOT/PSS - - PEDOT/PSS - Thickness (μm) 75 170 50 - - 15 - Antistatic substrate Main material - - - Polyacrylate Urethane - - Polyacrylate Urethane Thickness (μm) - - - 80 - - 80 Antistatic agent (content ratio (mass%)) - - - Phosphonium series ionic liquid (9) - - Phosphonium-based ionic liquid (3) Evaluation results Voltage half-life of composite sheet for protective film formation (seconds) 1 3.5 5 15 >120 twenty two 32 The effect of suppressing foreign matter mixing between the protective film forming film and the semiconductor wafer A A B B C C C Maximum charging voltage of composite sheet for protective film formation (V) 10 215 370 730 1400 820 970 Total light transmittance of support sheet (%) 80 91 91 91 92 92 93 Scratch resistance of antistatic layer or substrate A A A A B A A

由上述結果可明確，實施例1至實施例4的保護膜形成用複合片中，帶電壓的半衰期為15秒以下(1秒至15秒)，於使用這些保護膜形成用複合片之情形時，保護膜形成用膜及半導體晶圓間的異物混入得到抑制。尤其是，於使用帶電壓的半衰期為3.5秒以下(1秒至3.5秒)之實施例1至實施例2的保護膜形成用複合片之情形時，上述異物混入得到高度抑制。 實施例1至實施例4的保護膜形成用複合片具備背面抗靜電層或抗靜電性基材，將剝離膜自保護膜形成用膜移除時，具有剝離帶電的抑制效果。From the above results, it is clear that in the composite sheets for forming a protective film of Examples 1 to 4, the half-life of voltage is 15 seconds or less (1 second to 15 seconds), when these composite sheets for forming a protective film are used , The mixing of foreign matter between the protective film forming film and the semiconductor wafer is suppressed. In particular, when the composite sheet for forming a protective film of Examples 1 to 2 having a charged half-life of 3.5 seconds or less (1 second to 3.5 seconds) is used, the mixing of the above-mentioned foreign substances is highly suppressed. The composite sheet for forming a protective film of Examples 1 to 4 includes a back surface antistatic layer or an antistatic base material, and when the release film is removed from the film for forming a protective film, it has a peeling charge suppression effect.

實施例1至實施例4的保護膜形成用複合片於上述之帶電壓之測定時的初始帶電壓均與最大帶電壓相同，為730V以下(10V至730V)，這些片的特性良好。尤其是，實施例1至實施例2的保護膜形成用複合片的初始帶電壓為215V以下(10V至215V)，特性更良好。The initial charging voltage of the composite sheet for forming a protective film of Examples 1 to 4 at the time of the above charging voltage measurement was the same as the maximum charging voltage, which was 730V or less (10V to 730V), and the characteristics of these sheets were good. In particular, the composite sheet for forming a protective film of Examples 1 to 2 had an initial charging voltage of 215V or less (10V to 215V), and the characteristics were more favorable.

實施例1至實施例4的保護膜形成用複合片中的支撐片的全光線透過率為80%以上(80%至91%)，這些複合片具有較佳的光學特性。The total light transmittance of the supporting sheet in the protective film forming composite sheet of Examples 1 to 4 is more than 80% (80% to 91%), and these composite sheets have better optical properties.

實施例1至實施例3的保護膜形成用複合片中的背面抗靜電層、及實施例4的保護膜形成用複合片中的抗靜電性基材的耐擦傷性均高，這些複合片的保護膜形成用膜的檢查性良好。The back antistatic layer in the composite sheet for forming a protective film of Examples 1 to 3 and the antistatic base material in the composite sheet for forming a protective film of Example 4 have high scratch resistance. The inspectability of the protective film formation film is good.

相對於此，比較例1至比較例3的保護膜形成用複合片中，帶電壓的半衰期為22秒以上，於使用這些保護膜形成用複合片之情形時，保護膜形成用膜及半導體晶圓間的異物混入未得到抑制。 比較例1的保護膜形成用複合片不具備背面抗靜電層及抗靜電性基材，帶電壓的半衰期明顯長。 比較例2的保護膜形成用複合片具備背面抗靜電層，但該背面抗靜電層的厚度薄，該背面抗靜電層中的抗靜電劑的含量少，帶電壓的半衰期長。 比較例3的保護膜形成用複合片具備抗靜電性基材，但該抗靜電性基材中的抗靜電劑的含量少，帶電壓的半衰期長。 比較例1至比較例3的保護膜形成用複合片不具備背面抗靜電層及抗靜電性基材，或者即便具備，抗靜電能力亦不充分，因此於將剝離膜自保護膜形成用膜移除時，不具有剝離帶電的抑制效果。In contrast, in the composite sheets for forming a protective film of Comparative Examples 1 to 3, the charged half-life is 22 seconds or more. When these composite sheets for forming a protective film are used, the protective film forming film and the semiconductor crystal The mixing of foreign matter between the circles is not suppressed. The composite sheet for forming a protective film of Comparative Example 1 does not include a back surface antistatic layer and an antistatic base material, and has a significantly longer half-life with voltage. The composite sheet for forming a protective film of Comparative Example 2 includes a back surface antistatic layer, but the back surface antistatic layer has a thin thickness, the content of the antistatic agent in the back surface antistatic layer is small, and the half-life of charged voltage is long. The composite sheet for forming a protective film of Comparative Example 3 includes an antistatic base material, but the antistatic base material contains a small amount of antistatic agent and has a long half-life with voltage. The composite sheet for forming a protective film of Comparative Example 1 to Comparative Example 3 does not have a back antistatic layer and an antistatic base material, or even if they do, the antistatic ability is insufficient. Therefore, the release film is removed from the protective film forming film. When removing, it does not have the effect of suppressing peeling charge.

比較例1至比較例3的保護膜形成用複合片的初始帶電壓均與最大帶電壓相同，為820V以上(820V至1400V)，這些片的特性差。The initial charging voltage of the composite sheet for forming a protective film of Comparative Example 1 to Comparative Example 3 is the same as the maximum charging voltage, which is 820V or more (820V to 1400V), and these sheets have poor characteristics.

比較例1的保護膜形成用複合片中的基材的耐擦傷性低，該複合片的保護膜形成用膜的檢查性差。 [產業可利用性]The composite sheet for forming a protective film of Comparative Example 1 had a low scratch resistance of the base material, and the film for forming a protective film of the composite sheet had poor inspection properties. [Industry Availability]

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

8:扯離機構 9:半導體晶圓 9b:半導體晶圓的內面 9':半導體晶片 10,20,30,40,50,60,70:支撐片 10a,20a,30a,40a,50a,60a,70a:支撐片的第1面 11:基材 11a:基材的第1面 11b:基材的第2面 11':抗靜電性基材 11a':抗靜電性基材的第1面 11b':抗靜電性基材的第2面 12:黏著劑層 12a:黏著劑層的第1面 13,23:保護膜形成用膜 13a,23a:保護膜形成用膜的第1面 13':保護膜 15:剝離膜 16:治具用接著劑層 16a:治具用接著劑層的第1面 16c:治具用接著劑層的側面 17:背面抗靜電層 17a:背面抗靜電層的第1面 18:中間層 18a:中間層的第1面 18b:中間層的第2面 18c:中間層的側面 19:表面抗靜電層 19a:表面抗靜電層的第1面 23b:保護膜形成用膜的第2面 23c:保護膜形成用膜的側面 101,101',102,103,104,105,201,202,203,204,205,301,401,501:保護膜形成用複合片 130:切斷後的保護膜形成用膜 130':切斷後的保護膜 I:拾取方向8: Pull off the organization 9: Semiconductor wafer 9b: The inner surface of the semiconductor wafer 9': Semiconductor wafer 10, 20, 30, 40, 50, 60, 70: support piece 10a, 20a, 30a, 40a, 50a, 60a, 70a: the first side of the support sheet 11: Substrate 11a: The first side of the substrate 11b: The second side of the substrate 11': Antistatic substrate 11a': The first side of the antistatic substrate 11b': The second side of the antistatic substrate 12: Adhesive layer 12a: The first side of the adhesive layer 13,23: Film for forming protective film 13a, 23a: The first side of the protective film formation film 13': protective film 15: peeling film 16: Adhesive layer for jig 16a: The first side of the adhesive layer for jigs 16c: Side of the adhesive layer for jig 17: Antistatic layer on the back 17a: The first side of the antistatic layer on the back 18: Middle layer 18a: First side of the middle layer 18b: The second side of the middle layer 18c: the side of the middle layer 19: Surface antistatic layer 19a: The first side of the surface antistatic layer 23b: The second side of the protective film formation film 23c: Side of the protective film formation film 101,101',102,103,104,105,201,202,203,204,205,301,401,501: Composite sheet for forming protective film 130: Film for forming protective film after cutting 130': Protective film after cutting I: Picking direction

[圖1]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖2]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖3]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖4]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖5]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖6]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖7]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖8]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖9]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖10]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖11]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖12]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖13]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖14A]係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。 [圖14B]係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。 [圖14C]係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。 [圖14D]係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。 [圖14E]係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。 [圖15A]係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。 [圖15B]係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。 [圖15C]係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。 [圖15D]係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。 [圖15E]係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。 [圖16A]係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。 [圖16B]係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。 [圖16C]係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。 [圖16D]係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。 [圖16E]係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。Fig. 1 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. Fig. 2 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. Fig. 3 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. Fig. 4 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. Fig. 5 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. Fig. 6 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. Fig. 7 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. Fig. 8 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. Fig. 9 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. Fig. 10 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. Fig. 11 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. Fig. 12 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. Fig. 13 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. [FIG. 14A] is a cross-sectional view for schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [FIG. 14B] is a cross-sectional view for schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [FIG. 14C] is a cross-sectional view for schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [FIG. 14D] is a cross-sectional view for schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [FIG. 14E] is a cross-sectional view for schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [FIG. 15A] is a cross-sectional view for schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [FIG. 15B] is a cross-sectional view for schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [FIG. 15C] is a cross-sectional view for schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [FIG. 15D] is a cross-sectional view for schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [FIG. 15E] is a cross-sectional view for schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [FIG. 16A] is a cross-sectional view for schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [FIG. 16B] is a cross-sectional view for schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [FIG. 16C] is a cross-sectional view for schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [FIG. 16D] is a cross-sectional view for schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [FIG. 16E] is a cross-sectional view for schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention.

10:支撐片 10: Support piece

10a:支撐片的第1面 10a: The first side of the support sheet

11:基材 11: Substrate

11a:基材的第1面 11a: The first side of the substrate

11b:基材的第2面 11b: The second side of the substrate

12:黏著劑層 12: Adhesive layer

12a:黏著劑層的第1面 12a: The first side of the adhesive layer

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

13a:保護膜形成用膜的第1面 13a: The first side of the protective film formation film

15:剝離膜 15: peeling film

16:治具用接著劑層 16: Adhesive layer for jig

16a:治具用接著劑層的第1面 16a: The first side of the adhesive layer for jigs

16c:治具用接著劑層的側面 16c: Side of the adhesive layer for jig

17:背面抗靜電層 17: Antistatic layer on the back

17a:背面抗靜電層的第1面 17a: The first side of the antistatic layer on the back

101:保護膜形成用複合片 101: Composite sheet for forming protective film

Claims (7)

一種保護膜形成用複合片，具備支撐片、及形成於前述支撐片的一面上之保護膜形成用膜； 前述保護膜形成用複合片的帶電壓的半衰期為20秒以下。A composite sheet for forming a protective film, comprising a supporting sheet and a protective film forming film formed on one side of the supporting sheet; The charged half-life of the composite sheet for forming a protective film is 20 seconds or less. 如請求項1所記載之保護膜形成用複合片，其中依據JIS L 1094：2014所測定之前述保護膜形成用複合片的最大帶電壓為1kV以下。The composite sheet for forming a protective film as described in claim 1, wherein the maximum charging voltage of the composite sheet for forming a protective film as measured in accordance with JIS L 1094:2014 is 1 kV or less. 如請求項1或2所記載之保護膜形成用複合片，其中前述支撐片具備基材、及形成於前述基材的單面或雙面上之抗靜電層；或者 前述支撐片具備具有抗靜電性之基材作為抗靜電層。The composite sheet for forming a protective film according to claim 1 or 2, wherein the support sheet includes a substrate and an antistatic layer formed on one or both sides of the substrate; or The aforementioned support sheet has an antistatic substrate as an antistatic layer. 如請求項3所記載之保護膜形成用複合片，其中形成於前述基材的單面或雙面上之抗靜電層的厚度為100nm以下。The composite sheet for forming a protective film according to claim 3, wherein the thickness of the antistatic layer formed on one side or both sides of the aforementioned substrate is 100 nm or less. 如請求項1至4中任一項所記載之保護膜形成用複合片，其中前述支撐片的全光線透過率為80%以上。The composite sheet for forming a protective film according to any one of claims 1 to 4, wherein the support sheet has a total light transmittance of 80% or more. 如請求項3至5中任一項所記載之保護膜形成用複合片，其中於具有面積為2cm×2cm且為平面狀之按壓面之按壓機構的前述按壓面，被覆法蘭絨布，將被覆有前述法蘭絨布之前述按壓面壓抵於前述抗靜電層的表面，以前述狀態，一邊藉由前述按壓機構對前述抗靜電層施加125g/cm2 之荷重而進行按壓，一邊使前述按壓機構以10cm之直線距離往返運動10次，藉此摩擦前述抗靜電層之後，目視觀察前述抗靜電層的前述摩擦面中面積為2cm×2cm之區域時，未確認到傷痕。The composite sheet for forming a protective film according to any one of claims 3 to 5, wherein the pressing surface of the pressing mechanism having a planar pressing surface having an area of 2cm×2cm is covered with a flannel cloth to cover The pressing surface of the flannel cloth is pressed against the surface of the antistatic layer, and the pressing mechanism is used to press the antistatic layer by applying a load of 125g/cm 2 to the antistatic layer in the above state. After reciprocating 10 times in a linear distance of 10 cm, after rubbing the antistatic layer, when visually observing the area of the rubbing surface of the antistatic layer having an area of 2 cm×2 cm, no scratches were confirmed. 一種半導體晶片之製造方法，具有： 使用於保護膜形成用複合片中的保護膜形成用膜上具備剝離膜之保護膜形成用複合片作為如請求項1至6中任一項所記載之保護膜形成用複合片，自前述保護膜形成用膜移除前述剝離膜之步驟； 將移除前述剝離膜後的前述保護膜形成用複合片中的保護膜形成用膜貼附於半導體晶圓之步驟； 使貼附於前述半導體晶圓後的前述保護膜形成用膜硬化而形成保護膜之步驟； 分割前述半導體晶圓，切斷前述保護膜或保護膜形成用膜，獲得具備切斷後的保護膜或保護膜形成用膜之多個半導體晶片之步驟；以及 將具備前述切斷後的保護膜或保護膜形成用膜之半導體晶片自前述支撐片扯離而進行拾取之步驟。A method for manufacturing semiconductor wafers, including: The composite sheet for forming a protective film having a release film on the film for forming a protective film used in the composite sheet for forming a protective film is a composite sheet for forming a protective film as described in any one of claims 1 to 6, which is protected from the foregoing The step of removing the aforementioned peeling film from the film for film formation; The step of attaching the protective film forming film in the protective film forming composite sheet after the peeling film is removed to the semiconductor wafer; A step of curing the protective film forming film attached to the semiconductor wafer to form a protective film; The step of dividing the semiconductor wafer, cutting the protective film or the protective film forming film, and obtaining a plurality of semiconductor wafers having the cut protective film or the protective film forming film; and The step of picking up the semiconductor wafer provided with the protective film or protective film forming film after cutting from the supporting sheet.
TW108144085A 2018-12-05 2019-12-03 Composite sheet for forming protective film and method for manufacturing semiconductor chip TW202027993A (en)

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