TWI826601B - 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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TWI826601B
TWI826601B TW108143990A TW108143990A TWI826601B TW I826601 B TWI826601 B TW I826601B TW 108143990 A TW108143990 A TW 108143990A TW 108143990 A TW108143990 A TW 108143990A TW I826601 B TWI826601 B TW I826601B
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protective film
forming
composite sheet
film
antistatic
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TW108143990A
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TW202028393A (en
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佐伯尚哉
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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
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/562—Protection against mechanical damage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • 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
    • 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

Abstract

The surface resistivity of a back surface antistatic layer 17 in a composite sheet for protective film formation 101 comprising a support sheet 10 and a film for protective film formation 13 formed on the first surface 10a of the support sheet 10 is set to 1.0×1011 Ω/□ or less, and the frictional force between the test piece cut out from the composite sheet for protective film formation 101 after heating at 70 ° C for 1 minute and the porous table is set to 20 N 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 protective film formation, and method of 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特願2018-228523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 manufacturing method of a semiconductor wafer. This application claims priority based on Special Application No. 2018-228523 filed in Japan on December 5, 2018, and the contents of this application are incorporated into this article.

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，使用於電路形成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，有時半導體晶片中的與電路形成面為相反側的面(內面)裸露。In recent years, the industry has used 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 formation surface is used, and the electrodes are bonded to the substrate. Therefore, the surface (inner surface) of the semiconductor wafer opposite to the circuit-formed 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中產生龜裂。Sometimes, a resin film containing organic material is formed as a protective film on the inner surface of the exposed semiconductor wafer, and is incorporated into the semiconductor device in the form of a semiconductor wafer with a protective film. The protective film is used to prevent cracks in the semiconductor wafer after the dicing step or packaging.

為了形成此種保護膜，例如使用一種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, for example, a protective film-forming composite sheet including a protective film-forming film for forming a protective film on a support sheet is used. The protective film-forming film can be cured to form a protective film. In addition, the support sheet can be used to fix the semiconductor wafer having a protective film forming film or a protective film on its inner surface when dividing the semiconductor wafer into semiconductor wafers. Furthermore, the support sheet can also be used as a dicing sheet, and the protective film-forming composite sheet can also be used as a composite sheet in which the protective film-forming film and the dicing sheet are integrated.

更具體而言，保護膜形成用複合片係以如下之方式進行使用。 亦即，首先，於半導體晶圓的前述內面，貼附保護膜形成用複合片中的保護膜形成用膜，獲得積層體(以下，簡稱為「分割前積層體」)。More specifically, the composite sheet for protective film formation is used in the following manner. That is, first, the protective film forming film in the protective film forming composite sheet is attached to the inner surface of the semiconductor wafer to obtain a laminated body (hereinafter, simply referred to as "pre-dividing laminated body").

繼而，使前述分割前積層體中的保護膜形成用膜硬化而形成保護膜，將該積層體(以下，簡稱為「已硬化的積層體」)固定於切割台上。或者，不使前述分割前積層體中的保護膜形成用膜硬化而以原有的狀態固定於切割台上。 繼而，於前述已硬化的積層體之情形時，於固定於切割台上之狀態的該積層體中，分割半導體晶圓，切斷保護膜，獲得於支撐片上依序具備切斷後的保護膜、及分割後的半導體晶圓(亦即半導體晶片)之積層體(以下，簡稱為「硬化及已分割的積層體」)。或者，於前述分割前積層體之情形時，於固定於切割台上之狀態的該積層體中，分割半導體晶圓，切斷保護膜形成用膜，獲得於支撐片上依序具備切斷後的保護膜形成用膜、及半導體晶片之積層體(以下，簡稱為「未硬化及已分割的積層體」)。此處所進行的皆係通常的切割。Next, the protective film-forming film in the pre-dividing laminated body is cured to form a protective film, and the laminated body (hereinafter, simply referred to as the "cured laminated body") is fixed on the cutting table. Alternatively, the film for forming a protective film in the pre-dividing laminate is fixed to the cutting table in its original state without being hardened. Next, in the case of the above-mentioned hardened laminated body, in the state of being fixed on the cutting table, the semiconductor wafer is divided into the laminated body, and the protective film is cut to obtain the cut protective film, and a laminated body of divided semiconductor wafers (ie, semiconductor wafers) (hereinafter referred to as "hardened and divided laminated body"). Alternatively, in the case of the laminated body before dividing as described above, in the laminated body fixed on the cutting table, the semiconductor wafer is divided, the film for forming the protective film is cut, and the protection after cutting is obtained sequentially on the support sheet. A laminate of a film-forming film and a semiconductor wafer (hereinafter, simply referred to as "an uncured and divided laminate"). What is done here is normal cutting.

繼而，將硬化及已分割的積層體或未硬化及已分割的積層體於切割台上的固定狀態予以解除，將這些積層體搬運至洗淨用台上，並固定於該台上。 繼而，將固定於洗淨用台上之狀態的這些積層體(亦即，硬化及已分割的積層體或未硬化及已分割的積層體)用水洗淨，將前續步驟的切割時所產生且附著之切削屑沖洗而去除。該切削屑係來自半導體晶圓、保護膜或保護膜形成用膜。洗淨通常一邊使洗淨用台旋轉一邊進行。Next, the fixed state of the hardened and divided laminated body or the unhardened and divided laminated body on the cutting table is released, and these laminated bodies are conveyed to the washing table and fixed on this table. Next, these laminated bodies (that is, hardened and divided laminated bodies or unhardened and divided laminated bodies) fixed on the washing table are washed with water, and the laminated bodies produced during the cutting in the previous step are washed. And the attached cutting chips are washed and removed. The cutting chips come from semiconductor wafers, protective films, or films for forming protective films. Washing is usually performed while rotating the washing table.

繼而，將該洗淨後的硬化及已分割的積層體或未硬化及已分割的積層體於洗淨用台上的固定狀態予以解除，將這些積層體搬運至乾燥用台上，並固定於該台上。 繼而，使固定於乾燥用台上之狀態的這些積層體(亦即，硬化及已分割的積層體或未硬化及已分割的積層體)乾燥，將前續步驟中的洗淨時所附著之水去除。乾燥通常一邊使乾燥用台旋轉一邊進行。Then, the fixed state of the washed hardened and divided laminated body or the unhardened and divided laminated body on the washing table is released, and these laminated bodies are transported to the drying table and fixed on the drying table. on the stage. Next, these laminated bodies (i.e., hardened and divided laminated bodies or unhardened and divided laminated bodies) fixed on the drying table are dried, and the adhering layers during washing in the previous step are removed. water removal. Drying is usually performed while rotating the drying table.

繼而，將該乾燥後的硬化及已分割的積層體或未硬化及已分割的積層體於乾燥用台上的固定狀態予以解除，將這些積層體搬運至進行後續步驟之裝置，進行後續步驟。然後，最終將內面具備已切斷的保護膜之半導體晶片(附保護膜之半導體晶片)、或內面具備已切斷的保護膜形成用膜之半導體晶片(附保護膜形成用膜之半導體晶片)自支撐片扯離而進行拾取。已切斷的保護膜形成用膜於任一階段硬化而成為保護膜。Then, the fixed state of the dried hardened and divided laminated body or the unhardened and divided laminated body on the drying table is released, and these laminated bodies are transported to a device for performing subsequent steps, and the subsequent steps are performed. Then, the semiconductor wafer having the cut protective film on the inner surface (semiconductor wafer with protective film) or the semiconductor wafer having the protective film forming film cut on the inner surface (semiconductor with protective film forming film) is finally The wafer) is pulled away from the supporting sheet and picked up. The cut protective film forming film is cured at any stage and becomes a protective film.

以上述方式將硬化及已分割的積層體或未硬化及已分割的積層體固定於任一台上而進行作業後，解除該固定狀態，搬運至進行後續步驟之部位。這些積層體例如於任一台均藉由吸附而固定，解除吸附後，自台扯離，搬運至下一部位。通常，這些台均具有於台的厚度方向貫通之空隙部，藉由將台之與前述積層體接觸之側的相反側予以減壓，前述積層體吸附而固定於台上。本說明書中，有時將此種固定用台稱為吸附台。After the hardened and divided laminated body or the unhardened and divided laminated body is fixed on any table in the above manner and the work is performed, the fixed state is released and transported to the location where the subsequent steps are performed. For example, these laminated bodies are fixed by adsorption on any table. After the adsorption is released, they are pulled off from the table and transported to the next location. Usually, these tables have a gap portion penetrating in the thickness direction of the table. By depressurizing the side of the table opposite to the side in contact with the laminated body, the laminated body is adsorbed and fixed to the table. In this specification, this type of fixing table may be called an adsorption table.

另一方面，硬化及已分割的積層體或未硬化及已分割的積層體如上述般為了搬運而解除於台之利用吸附之固定，自台扯離時，容易帶電。此種帶電係因相互接觸的層彼此的剝離而導致這些層帶電，亦即所謂「剝離帶電」的1種。若如此帶電，且此時的帶電量變多，則有時會因靜電的影響而使半導體晶片中的電路遭破壞。其中，如上述般將這些積層體固定於乾燥用台上並乾燥後，自台扯離時，帶電量特別容易變多，電路特別容易遭破壞。關於先前的保護膜形成用複合片，為了防止該複合片的帶電，有的複合片於任一層中含有抗靜電劑。但是，若僅使用此種先前的保護膜形成用複合片，則難以抑制因帶電所致之半導體晶片中的電路的破壞。On the other hand, when the hardened and divided laminated body or the unhardened and divided laminated body is released from the suction fixation on the table for transportation as mentioned above and is pulled away from the table, it is easy to become charged. This kind of charging is a type of so-called "peeling charging" in which layers in contact with each other are charged due to peeling off of these layers. If such charging occurs and the amount of charging at this time increases, the circuit in the semiconductor chip may be damaged due to the influence of static electricity. Among them, when these laminates are fixed to a drying table and dried as described above, and then pulled away from the table, the amount of charge is particularly likely to increase, and the circuit is particularly susceptible to damage. Regarding conventional composite sheets for forming protective films, some composite sheets contain an antistatic agent in any layer in order to prevent the composite sheet from being charged. However, if only such a conventional composite sheet for forming a protective film is used, it is difficult to suppress damage to the circuit in the semiconductor wafer due to electrification.

對此，作為抑制剝離帶電之半導體加工用片，揭示有以下之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，於進行將內面具備接著片之半導體晶片自切割帶扯離，亦即所謂拾取時，能夠抑制接著片與切割帶之間的剝離帶電，抑制靜電的產生，抑制因該靜電所致之半導體晶片上的電路的破壞。 [先前技術文獻] [專利文獻]In this regard, as a sheet for semiconductor processing that suppresses peeling charge, a dicing tape-integrated adhesive sheet is disclosed: a dicing tape (equivalent to the aforementioned support sheet) with an adhesive layer laminated on a base material, and a dicing tape formed on the aforementioned adhesive layer. The absolute value of the peeling charging voltage when peeling off the adhesive layer and the adhesive sheet at a peeling speed of 10 m/min and a peeling angle of 150° is 0.5 kV or less (see Patent Document 1). According to Patent Document 1, by using this dicing tape-integrated adhesive sheet, when a semiconductor wafer having an adhesive sheet on its inner surface is pulled away from the dicing tape, that is, when picking up, it is possible to suppress peeling between the adhesive sheet and the dicing tape. It is charged to suppress the generation of static electricity and suppress the damage to the circuit on the semiconductor chip caused by the static electricity. [Prior technical literature] [Patent Document]

[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][Problem to be solved by the invention]

但是，剝離帶電的容易度通常是大受相互接觸的面的影響。並且，專利文獻1中所揭示之切割帶的表面與吸附台的表面的構成材料及表面狀態差異大。因此，於使用專利文獻1中所揭示之切割帶一體型接著片之情形時，如上文所說明，尚不確定於將硬化及已分割的積層體或未硬化及已分割的積層體自吸附台扯離時，能否抑制因帶電所致之半導體晶片中的電路的破壞。However, the ease of stripping and charging is usually greatly affected by the surfaces in contact with each other. Furthermore, the surface of the dicing tape disclosed in Patent Document 1 and the surface of the adsorption table are greatly different in constituent materials and surface conditions. Therefore, when using the dicing tape integrated adhesive sheet disclosed in Patent Document 1, it is not certain whether the hardened and divided laminated body or the unhardened and divided laminated body will be self-adsorbed from the adsorption table as explained above. When being pulled apart, can the damage to the circuit in the semiconductor chip caused by charging be suppressed?

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，並且將使用前述保護膜形成用複合片所獲得之支撐片、切斷後的保護膜或保護膜形成用膜、及半導體晶片依序積層而構成之積層體設為固定於台上之狀態，繼而，將前述積層體自台上的固定面扯離時，能夠抑制因帶電所致之半導體晶片中的電路的破壞。 [用以解決課題之手段]An object of the present invention is to provide a composite sheet for forming a protective film, which is provided with a support sheet and a film for forming a protective film, and a method for manufacturing a semiconductor wafer using the composite sheet for forming a protective film. The support sheet obtained from the protective film forming composite sheet, the cut protective film or protective film forming film, and the semiconductor wafer are sequentially laminated to form a laminated body that is fixed on a table, and then the laminated body is When the body is pulled away from the fixed surface on the table, damage to the circuit in the semiconductor chip due to charging can be suppressed. [Means used to solve problems]

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中之前述支撐片側的最表層的表面電阻率為1.0×1011 Ω/□以下；自於70℃加熱1分鐘後的前述保護膜形成用複合片，切取大小為10cm×20cm之試片，使前述試片中之前述支撐片側的最表層接觸於多孔台的表面，藉此將前述試片載置於前述多孔台上，使大小為6cm×10cm×2cm且質量為1kg之重物之大小為6cm×10cm之面接觸於前述試片中的保護膜形成用膜，將前述重物載置於前述保護膜形成用膜上，沿相對於前述試片之與前述多孔台之接觸面為平行的方向，使前述重物以10mm/min之速度移動，測定前述重物的即將開始移動前的荷重時，前述荷重的測定值為20N以下。The present invention provides a protective film-forming composite sheet, which includes a support sheet and a protective film-forming film formed on one side of the support sheet; and has a surface resistance of the outermost layer on the support sheet side in the protective film-forming composite sheet. The ratio is 1.0 × 10 11 Ω/□ or less; from the composite sheet for forming a protective film after heating at 70°C for 1 minute, cut a test piece with a size of 10 cm × 20 cm, so that the outermost layer on the side of the supporting sheet in the test piece Contact the surface of the porous stage, thereby placing the aforementioned test piece on the aforementioned porous stage, so that the 6cm × 10cm surface of a weight with a size of 6cm×10cm×2cm and a mass of 1kg contacts the aforementioned test piece For a protective film forming film, the aforementioned heavy object is placed on the aforementioned protective film forming film, and in a direction parallel to the contact surface of the aforementioned test piece and the aforementioned porous stage, the aforementioned heavy object is moved at a speed of 10 mm/min. When moving at a speed and measuring the load immediately before the weight starts moving, the measured value of the load is 20N or less.

本發明的保護膜形成用複合片中，前述保護膜形成用膜亦可為熱硬化性，前述表面電阻率亦可為前述保護膜形成用複合片中的前述保護膜形成用膜於130℃熱硬化2小時後的表面電阻率。 本發明的保護膜形成用複合片中，亦可為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，形成於前述基材的單面或雙面上之抗靜電層的厚度亦可為100nm以下。In the protective film-forming composite sheet of the present invention, the protective film-forming film may be thermosetting, and the surface resistivity may be: The protective film-forming film in the protective film-forming composite sheet is heated at 130°C Surface resistivity after 2 hours of hardening. In the composite sheet for forming a protective film of the present invention, the support sheet may be provided with a base material and an antistatic layer formed on one or both sides of the base material, or the support sheet may be provided with a base having antistatic properties. material 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 base material may be 100 nm or less.

本發明的保護膜形成用複合片中，前述支撐片的全光線透過率亦可為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，具有下述步驟：將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，製作由具備有支撐片、設置於前述支撐片的一面上之切斷後的前述保護膜或保護膜形成用膜、及設置於前述切斷後的保護膜或保護膜形成用膜之與前述支撐片側為相反側的面上之半導體晶片而成之積層體之步驟；以及將前述積層體中的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；進而，於前述積層體製作步驟與前述拾取步驟之間，具有將固定於台上之前述積層體自前述台扯離之步驟；於前述扯離步驟中，固定於台上之前述積層體於前述積層體之前述支撐片側的最表層的表面接觸於前述台，前述台之前述積層體的固定面為陶瓷製或不銹鋼製。 [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 flat pressing surface with an area of 2 cm×2 cm may be covered with flannel cloth, and the pressing surface covered with the flannel cloth may be covered with flannel cloth. Press against the surface of the antistatic layer, and in this state, while applying a load of 125g/cm 2 to the antistatic layer by the pressing mechanism, the pressing mechanism is reciprocated 10 times in a straight line distance of 10cm, After the antistatic layer was rubbed in this way, when an area of 2 cm × 2 cm on the rubbed surface of the antistatic layer was visually observed, no scratches were confirmed. In addition, the present invention provides a method for manufacturing a semiconductor wafer, which includes the following steps: affixing the protective film-forming film in the protective film-forming composite sheet to the semiconductor wafer; The step of curing the protective film-forming film to form a protective film; dividing the semiconductor wafer, cutting the protective film or the protective film-forming film, and producing a cutter having a support sheet and disposed on one side of the support sheet. The step of placing the cut protective film or protective film-forming film and a laminate of semiconductor wafers on the surface of the cut protective film or protective film-forming film opposite to the support sheet side; and The step of picking up the semiconductor wafer having the cut protective film or protective film forming film in the laminated body from the supporting sheet; further, between the laminated body manufacturing step and the picking up step, there is The step of pulling off the laminated body fixed on the table from the table; in the step of pulling off, the surface of the outermost layer of the laminated body fixed on the table on the side of the supporting sheet in front of the laminated body is in contact with the table, The fixing surface of the laminated body before the table is made of ceramic or stainless steel. [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，並且將使用前述保護膜形成用複合片所獲得之支撐片、切斷後的保護膜或保護膜形成用膜、及半導體晶片依序積層而構成之積層體設為固定於台上之狀態，繼而，將前述積層體自台上的固定面扯離時，能夠抑制因帶電所致之半導體晶片中的電路的破壞。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 is provided with a supporting sheet and a film for forming a protective film, and uses the aforementioned composite sheet. The support sheet obtained from the protective film forming composite sheet, the cut protective film or protective film forming film, and the semiconductor wafer are sequentially laminated to form a laminated body in a state of being fixed on a table, and then the laminated body is When it is pulled away from the fixed surface on the table, damage to the circuit in the semiconductor chip due to electrification can be suppressed.

◇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中之前述支撐片側的最表層的表面電阻率為1.0×1011 Ω/□以下，自於70℃加熱1分鐘後的前述保護膜形成用複合片，切取大小為10cm×20cm之試片，使前述試片中之前述支撐片側的最表層接觸於多孔台的表面，藉此將前述試片載置於前述多孔台上，使大小為6cm×10cm×2cm且質量為1kg之重物之大小為6cm×10cm之面接觸於前述試片中的保護膜形成用膜，將前述重物載置於前述保護膜形成用膜上，沿相對於前述試片之與前述多孔台之接觸面為平行的方向，使前述重物以10mm/min之速度移動，測定前述重物的即將開始移動前的荷重時，前述荷重的測定值(本說明書中，有時稱為「靜摩擦力」)成為20N以下。◇ Composite sheet for protective film formation The composite sheet for protective film formation according to one embodiment of the present invention includes a support sheet and a protective film-forming film formed on one side of the support sheet, and the composite sheet for protective film formation has The surface resistivity of the outermost layer on the side of the supporting sheet is 1.0×10 11 Ω/□ or less. From the composite sheet for forming a protective film after heating at 70°C for 1 minute, cut out a test piece of size 10cm×20cm, and make the test piece The outermost layer of the support sheet side of the piece is in contact with the surface of the porous stage, whereby the aforementioned test piece is placed on the aforementioned porous stage, so that the size of the weight of 6cm×10cm×2cm and the mass of 1kg is 6cm× A 10cm surface of the protective film-forming film in contact with the test piece is placed on the protective film-forming film in a direction parallel to the contact surface of the test piece with the porous stage. When the weight is moved at a speed of 10 mm/min and the load immediately before the movement of the weight is measured, the measured value of the load (sometimes referred to as "static friction force" in this specification) is 20 N or less.

前述保護膜形成用複合片如此般前述表面電阻率為1.0×1011 Ω/□以下，平常時的帶電(本說明書中，有時稱為「平常時帶電」)得到抑制。 另一方面，於使用半導體晶圓及前述保護膜形成用複合片，製造內面具備保護膜之半導體晶片之過程中，製作支撐片、切斷後的保護膜或保護膜形成用膜、及半導體晶片依序積層而構成之積層體。並且，於該積層體之操作時，進行以下之操作：將該積層體設為固定於台上之狀態，繼而，自台上的固定面扯離。前述保護膜形成用複合片中，藉由前述表面電阻率為1.0×1011 Ω/□以下，且前述靜摩擦力為20N以下，前述積層體的扯離時的帶電(本說明書中，有時稱為「扯離時帶電」)得到抑制。結果，該扯離時的半導體晶片中的電路的破壞得到抑制。關於內面具備保護膜之半導體晶片之製造方法，將於後文詳細地進行說明。The composite sheet for forming a protective film has such a surface resistivity of 1.0×10 11 Ω/□ or less that normal charging (in this specification, may be referred to as “normal charging”) is suppressed. On the other hand, in the process of manufacturing a semiconductor wafer having a protective film on its inner surface using a semiconductor wafer and the aforementioned protective film-forming composite sheet, a support sheet, a cut protective film or a protective film-forming film, and a semiconductor wafer are produced A layered body formed by stacking layers in sequence. Furthermore, when handling the laminated body, the following operations are performed: fixing the laminated body on the table, and then pulling it off from the fixed surface on the table. In the composite sheet for forming a protective film, since the surface resistivity is 1.0×10 11 Ω/□ or less and the static friction force is 20 N or less, the charging when the laminated body is pulled off (herein, sometimes referred to as ("charged when pulled away") is suppressed. As a result, damage to the circuit in the semiconductor wafer during the separation is suppressed. The method of manufacturing a semiconductor wafer having a protective film on its inner surface will be described in detail later.

此外，本說明書中，所謂「保護膜形成用複合片的表面電阻率」，只要無特別說明，則意指上述之保護膜形成用複合片中之支撐片側的最表層的表面電阻率。另外，所謂「積層體的靜摩擦力」或「試片的靜摩擦力」，只要無特別說明，則意指利用上述方法所求出之靜摩擦力。另外，所謂「半導體晶片中的電路的破壞」，只要無特別說明，則意指上述之前述積層體的扯離時的半導體晶片中的電路的破壞。In addition, in this specification, the "surface resistivity of the composite sheet for protective film formation" means the surface resistivity of the outermost layer on the support sheet side in the above-mentioned composite sheet for protective film formation, unless otherwise specified. In addition, the so-called "static friction force of the laminated body" or "static friction force of the test piece" means the static friction force obtained by the above method unless otherwise specified. In addition, "destruction of the circuit in the semiconductor wafer" means damage to the circuit in the semiconductor wafer when the aforementioned laminated body is pulled apart unless otherwise specified.

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，而具有平常時帶電的抑制效果。 前述保護膜形成用複合片中，該保護膜形成用複合片的平常時帶電的抑制效果的程度、換言之前述表面電阻率的高低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」)的抗靜電劑的含量而進行調節。The composite sheet for forming a protective film according to this embodiment has an effect of suppressing normal charging because, for example, any layer of the composite sheet for forming a protective film contains an antistatic agent. In the composite sheet for forming a protective film, the degree of the normal charge-suppressing effect of the composite sheet for forming a protective film, in other words, the level of the surface resistivity, can be adjusted, for example, by adjusting the layer containing an antistatic agent (in this specification, there is The content of the antistatic agent (generally referred to as the "antistatic layer") is adjusted.

另外，本實施形態的保護膜形成用複合片中，該保護膜形成用複合片的扯離時帶電的抑制效果的程度、換言之前述靜摩擦力的大小可藉由調節前述保護膜形成用複合片中之前述支撐片側的最表層的構成(例如表面狀態或硬度等)而進行調節。此處，作為前述最表層的表面狀態，例如可列舉表面粗糙度等表面的凹凸度。In addition, in the protective film-forming composite sheet of this embodiment, the degree of the charge-suppressing effect when the protective film-forming composite sheet is pulled off, in other words, the magnitude of the aforementioned static friction force can be adjusted by adjusting the protective film-forming composite sheet. Adjustment is made based on the structure (for example, surface condition, hardness, etc.) of the outermost layer on the support sheet side. Here, examples of the surface state of the outermost layer include surface unevenness such as surface roughness.

[保護膜形成用複合片中之支撐片側的最表層的表面電阻率] 保護膜形成用複合片的前述表面電阻率為1.0×1011 Ω/□以下，較佳為9.5×1010 Ω/□以下，例如可為5.0×1010 Ω/□以下、6.0×109 Ω/□以下、以及1.0×109 Ω/□以下之任一者。藉由前述表面電阻率為前述上限值以下，保護膜形成用複合片的平常時帶電得到抑制。[Surface resistivity of the outermost layer on the supporting sheet side of the composite sheet for protective film formation] The surface resistivity of the composite sheet for protective film formation is 1.0×10 11 Ω/□ or less, preferably 9.5×10 10 Ω/□ below, for example, any of 5.0×10 10 Ω/□ or below, 6.0×10 9 Ω/□ or below, or 1.0×10 9 Ω/□ or below. When the surface resistivity is equal to or less than the upper limit, normal charging of the protective film-forming composite sheet is suppressed.

保護膜形成用複合片的前述表面電阻率的下限值越小越佳，並無特別限定。例如，前述表面電阻率為1.0×105 Ω/□以上之保護膜形成用複合片能夠更容易地製造。The lower limit value of the surface resistivity of the protective film-forming composite sheet is preferably as small as possible, and is not particularly limited. For example, the composite sheet for forming a protective film having a surface resistivity of 1.0×10 5 Ω/□ or more can be produced more easily.

前述保護膜形成用複合片的前述表面電阻率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，前述表面電阻率較佳為1.0×105 Ω/□至1.0×1011 Ω/□，更佳為1.0×105 Ω/□至9.5×1010 Ω/□，例如可為1.0×105 Ω/□至5.0×1010 Ω/□、1.0×105 Ω/□至6.0×109 Ω/□、以及1.0×105 Ω/□至1.0×109 Ω/□之任一者。但這些為前述表面電阻率的一例。The surface resistivity of the protective film-forming composite sheet can be appropriately adjusted to be within a range set by any combination of the above-mentioned preferred lower limit values and upper limit values. For example, in one embodiment, the surface resistivity is preferably 1.0×10 5 Ω/□ to 1.0×10 11 Ω/□, more preferably 1.0×10 5 Ω/□ to 9.5×10 10 Ω/□, for example Can be 1.0×10 5 Ω/□ to 5.0×10 10 Ω/□, 1.0×10 5 Ω/□ to 6.0×10 9 Ω/□, and 1.0×10 5 Ω/□ to 1.0×10 9 Ω/□ Any of them. However, these are examples of the aforementioned surface resistivity.

於保護膜形成用複合片中的保護膜形成用膜具有硬化性之情形時，無論為後述之熱硬化性及能量線硬化性之任一種，前文說明之保護膜形成用複合片的前述表面電阻率均可為保護膜形成用膜硬化前的表面電阻率，亦可為保護膜形成用膜硬化後的表面電阻率。When the protective film-forming film in the protective film-forming composite sheet has curability, the aforementioned surface resistance of the protective film-forming composite sheet described above regardless of the thermal curability or energy beam curability described below The surface resistivity may be the surface resistivity of the protective film-forming film before curing, or the surface resistivity of the protective film-forming film after curing.

前述保護膜形成用複合片的前述表面電阻率亦如後文實施例中所述，可將保護膜形成用複合片中之支撐片側的最表層設為測定對象，使用表面電阻率計，將施加電壓設為100V來進行測定。The surface resistivity of the protective film-forming composite sheet is also as described in the examples below. The outermost surface layer on the support sheet side of the protective film-forming composite sheet can be used as the measurement object, and a surface resistivity meter is used to measure the surface resistivity. The voltage was set to 100V for measurement.

[熱硬化性的保護膜形成用膜熱硬化後的前述表面電阻率] 於保護膜形成用膜如後述般為熱硬化性之情形時，較佳為保護膜形成用複合片中的保護膜形成用膜熱硬化後的保護膜形成用複合片的前述表面電阻率滿足上述之表面電阻率之條件(例如1.0×1011 Ω/□以下等之上限值以及／或者下限值)，該情形時的保護膜形成用複合片較佳為該保護膜形成用複合片中的保護膜形成用膜於130℃熱硬化2小時。亦即，作為此種保護膜形成用複合片的一實施形態，可列舉保護膜形成用複合片中的保護膜形成用膜於130℃熱硬化2小時後的前述表面電阻率為1.0×1011 Ω/□以下之保護膜形成用複合片。但，前述保護膜形成用複合片為滿足上述之表面電阻率之條件之保護膜形成用複合片的一例。[The aforementioned surface resistivity of the thermosetting protective film-forming film after thermosetting] When the protective film-forming film is thermosetting as described below, it is preferable to form the protective film in the protective film-forming composite sheet. In this case, the surface resistivity of the protective film-forming composite sheet after thermal curing of the film satisfies the above-mentioned surface resistivity conditions (for example, the upper limit value and/or the lower limit value of 1.0×10 11 Ω/□ or less). In the composite sheet for protective film formation, it is preferable that the film for protective film formation in the composite sheet for protective film formation is thermally cured at 130° C. for 2 hours. That is, as one embodiment of the protective film forming composite sheet, the protective film forming film in the protective film forming composite sheet has the aforementioned surface resistivity of 1.0×10 11 after thermal curing at 130° C. for 2 hours. Composite sheet for protective film formation with Ω/□ or less. However, the composite sheet for forming a protective film is an example of a composite sheet for forming a protective film that satisfies the above condition of surface resistivity.

[熱硬化性的保護膜形成用膜熱硬化前的前述表面電阻率] 於保護膜形成用膜如後述般為熱硬化性之情形時，保護膜形成用複合片中的保護膜形成用膜熱硬化前的保護膜形成用複合片的前述表面電阻率可為滿足上述之表面電阻率之條件(例如1.0×1011 Ω/□以下等之上限值以及／或者下限值)。[The aforementioned surface resistivity of the thermosetting protective film-forming film before thermosetting] When the protective film-forming film is thermosetting as described later, the protective film-forming film in the protective film-forming composite sheet is heated The surface resistivity of the protective film-forming composite sheet before curing may satisfy the above-mentioned surface resistivity conditions (for example, an upper limit value and/or a lower limit value of 1.0×10 11 Ω/□ or less).

但，本實施形態中，保護膜形成用複合片中的保護膜形成用膜熱硬化前的保護膜形成用複合片的前述表面電阻率較佳為5.0×1010 Ω/□以下，例如可為6.0×109 Ω/□以下、5.0×108 Ω/□以下、以及3.0×108 Ω/□以下之任一者。藉由熱硬化前的表面電阻率為前述上限值以下，能夠進一步抑制保護膜形成用膜熱硬化後的保護膜形成用複合片的平常時帶電。However, in this embodiment, the surface resistivity of the protective film-forming composite sheet before the protective film-forming film in the protective film-forming composite sheet is thermally cured is preferably 5.0×10 10 Ω/□ or less, and may be, for example, Any of 6.0×10 9 Ω/□ or less, 5.0×10 8 Ω/□ or less, or 3.0×10 8 Ω/□ or less. When the surface resistivity before thermal curing is equal to or less than the upper limit, normal charging of the protective film forming composite sheet after thermal curing of the protective film forming film can be further suppressed.

保護膜形成用膜熱硬化前的保護膜形成用複合片的前述表面電阻率的下限值越小越佳，並無特別限定。例如，熱硬化前的前述表面電阻率為1.0×105 Ω/□以上之保護膜形成用複合片能夠更容易地製造。The lower limit value of the surface resistivity of the protective film-forming composite sheet of the protective film-forming composite sheet before thermosetting is preferably as small as possible, and is not particularly limited. For example, a composite sheet for forming a protective film whose surface resistivity before thermal curing is 1.0×10 5 Ω/□ or more can be more easily produced.

保護膜形成用膜熱硬化前的保護膜形成用複合片的前述表面電阻率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，熱硬化前的前述表面電阻率較佳為1.0×105 Ω/□至5.0×1010 Ω/□，例如可為1.0×105 Ω/□至6.0×109 Ω/□、1.0×105 Ω/□至5.0×108 Ω/□、以及1.0×105 Ω/□至3.0×108 Ω/□之任一者。但這些為熱硬化前的前述表面電阻率的一例。The surface resistivity of the protective film-forming composite sheet before the protective film-forming film is thermally cured can be appropriately adjusted to a range set by any combination of the above-mentioned preferred lower limit values and upper limit values. For example, in one embodiment, the surface resistivity before thermal hardening is preferably 1.0×10 5 Ω/□ to 5.0×10 10 Ω/□, for example, it can be 1.0×10 5 Ω/□ to 6.0×10 9 Ω. /□, 1.0× 10 5 Ω/□ to 5.0×10 8 Ω/□, and any one of 1.0×10 5 Ω/□ to 3.0×10 8 Ω/□. However, these are examples of the aforementioned surface resistivity before thermal hardening.

於保護膜形成用膜為熱硬化性之情形時，本實施形態的保護膜形成用複合片較佳為一併滿足上述之熱硬化性的保護膜形成用膜熱硬化後的前述表面電阻率的條件、及熱硬化性的保護膜形成用膜熱硬化前的前述表面電阻率的條件。When the protective film-forming film is thermosetting, the protective film-forming composite sheet of the present embodiment preferably satisfies the aforementioned surface resistivity of the protective film-forming film after thermosetting of the protective film-forming film as well as the aforementioned thermosetting properties. conditions, and the aforementioned surface resistivity conditions of the thermosetting protective film-forming film before thermosetting.

[由保護膜形成用複合片所製作之試片的靜摩擦力] 從於70℃加熱1分鐘後的前述保護膜形成用複合片所製作之前述試片的靜摩擦力為20N以下，較佳為18N以下，例如可為16N以下、以及14N以下之任一者。藉由前述表面電阻率為1.0×1011 Ω/□以下，且前述靜摩擦力為前述上限值以下，前述積層體的扯離時帶電得到抑制，結果前述積層體的扯離時的半導體晶片中的電路的破壞得到抑制。 此外，製作試片時的「於70℃加熱1分鐘」之加熱條件與對於如下情況而言較理想的加熱條件相同：為了在使用保護膜形成用複合片時，將該片藉由該片中的保護膜形成用膜貼附於半導體晶圓時，使保護膜形成用膜軟化而使該貼附容易。[Static Friction of the Test Piece Made from the Composite Sheet for Protective Film Formation] The static friction force of the test piece made from the composite sheet for protective film formation heated at 70° C. for 1 minute is 20 N or less, preferably 18 N. below, for example, it may be any one of 16N or less and 14N or less. Since the surface resistivity is 1.0×10 11 Ω/□ or less and the static friction force is equal to or less than the upper limit, charging is suppressed during the separation of the laminated body. As a result, the semiconductor wafer during the separation of the laminated body damage to the circuit is suppressed. In addition, the heating conditions of "heating at 70°C for 1 minute" when preparing a test piece are the same as the ideal heating conditions when using a composite sheet for protective film formation and passing the sheet through the sheet. When the protective film-forming film is attached to a semiconductor wafer, the protective film-forming film is softened to facilitate the attachment.

前述試片的靜摩擦力的下限值越小越佳，並無特別限定。例如，前述靜摩擦力為1N以上之保護膜形成用複合片能夠更容易地製造。The lower limit of the static friction force of the test piece is preferably as small as possible, and is not particularly limited. For example, the composite sheet for forming a protective film having the static friction force of 1 N or more can be produced more easily.

前述試片的靜摩擦力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，前述靜摩擦力較佳為1N至20N，更佳為1N至18N，例如可為1N至16N、以及1N至14N之任一者。但這些為前述靜摩擦力的一例。The static friction force of the aforementioned test piece can be appropriately adjusted to be within a range set by any combination of the above-mentioned preferred lower limit values and upper limit values. For example, in one embodiment, the static friction force is preferably 1N to 20N, more preferably 1N to 18N, and may be any one of 1N to 16N, and 1N to 14N. However, these are examples of the aforementioned static friction force.

更具體而言，前述試片的靜摩擦力係利用以下所示之方法求出。 亦即，首先，將保護膜形成用複合片於70℃加熱1分鐘。這係用以將保護膜形成用複合片中之前述支撐片側的最表層於70℃加熱1分鐘之操作。 繼而，自該加熱後的保護膜形成用複合片，切取大小為10cm×20cm之試片。 繼而，將所獲得之試片載置於多孔台上。此時，使試片中之前述支撐片側的最表層接觸於多孔台的表面。換言之，此時，使試片中的保護膜形成用膜朝上而露出。此外，本說明書中，構成試片之各層亦以加熱前的構成保護膜形成用複合片之各層的名稱來稱呼。 繼而，如此，於載置於多孔台上之狀態的試片中的保護膜形成用膜的露出面載置重物。該重物係大小為6cm×10cm×2cm且質量為1kg，可為金屬製(亦即可為金屬重物)，亦可為非金屬製(亦即亦可為非金屬重物)。此時，使重物之大小為6cm×10cm之面接觸於保護膜形成用膜。 繼而，沿相對於試片之與前述多孔台之接觸面(換言之，試片中的保護膜形成用膜的表面)為平行的方向，使重物以10mm/min之速度移動。此時，針對重物，僅沿相對於前述接觸面平行的方向施加力，沿相對於前述接觸面垂直的方向不施加力，而使重物移動。然後，測定此時重物的即將開始移動前的荷重(亦稱為「峰值試驗力」)。該測定值相當於靜摩擦力。More specifically, the static friction force of the test piece was determined by the method shown below. That is, first, the composite sheet for protective film formation is heated at 70° C. for 1 minute. This is an operation for heating the outermost layer on the support sheet side of the protective film-forming composite sheet at 70° C. for 1 minute. Next, a test piece having a size of 10 cm×20 cm was cut out from the heated composite sheet for protective film formation. Then, the obtained test piece was placed on the porous stage. At this time, the outermost surface layer on the support sheet side of the test piece was brought into contact with the surface of the porous stage. In other words, at this time, the film for forming a protective film in the test piece was exposed upward. In addition, in this specification, each layer constituting the test piece is also called by the name of each layer constituting the composite sheet for forming a protective film before heating. Then, in this way, a heavy object was placed on the exposed surface of the protective film forming film in the test piece placed on the porous stage. The weight is 6cm×10cm×2cm in size and has a mass of 1kg. It can be made of metal (that is, it can also be a metal weight) or it can be made of non-metal (that is, it can also be a non-metal weight). At this time, the surface of the weight having a size of 6 cm×10 cm was brought into contact with the protective film forming film. Then, the weight was moved at a speed of 10 mm/min in a direction parallel to the contact surface of the test piece with the porous stage (in other words, the surface of the protective film forming film in the test piece). At this time, a force is applied to the weight only in a direction parallel to the contact surface, and no force is applied in a direction perpendicular to the contact surface, so that the weight is moved. Then, measure the load immediately before the weight starts to move (also called "peak test force"). This measured value corresponds to static friction.

圖18係以示意方式表示測定上述之試片的靜摩擦力時的試片的配置形態的一例之側視圖。此處，對如下情形進行表示：使試片1之支撐片側的最表層的露出面(表面)1b接觸於多孔台4的表面4a，使試片1之與支撐片側為相反側的最表層(亦即保護膜形成用膜)的露出面(表面)1a朝上。然後，將重物5載置於試片1的前述露出面1a，使重物5向箭頭II的方向移動，測定靜摩擦力。符號5b表示重物5之與試片1之接觸面(換言之，大小為6cm×10cm之面)。箭頭II的方向係相對於試片1的前述露出面1b平行的方向。FIG. 18 is a side view schematically showing an example of the arrangement of the test pieces when measuring the static friction force of the test pieces. Here, a case is shown in which the exposed surface (surface) 1b of the outermost layer of the test piece 1 on the support sheet side is brought into contact with the surface 4a of the porous stage 4, and the outermost layer (surface) of the test piece 1 is on the opposite side to the support sheet side. That is, the exposed surface (surface) 1a of the protective film forming film (film) faces upward. Then, the weight 5 was placed on the exposed surface 1a of the test piece 1, the weight 5 was moved in the direction of arrow II, and the static friction force was measured. Symbol 5b represents the contact surface between the weight 5 and the test piece 1 (in other words, a surface with a size of 6 cm × 10 cm). The direction of arrow II is a direction parallel to the exposed surface 1 b of the test piece 1 .

前述台中之前述積層體的固定面的構成材料通常為陶瓷或不銹鋼。另外，台的前述固定面有時具有微細的凹凸形狀而不平滑。這係吸附台可見之特徵。所謂吸附台，係指以下之台：具有於該台的厚度方向貫通之空隙部，藉由將前述固定面側的相反側予以減壓，能夠將固定對象物(此處為前述積層體)吸附而固定於前述固定面上。作為吸附台，通常使用多孔質狀(多孔結構)的台、網狀的台、設置有貫通孔之板狀的台等。吸附台由於在前述固定面亦具有前述空隙部，故而前述固定面具有微細的凹凸形狀。於使用吸附台之情形時，相較於使用固定面不具有此種凹凸形狀之台之情形，扯離固定於該固定面上之積層體時，該積層體中所產生之扯離時帶電的量變多。 另一方面，上述之多孔台的表面(前述試片的固定面)的粗糙度相對於實際使用之台的表面(前述積層體的固定面)的粗糙度為同等以上。因此，於前述試片與前述多孔台之間的前述靜摩擦力成為小如20N以下之值之情形時，實際自台扯離前述積層體時，能夠將前述積層體中所產生之扯離時帶電的量減少至能夠抑制半導體晶片中的電路的破壞之程度。The material constituting the fixing surface of the laminated body in the table is usually ceramic or stainless steel. In addition, the fixed surface of the table may have a fine uneven shape and not be smooth. This is a visible feature of the adsorption platform. The adsorption table refers to a table that has a void portion penetrating in the thickness direction of the table and is capable of adsorbing a fixed object (here, the laminated body) by depressurizing the side opposite to the fixed surface side. And fixed on the aforementioned fixed surface. As the adsorption table, a porous (porous structure) table, a mesh-shaped table, a plate-shaped table provided with through-holes, etc. are generally used. Since the suction table also has the void portion on the fixing surface, the fixing surface has a fine uneven shape. In the case of using an adsorption table, compared with the case of using a table with a fixed surface that does not have such a concave and convex shape, when the laminated body fixed on the fixed surface is pulled off, the electrical energy generated in the laminated body when pulled off is The quantity increases. On the other hand, the roughness of the surface of the porous table (the fixed surface of the test piece) is equal to or greater than the roughness of the surface of the table actually used (the fixed surface of the laminated body). Therefore, when the static friction force between the test piece and the porous table becomes a value as small as 20 N or less, when the laminated body is actually pulled away from the table, the charge generated in the laminated body during the separation can be The amount is reduced to a level that can suppress damage to the circuits in the semiconductor wafer.

本實施形態中，較佳為前述多孔台的表面(前述試片的固定面)中的凹凸差為5μm以下。原因在於，實際使用之台的表面(前述積層體的固定面)的凹凸差通常為5μm以下。 此外，本說明書中，所謂「面中的凹凸差」，意指面的凸部的頂點與相鄰該凸部之凹部的底之高低差。In this embodiment, it is preferable that the unevenness difference in the surface of the porous stage (the fixed surface of the test piece) is 5 μm or less. The reason is that the unevenness difference on the surface of the actually used table (the fixed surface of the laminated body) is usually 5 μm or less. In addition, in this specification, the "difference in unevenness in the surface" means the height difference between the apex of the convex part of the surface and the bottom of the concave part adjacent to the convex part.

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 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可相互相同亦可不同，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 piece 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 thicknesses of these multiple layers may be the same or different from each other. The combination of these multiple layers is not particularly limited as long as the effects of the present invention are not impaired.

此外，本說明書中，並不限於支撐片之情形，所謂「多層可相互相同亦可不同」，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 "multiple layers can be the same or different from each other" means "all the layers can be the same, all the layers can be different, or only some of the layers can be the same." Furthermore, The term "multiple layers are different from each other" means that "at least one of the constituent materials and thickness of each layer 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穿透之支撐片。 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 penetrate. For example, in order to optically inspect the film for protective film formation in the composite sheet for protective film formation 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, "energy lines" refer to electromagnetic waves or charged particle beams with energy quanta. Examples of energy rays include ultraviolet rays, radiation, electron beams, and the like. Ultraviolet rays can be irradiated by using, for example, 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. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like. In addition, in this specification, "energy ray hardenability" means the property of being hardened by irradiation with energy rays, and "non-energy ray hardenability" 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。Examples of the support sheet include a support sheet including a base material and an adhesive layer formed on the base material; a support sheet consisting only of the base material; 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 mentioned above, in the composite sheet for forming a protective film, any layer in the composite sheet for forming a protective film may be used as an antistatic layer. In this case, an example of a preferred supporting sheet includes a base material and a surface of the composite sheet for protective film formation formed on the side of the base material opposite to the film side for protective film formation. A support sheet with an antistatic layer (in this specification, sometimes referred to as the "back antistatic layer"); a base material with antistatic properties (in this specification, sometimes referred to as the "antistatic substrate") A supporting sheet for the antistatic layer; including a base material, and an antistatic layer formed on the surface of the base material on the side of the film for protective film formation in the composite sheet for protective film formation (in this specification, sometimes Referred to as "surface antistatic layer") support sheet. The aforementioned antistatic layers (back antistatic layer, antistatic base material, and surface antistatic layer) all contain antistatic agents.

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, preferred examples of the protective film-forming composite sheet include: a protective film-forming composite sheet in which the support sheet includes a base material and an antistatic layer formed on one or both sides of the base material; The support sheet is a composite sheet for forming a protective film having an antistatic base material (that is, an antistatic base material) as an antistatic layer. In this specification, "the antistatic layer formed on one side of the base material" means "the aforementioned backside antistatic layer or surface antistatic layer". Moreover, the so-called "antistatic layer formed on both sides of the substrate" means "the combination of the aforementioned backside antistatic layer and surface antistatic layer". Among these, a composite sheet for forming a protective film in which the support sheet is provided with the base material and an antistatic layer on the back surface, or a composite sheet for forming a protective film in which the support sheet is provided with the antistatic base material, is more preferred.

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之支撐片側的面上。但是，於使用此種保護膜形成用複合片來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，有可能因抗靜電層的介入而產生步驟異常。 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，不僅能夠抑制前述積層體的扯離時帶電，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的不良情況。 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 one 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 of the protective film forming film opposite to the support sheet side, or the protective film forming film may have antistatic properties. However, when a semiconductor device is manufactured using such a protective film-forming composite sheet while fully suppressing charge, the antistatic layer (that is, provided on the side of the protective film-forming film opposite to the support sheet side) The antistatic layer on the surface or a protective film forming film with antistatic properties) is attached to the semiconductor wafer, and the antistatic layer is incorporated into the semiconductor device. In this case, during the manufacturing process of the semiconductor device, it may be impossible to stably maintain the state in which the protective film forming film or the protective film is attached to the semiconductor wafer or the semiconductor wafer via the antistatic layer, and/or the resistivity may be lost. The state in which an electrostatic protective film-forming film or protective film is attached to a semiconductor wafer or semiconductor chip. In addition, in a 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 of the protective film forming film on the support sheet side. However, when a semiconductor device is manufactured using such a protective film-forming composite sheet, when the semiconductor wafer to which the protective film-forming film or the protective film is attached is peeled off from the antistatic layer on the supporting sheet and picked up, there may be a problem. Abnormal steps may occur due to the intervention of the antistatic layer. On the other hand, by using the back antistatic layer, the antistatic base material or the surface antistatic layer as the antistatic layer, it is possible not only to suppress charging when the laminated body is peeled off, but also to form a composite sheet for protective film formation. In many cases during the manufacturing process and/or storage process, defects caused by charging can be suppressed. From the above viewpoint, 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，以下之說明所使用之圖，為了易於理解本發明的特徵，方便起見，有時將成為主要部分之部分放大表示，各構成要素的尺寸比率等未必與實際相同。Hereinafter, an example of the overall structure of the protective film-forming composite sheet will be described for each arrangement form of the antistatic layer with reference to the drawings. In addition, in the drawings used in the following description, in order to facilitate understanding of the features of the present invention and for convenience, the main parts may be enlarged in some cases, and the dimensional ratio of each component may not be the same as the actual one.

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, a composite sheet for forming a protective film having the aforementioned backside antistatic layer as an 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 protective film-forming composite sheet 101 shown here includes a support sheet 10 and a protective film-forming film 13 formed on one side (sometimes referred to as “the first side” in this specification) 10 a of the support 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積層而構成。換言之，支撐片10的第1面10a係黏著劑層12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 base material 11, an adhesive layer 12 formed on one side 11a of the base material 11 (sometimes referred to as the "first side" in this specification), and an adhesive layer 12 formed on the other side of the base material 11 (in this specification, it is sometimes referred to as the "first side"). (sometimes referred to as the "second side") 11b on the back antistatic layer 17. That is, the support sheet 10 is formed by laminating the back antistatic layer 17, the base material 11, and the adhesive layer 12 in this order in the thickness direction of these layers. In other words, the first surface 10a of the support sheet 10 is the surface 12a of the adhesive layer 12 opposite to the base material 11 side (sometimes referred to as the "first surface" in this specification).

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 protective film-forming composite sheet 101 is composed of the back antistatic layer 17, the base material 11, the adhesive layer 12, and the protective film-forming film 13, which are sequentially laminated in the thickness direction of these layers. In addition, the composite sheet 101 for protective film formation further includes a release film 15 on the film 13 for protective film formation.

保護膜形成用複合片101中，於黏著劑層12的第1面12a的整面或大致整面係積層有保護膜形成用膜13，於保護膜形成用膜13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 laminated on the entire surface or substantially the entire surface of the first surface 12a of the adhesive layer 12, and on the side of the protective film-forming film 13 and the adhesive layer 12 The jig adhesive layer 16 is laminated on a part of the opposite surface (sometimes referred to as the "first surface" in this specification) 13a, that is, in the area near the peripheral edge. 1. Among the side 13a, the side on which the jig adhesive layer 16 is not laminated and the side of the jig adhesive layer 16 opposite to the adhesive layer 12 side (sometimes referred to as "the first side" in this specification) ) 16a has a release film 15 laminated thereon.

保護膜形成用複合片101中，亦可於剝離膜15與直接接觸該剝離膜15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 partial gap may be formed between the release film 15 and the layer directly contacting the release film 15 . For example, the state shown here is that the release film 15 is in contact with (laminated on) the side surface 16c of the jig adhesive layer 16, but there may be a case where the release film 15 is not in contact with the side surface 16c. In addition, the state shown here is that the release film 15 is in contact with (laminated on) the area near the jig adhesive layer 16 on the first surface 13 a of the protective film forming film 13 , but there is also a state where the release film is not in contact with the aforementioned area. 15 situation. In addition, there may be cases where the boundary between the first surface 16a and the side surface 16c of the jig adhesive layer 16 cannot be clearly distinguished. These are also the same in the composite sheet for protective film formation of other embodiments provided with the adhesive layer for a jig.

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 for the support sheet, one or both sides of the base material usually have an uneven surface having an uneven shape. The reason is that if the base material does not have such an uneven surface, when the base material is wound into a roll, the contact surfaces of the base materials will stick to each other and stick to each other, making use difficult. If at least one of the contact surfaces between the base materials has an uneven surface, the area of the contact surface becomes smaller, so adhesion can be suppressed. Therefore, in the protective film forming composite sheet 101, either or both surfaces of the first surface 11a and the second surface 11b of the base material 11 may have uneven surfaces. Furthermore, when only one of the first surface 11a and the second surface 11b of the base material 11 is an uneven surface, any surface may be an uneven surface. In this case, the other surface becomes a smooth surface with low unevenness. The conditions for such uneven surfaces and smooth surfaces are also the same for other composite sheets for forming protective films provided with 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 jig adhesive layer 16 is used to fix the protective film forming composite sheet 101 to a jig such as a ring frame. The adhesive layer 16 for a jig may have, for example, a single-layer structure containing an adhesive component, or may have a multi-layer structure in which a layer containing an adhesive component is laminated on both surfaces of a sheet serving as a core material.

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中之作為支撐片10側之最表層之背面抗靜電層17的表面電阻率成為1.0×1011 Ω/□以下。並且，保護膜形成用複合片101的平常時帶電得到抑制。 進而，調節了背面抗靜電層17的構成。藉此，從於70℃加熱1分鐘後的保護膜形成用複合片101所製作之前述試片的靜摩擦力成為20N以下。並且，使用保護膜形成用複合片101所獲得之前述積層體的扯離時帶電得到抑制。結果，前述積層體的扯離時的半導體晶片中的電路的破壞得到抑制。作為所調節之背面抗靜電層17的構成，例如如上文所說明，可列舉：背面抗靜電層17之與保護膜形成用膜13側為相反側的面(本說明書中，有時稱為「第2面」)17b的表面狀態、以及背面抗靜電層17的硬度等。 此外，符號17a表示背面抗靜電層17之保護膜形成用膜13側的面(本說明書中，有時稱為「第1面」)。The backside antistatic layer 17 contains an antistatic agent. Thereby, the surface resistivity of the back surface antistatic layer 17 which is the outermost layer on the support sheet 10 side of the protective film forming composite sheet 101 becomes 1.0×10 11 Ω/□ or less. Furthermore, normal charging of the protective film forming composite sheet 101 is suppressed. Furthermore, the composition of the back antistatic layer 17 was adjusted. Thereby, the static friction force of the said test piece produced from the composite sheet 101 for protective film formation after heating at 70 degreeC for 1 minute became 20N or less. Furthermore, the charging of the laminated body obtained by using the protective film forming composite sheet 101 during peeling is suppressed. As a result, damage to the circuit in the semiconductor wafer when the laminated body is pulled off is suppressed. As the structure of the adjusted back surface antistatic layer 17, for example, as described above, the surface of the back surface antistatic layer 17 that is opposite to the side of the protective film forming film 13 (sometimes referred to as "in this specification") can be used. The surface condition of the second side 17b, the hardness of the back antistatic layer 17, etc. In addition, reference numeral 17a represents the surface of the back surface antistatic layer 17 on the protective film forming film 13 side (sometimes referred to as "the first surface" in this specification).

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 protective film formation is used by attaching the inner surface of a semiconductor wafer (not shown) to the first surface 13 a of the film 13 for protective film formation with the release film 15 removed. , and then attach the first surface 16a of the jig adhesive layer 16 to a jig such as an annular 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，對於既已說明之圖所示相同的構成要素，標附與該已說明之圖之情形相同的符號，並省略該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 shown in the previously described drawings are assigned the same reference numerals as in the previously described drawings, 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，皆與圖1所示之保護膜形成用複合片101相同。The composite sheet 102 for protective film formation shown here is different except that the shape and size of the protective film forming film are different, and the jig adhesive layer is laminated on the first surface of the adhesive layer and is not laminated on the protective film forming film. Except for the first surface, it is the same as the protective film forming composite sheet 101 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 part of the first surface 12a of the adhesive layer 12, that is, in the width direction of the adhesive layer 12 (in FIG. 2 left and right direction) area on the central side. Furthermore, the jig adhesive layer 16 is laminated on the surface of the first surface 12 a of the adhesive layer 12 on which the protective film forming film 23 is not laminated, that is, in a region near the peripheral edge. In addition, the surface 23a of the protective film forming film 23 opposite to the adhesive layer 12 side (sometimes referred to as the "first surface" in this specification) and the first surface 16a of the jig adhesive layer 16 A release film 15 is laminated.

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)，例如具有圓形等平面形狀。When the protective film-forming composite sheet 102 is viewed from above, the surface area of the first surface 23 a of the protective film-forming film 23 is smaller than the first surface 12 a of the adhesive layer 12 (that is, the protective film-forming film 23 is laminated together. The area (the area obtained by the area and the area where the protective film forming film 23 is not laminated) has a planar shape such as a circle, for example.

保護膜形成用複合片102中，亦可於剝離膜15與直接接觸該剝離膜15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 partial gap may be formed between the release film 15 and the layer directly contacting the release film 15 . For example, the state where the release film 15 is in contact with (laminated on) the side surface 23c of the protective film forming film 23 is shown here. However, there may be a case where the release film 15 is not in contact with the side surface 23c. In addition, here it is shown that the release film 15 is in contact with (laminated on) the area where the protective film forming film 23 and the jig adhesive layer 16 are not laminated on the surface 12 a of the adhesive layer 12 , but the above-mentioned areas may also be present. There is no contact with the release film 15. 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 sheets for protective film formation of other embodiments which have the same shape and size of the film for protective film formation.

保護膜形成用複合片102中之作為支撐片10側之最表層之背面抗靜電層17的表面電阻率為1.0×1011 Ω/□以下，保護膜形成用複合片102的平常時帶電得到抑制。 進而，前述試片的靜摩擦力為20N以下，使用保護膜形成用複合片102所獲得之前述積層體的扯離時帶電得到抑制。結果，前述積層體的扯離時的半導體晶片中的電路的破壞得到抑制。The surface resistivity of the back antistatic layer 17 as the outermost layer on the support sheet 10 side of the protective film-forming composite sheet 102 is 1.0×10 11 Ω/□ or less, and normal charging of the protective film-forming composite sheet 102 is suppressed. . Furthermore, the static friction force of the test piece was 20 N or less, and the charging at the time of peeling off the laminated body obtained using the protective film forming composite sheet 102 was suppressed. As a result, damage to the circuit in the semiconductor wafer when the laminated body is pulled off is suppressed.

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 protective film formation is used in a state in which the release film 15 is removed, and the inner surface of a semiconductor wafer (not shown) is attached to the first surface 23 a of the film 23 for protective film formation. , and then attach the first surface 16a of the jig adhesive layer 16 to a jig such as an annular 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，皆與圖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 protective film forming composite sheet 103 shown here is the same as the protective film forming composite sheet 102 shown in FIG. 2 except that it does not include the jig adhesive layer 16 .

保護膜形成用複合片103中之作為支撐片10側之最表層之背面抗靜電層17的表面電阻率為1.0×1011 Ω/□以下，保護膜形成用複合片103的平常時帶電得到抑制。 進而，前述試片的靜摩擦力為20N以下，使用保護膜形成用複合片103所獲得之前述積層體的扯離時帶電得到抑制。結果，前述積層體的扯離時的半導體晶片中的電路的破壞得到抑制。The surface resistivity of the back antistatic layer 17 as the outermost layer on the support sheet 10 side of the protective film-forming composite sheet 103 is 1.0×10 11 Ω/□ or less, and normal charging of the protective film-forming composite sheet 103 is suppressed. . Furthermore, the static friction force of the test piece was 20 N or less, and the charging at the time of peeling off the laminated body obtained using the protective film forming composite sheet 103 was suppressed. As a result, damage to the circuit in the semiconductor wafer when the laminated body is pulled off is suppressed.

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 composite sheet 103 for protective film formation is used in a state in which the release film 15 is removed, and the inner surface of a semiconductor wafer (not shown) is attached to the first surface 23 a of the film 23 for protective film formation. , and then attach the area on the first surface 12a of the adhesive layer 12 where the protective film forming film 23 is not laminated 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，皆與圖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。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 protective film formation shown here is the same as the composite sheet 103 for protective film formation shown in FIG. 3 except that it further includes an intermediate layer 18 between the adhesive layer 12 and the film 23 for protective film formation. same. The protective film forming composite sheet 104 includes the intermediate layer 18 on the first surface 12 a of the adhesive layer 12 . The surface 18a of the intermediate layer 18 opposite to the adhesive layer 12 side (sometimes referred to as the "first surface" in this specification) is the layer on which the protective film forming film 23 is laminated.

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 protective film-forming composite sheet 104 is composed of the back antistatic layer 17, the base material 11, the adhesive layer 12, the intermediate layer 18, and the protective film-forming film 23, which are sequentially laminated in the thickness direction of these layers. In addition, the composite sheet 104 for protective film formation further includes the release film 15 on the film 23 for protective film formation.

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 protective film-forming composite sheet 104, the intermediate layer 18 is disposed between the protective film-forming film 23 and the adhesive layer 12, and is disposed at an intermediate position that is not the outermost layer. The intermediate layer 18 is not particularly limited as long as it is a layer that functions as the intermediate layer 18 at such an arrangement position. More specifically, the intermediate layer 18 may include, for example, a peelability-improving layer that has been peeled off on one side. The releasability improving layer has the function of improving the releasability of the semiconductor wafer self-supporting sheet provided with the protective film forming film or the protective film when the semiconductor wafer self-supporting sheet provided with the protective film forming film or the protective film is peeled off (peeled off) and picked up.

中間層18的第1面18a與保護膜形成用膜23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的面積及形狀為與保護膜形成用膜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 of the protective film forming film 23 on the adhesive layer 12 side (sometimes referred to as the "second surface" in this specification). When the protective film forming composite sheet 104 is viewed from above, the shape (ie, planar shape) and 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 exert 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 second surface 23b of the protective film forming film 23. For this reason, it is preferable that the first surface 18 a of the intermediate layer 18 has an area equal to or greater than that of the second surface 23 b of the protective film forming film 23 . On the other hand, the surface 18b of the intermediate layer 18 on the adhesive layer 12 side (sometimes referred to as the "second surface" in this specification) may be in contact with the entire first surface 12a of the adhesive layer 12, or may only be in contact with the first surface 12a of the adhesive layer 12. It is in contact with a part of the first surface 12a of the adhesive layer 12 . However, in order to fully exert the function of the intermediate layer 18, it is preferable that the entire first surface 12a of the adhesive layer 12 and the second surface 18b of the intermediate layer 18 be in contact. An example of a preferred intermediate layer 18 is a layer in which the area and shape of the first surface 18 a of the intermediate layer 18 are equal to the area and shape of the second surface 23 b of the protective film forming film 23 .

保護膜形成用複合片104中，亦可於剝離膜15與直接接觸該剝離膜15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 partial gap may be formed between the release film 15 and the layer directly contacting the release film 15 . For example, the state where the release film 15 is in contact with (laminated on) the side surface 18c of the intermediate layer 18 is shown here. However, there may be a case where the release film 15 is not in contact with the side surface 18c. In addition, here, it is shown that the area where the intermediate layer 18 is not laminated on the first surface 12a of the adhesive layer 12 also includes the area near the intermediate layer 18, which is in contact with (laminated on) the release film 15. However, there are also cases where The release film 15 is not 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中之作為支撐片10側之最表層之背面抗靜電層17的表面電阻率為1.0×1011 Ω/□以下，保護膜形成用複合片104的平常時帶電得到抑制。 進而，前述試片的靜摩擦力為20N以下，使用保護膜形成用複合片104所獲得之前述積層體的扯離時帶電得到抑制。結果，前述積層體的扯離時的半導體晶片中的電路的破壞得到抑制。The surface resistivity of the back antistatic layer 17 as the outermost layer on the support sheet 10 side of the protective film-forming composite sheet 104 is 1.0×10 11 Ω/□ or less, and normal charging of the protective film-forming composite sheet 104 is suppressed. . Furthermore, the static friction force of the test piece was 20 N or less, and the charging at the time of peeling off the laminated body obtained using the protective film forming composite sheet 104 was suppressed. As a result, damage to the circuit in the semiconductor wafer when the laminated body is pulled off is suppressed.

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 protective film formation is used in a state in which the release film 15 is removed, and the inner surface of a semiconductor wafer (not shown) is attached to the first surface 23 a of the film 23 for protective film formation. , and then attach the area on the first surface 12a of the adhesive layer 12 where the intermediate layer 18 is not laminated 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，皆與圖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來代替支撐片10之方面以外，皆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 protective film forming composite sheet 105 shown here is the same as the protective film forming composite sheet 101 shown in FIG. 1 except that it does not include the adhesive layer 12 . In other words, the protective film-forming composite sheet 105 is the same as the protective film-forming composite sheet 101 except that it has a support sheet 20 without the adhesive layer 12 instead of the support sheet 10 . In other words, the first surface 11a of the base material 11 is the surface 20a of the protective film forming film 13 side of the support sheet 20 (sometimes referred to as the "first surface" in this specification).

保護膜形成用複合片105中之作為支撐片20側之最表層之背面抗靜電層17的表面電阻率為1.0×1011 Ω/□以下，保護膜形成用複合片105的平常時帶電得到抑制。 進而，前述試片的靜摩擦力為20N以下，使用保護膜形成用複合片105所獲得之前述積層體的扯離時帶電得到抑制。結果，前述積層體的扯離時的半導體晶片中的電路的破壞得到抑制。The surface resistivity of the back antistatic layer 17 as the outermost layer on the support sheet 20 side of the protective film-forming composite sheet 105 is 1.0×10 11 Ω/□ or less, and normal charging of the protective film-forming composite sheet 105 is suppressed. . Furthermore, the static friction force of the test piece was 20 N or less, and the charging at the time of peeling off the laminated body obtained using the protective film forming composite sheet 105 was suppressed. As a result, damage to the circuit in the semiconductor wafer when the laminated body is pulled off is suppressed.

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 protective film formation is used in a state in which the release film 15 is removed, and the inner surface of a semiconductor wafer (not shown) is attached to the first surface 13 a of the film 13 for protective film formation. , and then attach the first surface 16a of the jig adhesive layer 16 to a jig such as an annular 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 having the aforementioned backside 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, in the protective film-forming composite sheet of this embodiment, a part of the structure of the protective film-forming composite sheet shown in FIGS. 1 to 5 may be changed or deleted within the scope that does not impair the effects of the present invention, or the structure of FIG. 1 may be changed. Further, other structures are added to the protective film forming composite sheet shown in FIG. 5 .

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 Figure 5 does not have an adhesive layer. As a composite sheet for protective film formation according to this embodiment without an adhesive layer, for example, the composite sheet for protective film formation shown in FIGS. 2 to 4 may be used, in which the lamination of the adhesive layer is omitted. piece.

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。Moreover, the composite sheet for protective film formation shown in FIG. 1, FIG. 2, and FIG. 5 is equipped with the adhesive layer for a jig. As the protective film-forming composite sheet of this embodiment having an adhesive layer for a jig, in addition to these, for example, the protective film-forming composite sheet shown in FIG. 4 may be provided on the first surface of the adhesive layer. A new composite sheet with an adhesive layer for fixtures is installed. In this case, the arrangement position of the adhesive layer for the jig on the first surface may be the same as the case of the protective film forming composite sheet 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 protective film formation shown in FIGS. 3 and 4 does not have an adhesive layer for a jig. As the composite sheet for protective film formation of this embodiment which does not have an adhesive layer for a jig, other than these, for example, the composite sheet for protective film formation shown in FIGS. 1 and 5 can also be exemplified, in which 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 protective film formation shown in FIG. 4 is provided with an intermediate layer. Examples of the composite sheet for protective film formation including the intermediate layer of this embodiment include the composite sheet for protective film formation shown in FIGS. 1 , 2 and 5 , and the film for protective film formation. A new composite sheet with an intermediate layer is installed on the second side. In this case, the arrangement of the intermediate layer on the 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 protective film formation shown in Figures 1 to 5 does not have any layer other than the back antistatic layer, the base material, the film for protective film formation, and the release film, or only has an adhesive layer, or It only has an adhesive layer and an intermediate layer. In addition to these, examples of the composite sheet for protective film formation in this embodiment include the composite sheet for protective film formation shown in FIGS. 1 to 5 , which includes a non-compliant back antistatic layer, a substrate, and an adhesive. A composite sheet of any one of the layers, the intermediate layer, the film for forming a protective film, and the 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 protective film-forming composite sheet 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 including the antistatic base material as an 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 protective film-forming composite sheet 201 shown here includes a support sheet 30 and a protective film-forming film 13 formed on one side (sometimes referred to as “the first side” in this specification) 30 a of the support 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 side (sometimes referred to as "the first side" in this specification) 11a' of the antistatic base material 11'. That is, the support sheet 30 is formed by laminating 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' represents the other side of the antistatic base material 11' (sometimes referred to as the "second side" in this specification).

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 protective film-forming composite sheet 201 is composed of the antistatic base material 11', the adhesive layer 12, and the protective film-forming film 13, which are laminated in this order in the thickness direction of these layers. In addition, the composite sheet 201 for protective film formation further includes the release film 15 on the film 13 for protective film formation.

保護膜形成用複合片201中，於黏著劑層12的第1面12a的整面或大致整面係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 laminated on the entire or substantially entire surface of the first surface 12a of the adhesive layer 12, and a part of the first surface 13a of the protective film-forming film 13 is laminated. , that is, the adhesive layer 16 for a jig is laminated in the area near the peripheral edge, and the adhesive layer 16 for a jig is not laminated on the first surface 13 a of the protective film forming film 13 and the adhesive layer for a jig is not laminated The release film 15 is laminated on the first surface 16a of 16.

保護膜形成用複合片201除具備抗靜電性基材11'來代替背面抗靜電層17及基材11之積層物之方面以外，皆與圖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 has an antistatic base material 11' instead of the laminate of the back 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中之作為支撐片30側之最表層之抗靜電性基材11'的表面電阻率成為1.0×1011 Ω/□以下。並且，保護膜形成用複合片201的平常時帶電得到抑制。 進而，調節了抗靜電性基材11'的構成。藉此，從於70℃加熱1分鐘後的保護膜形成用複合片201所製作之前述試片的靜摩擦力成為20N以下。並且，使用保護膜形成用複合片201所獲得之前述積層體的扯離時帶電得到抑制。結果，前述積層體的扯離時的半導體晶片中的電路的破壞得到抑制。作為所調節之抗靜電性基材11'的構成，例如如上文所說明，可列舉：抗靜電性基材11'的第2面11b'的表面狀態、以及抗靜電性基材11'的硬度等。The antistatic base material 11' contains an antistatic agent. Thereby, the surface resistivity of the antistatic base material 11' which is the outermost layer on the support sheet 30 side of the protective film forming composite sheet 201 becomes 1.0×10 11 Ω/□ or less. Furthermore, normal charging of the protective film forming composite sheet 201 is suppressed. Furthermore, the structure of the antistatic base material 11' was adjusted. Thereby, the static friction force of the said test piece produced from the composite sheet 201 for protective film formation after heating at 70 degreeC for 1 minute became 20N or less. Furthermore, the charging of the laminate obtained by using the protective film forming composite sheet 201 is suppressed when the laminate is peeled off. As a result, damage to the circuit in the semiconductor wafer when the laminated body is pulled off is suppressed. Examples of the adjusted composition of the antistatic base material 11' include, as described above, the surface state of the second surface 11b' of the antistatic base material 11' and the hardness of the antistatic base material 11'. wait.

作為抗靜電性基材11'，例如可列舉除了進而含有抗靜電劑之方面以外，皆與上述之基材11相同的基材。Examples of the antistatic base material 11' include base materials that are the same as the base material 11 described above, except that they further contain 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 protective film formation is used in a state in which the release film 15 is removed, and the inner surface of a semiconductor wafer (not shown) is attached to the first surface 13 a of the film 13 for protective film formation. , and then attach the first surface 16a of the jig adhesive layer 16 to a jig such as an annular 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，且治具用接著劑層是積層於黏著劑層的第1面而不是積層於保護膜形成用膜的第1面之方面以外，皆與圖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'來代替背面抗靜電層17及基材11之積層物之方面以外，皆與圖2所示之保護膜形成用複合片102相同。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 is different except that the protective film-forming film has a different shape and size, and the jig adhesive layer is laminated on the first surface of the adhesive layer instead of the protective film-forming film. Except for the first side, it is the same as the protective film forming composite sheet 201 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 has an antistatic base material 11' instead of the laminate of the back antistatic layer 17 and the base material 11. same.

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 protective film forming composite sheet 202 is formed by laminating the antistatic base material 11', the adhesive layer 12, and the protective film forming film 23 in this order in the thickness direction of these layers. In addition, the composite sheet 202 for protective film formation further includes the release film 15 on the film 23 for protective film formation.

保護膜形成用複合片202中之作為支撐片30側之最表層之抗靜電性基材11'的表面電阻率為1.0×1011 Ω/□以下，保護膜形成用複合片202的平常時帶電得到抑制。 進而，前述試片的靜摩擦力為20N以下，使用保護膜形成用複合片202所獲得之前述積層體的扯離時帶電得到抑制。結果，前述積層體的扯離時的半導體晶片中的電路的破壞得到抑制。The surface resistivity of the antistatic base material 11' as the outermost layer on the support sheet 30 side of the protective film-forming composite sheet 202 is 1.0×10 11 Ω/□ or less, and the protective film-forming composite sheet 202 is normally charged be suppressed. Furthermore, the static friction force of the test piece is 20 N or less, and the charging at the time of peeling off the laminated body obtained using the protective film forming composite sheet 202 is suppressed. As a result, damage to the circuit in the semiconductor wafer when the laminated body is pulled off is suppressed.

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 protective film formation is used in a state in which the release film 15 is removed, and the inner surface of a semiconductor wafer (not shown) is attached to the first surface 23 a of the film 23 for protective film formation. , and then attach the first surface 16a of the jig adhesive layer 16 to a jig such as an annular 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，皆與圖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'來代替背面抗靜電層17及基材11之積層物之方面以外，皆與圖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 protective film forming composite sheet 203 shown here is the same as the protective film forming composite sheet 202 shown in FIG. 7 except that it does not include the jig adhesive layer 16 . 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 has an antistatic base material 11' instead of the laminate of the back antistatic layer 17 and the base material 11. same.

保護膜形成用複合片203中之作為支撐片30側之最表層之抗靜電性基材11'的表面電阻率為1.0×1011 Ω/□以下，保護膜形成用複合片203的平常時帶電得到抑制。 進而，前述試片的靜摩擦力為20N以下，使用保護膜形成用複合片203所獲得之前述積層體的扯離時帶電得到抑制。結果，前述積層體的扯離時的半導體晶片中的電路的破壞得到抑制。The surface resistivity of the antistatic base material 11' as the outermost layer on the support sheet 30 side of the protective film-forming composite sheet 203 is 1.0×10 11 Ω/□ or less, and the protective film-forming composite sheet 203 is normally charged be suppressed. Furthermore, the static friction force of the test piece is 20 N or less, and the charging at the time of peeling off the laminated body obtained using the protective film forming composite sheet 203 is suppressed. As a result, damage to the circuit in the semiconductor wafer when the laminated body is pulled off is suppressed.

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 composite sheet 203 for protective film formation is used in a state in which the release film 15 is removed, and the inner surface of a semiconductor wafer (not shown) is attached to the first surface 23 a of the film 23 for protective film formation. , and then attach the area on the first surface 12a of the adhesive layer 12 where the protective film forming film 23 is not laminated 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，皆與圖8所示之保護膜形成用複合片203相同。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 protective film formation shown here is the same as the composite sheet 203 for protective film formation shown in FIG. 8 except that it further includes an intermediate layer 18 between the adhesive layer 12 and the film 23 for protective film formation. same.

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 protective film-forming composite sheet 204 is composed of the antistatic base material 11', the adhesive layer 12, the intermediate layer 18, and the protective film-forming film 23, which are sequentially laminated in the thickness direction of these layers. In addition, the composite sheet 204 for protective film formation further includes the release film 15 on the film 23 for protective film formation.

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'來代替背面抗靜電層17及基材11之積層物之方面以外，皆與圖4所示之保護膜形成用複合片104相同。Furthermore, in other words, the composite sheet for protective film formation 204 is the same as the composite sheet for protective film formation shown in FIG. 4 except that it has an antistatic base material 11' instead of the laminate of the back antistatic layer 17 and the base material 11. 104 is the same.

保護膜形成用複合片204中之作為支撐片30側之最表層之抗靜電性基材11'的表面電阻率為1.0×1011 Ω/□以下，保護膜形成用複合片204的平常時帶電得到抑制。 進而，前述試片的靜摩擦力為20N以下，使用保護膜形成用複合片204所獲得之前述積層體的扯離時帶電得到抑制。結果，前述積層體的扯離時的半導體晶片中的電路的破壞得到抑制。The surface resistivity of the antistatic base material 11' as the outermost layer on the support sheet 30 side of the protective film-forming composite sheet 204 is 1.0×10 11 Ω/□ or less, and the protective film-forming composite sheet 204 is normally charged be suppressed. Furthermore, the static friction force of the test piece is 20 N or less, and the charging at the time of peeling off the laminated body obtained using the protective film forming composite sheet 204 is suppressed. As a result, damage to the circuit in the semiconductor wafer when the laminated body is pulled off is suppressed.

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 composite sheet 204 for protective film formation is used in a state in which the peeling film 15 is removed, and the inner surface of a semiconductor wafer (not shown) is attached to the first surface 23 a of the film 23 for protective film formation. , and then attach the area on the first surface 12a of the adhesive layer 12 where the intermediate layer 18 is not laminated 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，皆與圖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來代替支撐片30之方面以外，皆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 protective film forming composite sheet 205 shown here is the same as the protective film forming composite sheet 201 shown in FIG. 6 except that it does not include the adhesive layer 12 . In other words, the protective film-forming composite sheet 205 is the same as the protective film-forming composite sheet 201 except that it has 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。換言之，此處抗靜電性基材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 only of the antistatic base material 11'. In other words, the first surface 11a' of the antistatic base material 11' here is the surface 40a on the protective film forming film 13 side of the support sheet 40 (sometimes referred to as the "first surface" in this specification), and It is the laminated layer of the protective film forming film 13 .

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 protective film-forming composite sheet 205 is composed of the antistatic base material 11' and the protective film-forming film 13 laminated in this order. In addition, the composite sheet 205 for protective film formation further includes the release film 15 on the film 13 for protective film formation.

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'來代替背面抗靜電層17及基材11之積層物之方面以外，皆與圖5所示之保護膜形成用複合片105相同。Furthermore, in other words, the composite sheet for protective film formation 205 is the same as the composite sheet for protective film formation shown in FIG. 5 except that it has an antistatic base material 11' instead of the laminate of the back antistatic layer 17 and the base material 11. 105 is the same.

保護膜形成用複合片205中之作為支撐片40側之最表層之抗靜電性基材11'的表面電阻率為1.0×1011 Ω/□以下，保護膜形成用複合片205的平常時帶電得到抑制。 進而，前述試片的靜摩擦力為20N以下，使用保護膜形成用複合片205所獲得之前述積層體的扯離時帶電得到抑制。結果，前述積層體的扯離時的半導體晶片中的電路的破壞得到抑制。The surface resistivity of the antistatic base material 11' as the outermost layer on the support sheet 40 side of the protective film-forming composite sheet 205 is 1.0×10 11 Ω/□ or less, and the protective film-forming composite sheet 205 is normally charged be suppressed. Furthermore, the static friction force of the test piece is 20 N or less, and the charging at the time of peeling off the laminated body obtained using the protective film forming composite sheet 205 is suppressed. As a result, damage to the circuit in the semiconductor wafer when the laminated body is pulled off is suppressed.

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 protective film formation is used in a state in which the release film 15 is removed, and the inner surface of a semiconductor wafer (not shown) is attached to the first surface 13 a of the film 13 for protective film formation. , and then attach the first surface 16a of the jig adhesive layer 16 to a jig such as an annular 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 protective film formation according to this embodiment including the antistatic base material as the antistatic layer is not limited to the composite sheet for protective film formation shown in FIGS. 6 to 10 . For example, in the protective film-forming composite sheet of this embodiment, a part of the structure of the protective film-forming composite sheet shown in FIGS. 6 to 10 may be changed or deleted within the scope that does not impair the effects of the present invention, or the structure of FIG. 6 Further, other structures are added to the protective film forming composite sheet shown in FIG. 10 .

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 Figure 10 does not have an adhesive layer. As a composite sheet for forming a protective film in this embodiment without an adhesive layer, for example, the composite sheet for forming a protective film shown in FIGS. 7 to 9 is also exemplified, and the composite sheet for forming an adhesive layer is omitted. piece.

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。Moreover, the composite sheet for protective film formation shown in FIG. 6, FIG. 7, and FIG. 10 is equipped with the adhesive layer for a jig. As the protective film-forming composite sheet of this embodiment having an adhesive layer for a jig, in addition to these, for example, the protective film-forming composite sheet shown in FIG. 9 can also be used on the first surface of the adhesive layer. A new composite sheet with an adhesive layer for fixtures is installed. In this case, the arrangement position of the adhesive layer for the jig on the first surface may be the same as the case of the protective film forming composite sheet 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 protective film formation shown in FIGS. 8 and 9 does not have an adhesive layer for a jig. As the composite sheet for protective film formation of this embodiment which does not have an adhesive layer for a jig, other than these, for example, the composite sheet for protective film formation shown in FIGS. 6 and 10 can also be exemplified, in which 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 protective film formation shown in FIG. 9 is provided with an intermediate layer. Examples of the composite sheet for protective film formation including the intermediate layer in this embodiment include the composite sheet for protective film formation shown in FIGS. 6 , 7 and 10 , and the film for protective film formation. The second side is newly equipped with a composite sheet with an intermediate layer. In this case, the arrangement of the intermediate layer on the second surface may 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，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 protective film formation shown in Figures 6 to 10 does not have any layer other than the antistatic base material, the film for protective film formation, and the release film, or only has an adhesive layer, or only has an adhesive layer. agent layer and middle layer. In addition to these, the composite sheet for forming a protective film according to this embodiment may also be exemplified by the composite sheet for forming a protective film shown in FIGS. 6 to 10 , which includes a non-antistatic base material, an adhesive layer, A composite sheet of any one of the intermediate layer, the film for forming a protective film, and the release film and the other layer.

另外，本實施形態的保護膜形成用複合片中，亦可於剝離膜與直接接觸該剝離膜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 protective film formation of this embodiment, a partial gap may be generated between the release film and the layer directly contacting the release film. In addition, in the protective film-forming composite sheet 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 including the above-mentioned 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 protective film-forming composite sheet 301 shown here includes a support sheet 50 and a protective film-forming film 13 formed on one side (sometimes referred to as “the first side” in this specification) 50 a of the support 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。 此外，符號19b表示表面抗靜電層19之基材11側的面(本說明書中，有時稱為「第2面」)。The support sheet 50 includes a base material 11, a surface antistatic layer 19 formed on the first surface 11a of the base material 11, and a surface of the surface antistatic layer 19 opposite to the base material 11 side (in this specification, Adhesive layer 12 on (sometimes referred to as "side 1") 19a. That is, the support sheet 50 is formed by laminating 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. In addition, symbol 19b represents the surface of the surface antistatic layer 19 on the base material 11 side (sometimes referred to as the "second surface" in this specification).

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 protective film-forming composite sheet 301 is composed of the base material 11, the surface antistatic layer 19, the adhesive layer 12, and the protective film-forming film 13, which are sequentially laminated in the thickness direction of these layers. In addition, the composite sheet 301 for protective film formation further includes the release film 15 on the film 13 for protective film formation.

保護膜形成用複合片301中，於黏著劑層12的第1面12a的整面或大致整面係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 laminated on the entire or substantially entire surface of the first surface 12a of the adhesive layer 12, and a part of the first surface 13a of the protective film-forming film 13 is laminated. , that is, the adhesive layer 16 for a jig is laminated in the area near the peripheral edge, and the adhesive layer 16 for a jig is not laminated on the first surface 13 a of the protective film forming film 13 and the adhesive layer for a jig is not laminated The release film 15 is laminated on the first surface 16a of 16.

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，皆與圖1所示之保護膜形成用複合片101相同。The protective film forming composite sheet 301 does not have the back antistatic layer 17 except on the second surface 11b of the base material 11, and on the first surface 11a of the base material 11, more specifically, between the base material 11 and the adhesive layer The composite sheet 101 for forming a protective film shown in FIG. 1 is the same except that the surface antistatic layer 19 is provided between the sheets 12 .

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之間而成的複合片。The surface antistatic layer 19 is the same as the backside antistatic layer 17 described above. That is, the protective film-forming composite sheet 301 can be said to have changed the arrangement position of the antistatic layer from the second surface 11 b of the base material 11 to between the base material 11 and the adhesive layer 12 in the protective film-forming composite sheet 101 . Composite piece formed from space.

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中之作為支撐片50側之最表層之基材11的表面電阻率成為1.0×1011 Ω/□以下。並且，保護膜形成用複合片301的平常時帶電得到抑制。 進而，調節了基材11的構成。藉此，從於70℃加熱1分鐘後的保護膜形成用複合片301所製作之前述試片的靜摩擦力成為20N以下。並且，使用保護膜形成用複合片301所獲得之前述積層體的扯離時帶電得到抑制。結果，前述積層體的扯離時的半導體晶片中的電路的破壞得到抑制。作為所調節之基材11的構成，例如如上文所說明，可列舉：基材11的第2面11b的表面狀態、以及基材11的硬度等。Surface antistatic layer 19 contains an antistatic agent. Thereby, the surface resistivity of the base material 11 serving as the outermost layer on the support sheet 50 side of the protective film forming composite sheet 301 becomes 1.0×10 11 Ω/□ or less. Furthermore, normal charging of the protective film forming composite sheet 301 is suppressed. Furthermore, the structure of the base material 11 was adjusted. Thereby, the static friction force of the said test piece produced from the protective film formation composite sheet 301 after heating at 70 degreeC for 1 minute became 20N or less. Furthermore, the charging of the laminate obtained by using the protective film-forming composite sheet 301 during peeling is suppressed. As a result, damage to the circuit in the semiconductor wafer when the laminated body is pulled off is suppressed. Examples of the adjusted structure of the base material 11 include, as described above, the surface state of the second surface 11 b of the base material 11 , the hardness of the base material 11 , and the like.

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 protective film formation is used in a state in which the release film 15 is removed, and the inner surface of a semiconductor wafer (not shown) is attached to the first surface 13 a of the film 13 for protective film formation. , and then attach the first surface 16a of the jig adhesive layer 16 to a jig such as an annular 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 having the aforementioned 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 according to this embodiment, the composite sheet for forming a protective film shown in FIGS. 2 to 5 may also be exemplified, in which the back surface antistatic layer is not provided and the first surface of the base material is disposed. A composite sheet composed of a surface antistatic layer (in other words, a composite sheet in which the position of the antistatic layer is changed from the second side of the base material to the first side of the base material), 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，可列舉所有經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, the composite sheet for forming a protective film having the aforementioned surface antistatic layer as an antistatic layer is not limited to the above-mentioned composite sheet for forming a protective film, and may include all the protective films having a backside antistatic layer described above. In the composite sheet for formation, the arrangement position of the antistatic layer is changed from the second surface of the base material to the first surface 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 protective film-forming composite sheet of this embodiment, the size or shape of each layer can be arbitrarily adjusted according to the purpose.

至此已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變得特別高。So far, 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 has been described. However, the present invention The composite sheet for forming a protective film according to one embodiment may also include 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. Antistatic layer. This composite sheet for protective film formation has a particularly high effect of suppressing peeling charging, and as a result, has a particularly high effect of suppressing the mixing of foreign matter between the film for protective film formation and the semiconductor wafer.

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。Among such protective film-forming composite sheets, examples of the protective film-forming composite sheet having both the backside antistatic layer and the antistatic base material as antistatic layers include those shown in FIGS. 1 to 5 . In the composite sheet for film formation, the base material 11 is replaced by a composite sheet 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 protective film-forming composite sheets are the protective film-forming composite sheets shown in FIGS. 6 to 10 , and are further provided with a back antistatic layer (for example, on the second surface 11b' of the antistatic base material 11' The composite sheet of the back antistatic layer 17) in the composite sheet for forming a protective film shown in Figures 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'來代替基材11之方面以外，皆與保護膜形成用複合片401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 protective film forming composite sheet 401 shown in FIG. 12 is a composite sheet obtained by replacing the base material 11 with the antistatic base material 11' in the protective film forming composite sheet 101 shown in FIG. 1 . The composite sheet 401 for forming a protective film is the same as the composite sheet 401 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 protective film forming composite sheet 401 is composed of the back antistatic layer 17, the antistatic base material 11' and the adhesive layer 12, which are sequentially laminated in the thickness direction of these layers. In other words, one side 60 a of the support sheet 60 (sometimes referred to as the “first side” in this specification) is the first side 12 a of the adhesive layer 12 .

背面抗靜電層17及抗靜電性基材11'含有抗靜電劑。藉此，保護膜形成用複合片401中之作為支撐片60側之最表層之背面抗靜電層17的表面電阻率成為1.0×1011 Ω/□以下。並且，保護膜形成用複合片401的平常時帶電得到抑制。 進而，調節了背面抗靜電層17的構成。藉此，從於70℃加熱1分鐘後的保護膜形成用複合片401所製作之前述試片的靜摩擦力成為20N以下。並且，使用保護膜形成用複合片401所獲得之前述積層體的扯離時帶電得到抑制。結果，前述積層體的扯離時的半導體晶片中的電路的破壞得到抑制。The back antistatic layer 17 and the antistatic base material 11' contain an antistatic agent. Thereby, the surface resistivity of the back surface antistatic layer 17 which is the outermost layer on the support sheet 60 side of the protective film forming composite sheet 401 becomes 1.0×10 11 Ω/□ or less. Furthermore, normal charging of the protective film forming composite sheet 401 is suppressed. Furthermore, the composition of the back antistatic layer 17 was adjusted. Thereby, the static friction force of the said test piece produced from the protective film formation composite sheet 401 after heating at 70 degreeC for 1 minute became 20N or less. Furthermore, the charging of the laminate obtained by using the protective film forming composite sheet 401 is suppressed when the laminate is peeled off. As a result, damage to the circuit in the semiconductor wafer when the laminated body is pulled off is suppressed.

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 protective film forming composite sheet 401 is used in the same manner as the protective film forming composite sheet 101 and the protective film forming composite sheet 201 .

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 protective film-forming composite sheet of this embodiment including both the back antistatic layer and the 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, examples of the composite sheet for forming a protective film having both the aforementioned antistatic base material and the surface antistatic layer as antistatic layers include: the composite sheet for forming a protective film shown in FIGS. 6 to 10 In the antistatic base material 11' and the layer adjacent to the first surface 11a' side of the antistatic base material 11' and the antistatic base material 11' (more specifically, the adhesive layer 12 or A composite sheet with a surface antistatic layer (for example, the surface antistatic layer 19 in the protective film forming composite sheet 301 shown in FIG. 11 ) is further provided between the protective film forming films 13).

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'來代替基材11之方面以外，皆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 protective film forming composite sheet 501 shown in FIG. 13 is an example of the protective film forming composite sheet 301 shown in FIG. 11 , in which the base material 11 is replaced with an antistatic base material. 11' composite film. The protective film forming composite sheet 501 is the same as the protective film forming composite sheet 301 except that it has an antistatic base material 11' instead of the base material 11. The support sheet 70 in the protective film forming composite sheet 501 is composed of the antistatic base material 11', the surface antistatic layer 19, and the adhesive layer 12, which are sequentially laminated in the thickness direction of these layers. In other words, one side 70 a of the support sheet 70 (sometimes referred to as the “first side” in this specification) is the first side 12 a of the adhesive layer 12 .

抗靜電性基材11'及表面抗靜電層19含有抗靜電劑。藉此，保護膜形成用複合片501中之作為支撐片70側之最表層之抗靜電性基材11'的表面電阻率成為1.0×1011 Ω/□以下。並且，保護膜形成用複合片501的平常時帶電得到抑制。 進而，調節了抗靜電性基材11'的構成。藉此，從於70℃加熱1分鐘後的保護膜形成用複合片501所製作之前述試片的靜摩擦力成為20N以下。並且，使用保護膜形成用複合片501所獲得之前述積層體的扯離時帶電得到抑制。結果，前述積層體的扯離時的半導體晶片中的電路的破壞得到抑制。The antistatic base material 11' and the surface antistatic layer 19 contain an antistatic agent. Thereby, the surface resistivity of the antistatic base material 11' which is the outermost layer on the support sheet 70 side of the protective film forming composite sheet 501 becomes 1.0×10 11 Ω/□ or less. Furthermore, normal charging of the protective film forming composite sheet 501 is suppressed. Furthermore, the structure of the antistatic base material 11' was adjusted. Thereby, the static friction force of the above-mentioned test piece produced from the composite sheet 501 for forming a protective film after heating at 70° C. for 1 minute became 20 N or less. Furthermore, the charging of the laminate obtained by using the protective film-forming composite sheet 501 during peeling is suppressed. As a result, damage to the circuit in the semiconductor wafer when the laminated body is pulled off is suppressed.

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 protective film forming composite sheet 501 is used in the same manner as the protective film forming composite sheet 301 and the protective film forming composite sheet 201 .

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 protective film-forming composite sheet of this embodiment that has both an antistatic base material and a surface antistatic layer, the size or shape of each layer can be arbitrarily adjusted 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 backside 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。Examples of a composite sheet for protective film formation that includes a back antistatic layer, an antistatic base material, and a surface antistatic layer include a composite sheet for protective film formation that includes a support sheet and one side formed on the support sheet. (i.e., the first side), and the supporting sheet is composed of a back antistatic layer, an antistatic base material, a surface antistatic layer, and an adhesive layer that are sequentially laminated in the thickness direction of these layers. , the adhesive layer is arranged toward the protective film forming film side. As such a protective film forming composite sheet, more specifically, the protective film forming composite sheet 401 shown in FIG. 12 is further provided between the antistatic base material 11' and the adhesive layer 12. A composite sheet of a surface antistatic layer (such as the surface antistatic layer 19 shown in Figure 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)來代替黏著劑層12之複合片。In addition, as a composite sheet for protective film formation that includes all of a back antistatic layer, an antistatic base material, and a surface antistatic layer, examples of the composite sheet for protective film formation include: a support sheet, and a support sheet formed on the support sheet A film for forming a protective film on one side (that is, the first side), and the aforementioned supporting sheet is composed of a back antistatic layer, an antistatic base material, and a surface antistatic layer sequentially laminated in the thickness direction of these layers. The surface antistatic layer is disposed toward the protective film forming film side. As such a protective film forming composite sheet, more specifically, a protective film forming composite sheet 401 shown in FIG. 12 is provided with a surface antistatic layer (for example, the surface antistatic layer 19 shown in FIG. 11 ) to replace the composite sheet of 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 examples of protective film-forming composite sheets having all of a back antistatic layer, an antistatic base material, and a 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僅具備選自由反面抗靜電層、抗靜電性基材及正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，平常時帶電的抑制效果高，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，就具有充分的平常時帶電的抑制效果，且此種片就能夠低價且簡便地製造之方面而言有利。As described above, a composite sheet for forming a protective film that is provided with two or more types selected from the group consisting of a back antistatic layer, an antistatic base material, and a surface antistatic layer is better than having only a back antistatic layer. , an antistatic base material and a front antistatic layer, which is only one type of composite sheet for forming a protective film. It has a high suppression effect on normal charging and is advantageous in this regard. In contrast, a protective film-forming composite sheet including only one selected from the group consisting of a back antistatic layer, an antistatic base material, and a surface antistatic layer has sufficient suppression of normal charging. effect, and such a sheet is advantageous in that it can be manufactured cheaply and easily.

至此已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。So far, the overall structure of the protective film-forming composite sheet has been described for each arrangement form of the antistatic layer, and then the support sheet has been 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 support sheet in the protective film-forming composite sheet is not particularly limited, but is preferably 70% or more, more preferably 75% or more, and particularly preferably 80% or more. When the total light transmittance of the support sheet is equal to or higher than the lower limit, the laser printability of the protective film or protective film forming film and the print visibility of the protective film are improved, and the semiconductor wafer or protective film can be inspected with higher accuracy. cracked or damaged.

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低等，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 the value, the better. Taking into account the ease of manufacturing the support sheet and the degree of freedom of the structure of the support sheet, 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 can also be measured in accordance with JIS K 7375:2008 as described in the examples below.

[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 protective film-forming composite sheet 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 equal to or less than the upper limit, the laser printability of the protective film or protective film-forming film, the print visibility of the protective film, and the suitability for inspecting 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低等，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 protective film-forming composite sheet is not particularly limited, and the lower the value, the better. Taking into account the ease of manufacturing the support sheet and the degree of freedom in the structure of the support sheet, 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 protective film-forming composite sheet affects the inspection properties of the protective film-forming film of the composite sheet. The so-called "scratch resistance of the antistatic layer" means that when the antistatic layer is rubbed by other objects, the friction surface of the antistatic layer is not easily damaged. If the scratch resistance of the antistatic layer is high, the surface of the antistatic layer will cover the entire surface and will not be easily damaged when in contact with other items. 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 deviations in the inspection results due to different inspection locations, and Able to inspect with high precision. On the other hand, if the scratch resistance of the antistatic layer is low, at least part of the surface of the antistatic layer will be easily damaged when it comes into contact with another article. Therefore, when the protective film-forming film in the protective film-forming composite sheet is inspected in the above manner, variations in inspection results occur due to differences in inspection locations, 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 using the following method. That is, first, the surface of the pressing mechanism (hereinafter referred to as "pressing surface") for applying a load to the antistatic layer is covered with flannel cloth. At this time, the pressing surface of the pressing mechanism is a square and planar 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 extremely high reliability of the evaluation results, it may be 1 μm to 4 μm. The pressing surface may be covered with one piece of flannel cloth, or 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 flannel cloths in the laminated sheet may all have the same thickness, may all have different thicknesses, or may only have the same thickness partially. When using the laminated sheet, the entire thickness of the laminated sheet, that is, the total thickness of each flannel cloth in the laminated 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, with the pressing mechanism pressed against the antistatic layer through the flannel cloth, the pressing mechanism is pressed back and forth at a straight line distance of 10cm while applying a load of 125g/cm 2 to the antistatic layer. Exercise 10 times. Thereby, the antistatic layer was rubbed while applying a load of 125g/cm 2 through the flannel cloth. At this time, the area on the surface of the antistatic layer that is rubbed by the flannel cloth is 2 cm wide and 10 cm long.

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之包含中央部之區域，亦可為相同方向之包含端部之區域。Then, the scratch resistance of the antistatic layer can be evaluated by visually observing an area of 2 cm × 2 cm in the surface of the antistatic layer rubbed with the flannel cloth to confirm whether there are scratches. For example, if there are scratches in the observation area, stripe-like scratches are observed, or the light reflectivity of the observation surface is reduced and the gloss is reduced. If no scratches are confirmed, the scratch resistance can be determined to be high. If scratches are confirmed, the scratch resistance can be determined to be low. The aforementioned area for visual observation on the surface of the antistatic layer may be any area of 2 cm in width and 10 cm in length rubbed by the flannel cloth. For example, it may be the area including the central portion in the longitudinal direction of the aforementioned area, or It can be a region including the ends 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。It is preferable that the antistatic layer in the composite sheet for forming a protective film has no scratches when the scratch resistance of the antistatic layer is evaluated by the above method. Here, the so-called antistatic layer refers to the backside antistatic layer, the antistatic base material and the surface antistatic layer described above. As a more preferable composite sheet for forming a protective film, for example, it can include such a scratch-resistant composite sheet. Antistatic layer on the back or composite sheet of 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 types of antistatic layers selected from the group consisting of a back surface antistatic layer, an antistatic base material, and a surface antistatic layer, it is preferable that at least the protective film The outermost layer of the film-forming composite sheet was evaluated for 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 base material, and when a back surface antistatic layer and a surface antistatic layer are provided together, it is preferable that at least The backside antistatic layer is evaluated for scratch resistance. For example, when the composite sheet for forming a protective film is provided with both an antistatic base material and a surface antistatic layer, it is preferable that at least the antistatic base material is the subject of evaluation of scratch resistance. For example, when the composite sheet for forming a protective film includes all of a back antistatic layer, an antistatic base material, and a surface antistatic layer, it is preferable that at least the back antistatic layer is the subject of evaluation 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 Next, base materials other than the antistatic base material will be described. In this specification, unless otherwise specified, the simple "base material" means "a base material other than an 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 base material is in the form of a sheet or film, and examples of the constituent material of the base material include various resins. Examples of the aforementioned resin include polyethylene 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- Ethylene-based copolymers such as (meth)acrylate copolymer and ethylene-norbornene copolymer (copolymers obtained using ethylene as a monomer); vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymers (using chlorine Resins obtained from ethylene as a monomer); polystyrene; polycyclic olefins; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate Polyesters such as diester, polyethylene-2,6-naphthalate, fully aromatic polyesters in which all structural units have aromatic ring groups; copolymers of two or more of the above-mentioned polyesters; poly(methyl) ) Acrylate; polyurethane; polyacrylic urethane; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; Polyester; polyetherketone, etc. Examples of the resin include polymer alloys such as mixtures of the polyester and resins other than the polyester. The polymer alloy of the polyester and the resin other than the polyester preferably contains a relatively small amount of the resin other than the polyester. Examples of the resin include cross-linked resins obtained by cross-linking one or more of the above-described resins; ionic polymerization using one or two or more of the above-described resins; Materials and other modified resins.

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，這些樹脂的組合及比率可任意選擇。The resin constituting the base material may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these resins can be selected arbitrarily.

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，這些多層可相互相同亦可不同，這些多層的組合並無特別限定。The base material may be composed of one layer (single layer), or may be composed of two or more multiple layers. When it 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.

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 base material is preferably 30 μm to 300 μm, more preferably 50 μm to 140 μm. When the thickness of the base material is within such a 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 the 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 base material is preferably a base material with high thickness accuracy, that is, a base material 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 base material with high thickness accuracy include, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymer. 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。In addition to the main constituent materials such as the aforementioned resin, the base material may also contain various known additives such as fillers, colorants, antioxidants, organic lubricants, catalysts, softeners (plasticizers), and the like.

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 base material can be transparent or opaque, and can be colored according to the purpose, and other layers can be evaporated. For example, when the film for forming a protective film has energy ray curability, it is preferable that the base material transmits energy rays. For example, in order to optically inspect the protective film-forming film in the protective film-forming 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 base material and a layer provided on the base material (such as an adhesive layer, an intermediate layer or a film for forming a protective film), the surface of the base material may also be roughened by sand blasting, 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, etc. In addition, the substrate surface 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 base material can be produced by a known method. For example, a base material containing a resin can be produced by molding a resin composition containing the aforementioned resin.

○黏著劑層 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 adhesive include acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin and other adhesives. 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 resin includes not only resins that have adhesive properties by themselves, but also resins that exhibit adhesiveness by being used in combination with other components such as additives, and resins that exhibit adhesiveness by the presence of a trigger such as heat or water. 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，這些多層可相互相同亦可不同，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 may be composed of two or more multiple layers. When it 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.

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 an adhesive layer composed of multiple layers means the total thickness of all the 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 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 adhesive layer transmits energy rays. For example, in order to optically inspect the protective film-forming film in the protective film-forming composite sheet through 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 may be formed using an energy ray curable adhesive or a non-energy ray curable 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。黏著劑組成物中的在常溫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 layer can be formed on the target site by applying the adhesive composition on the surface to be formed and drying it if necessary. The content ratio of components that do not vaporize at normal temperature in the adhesive composition is usually the same as the content ratio of the aforementioned components in the adhesive layer. In this specification, "normal temperature" means a temperature that is not particularly cold or hot, that is, an ordinary temperature. For example, a temperature of 15°C to 25°C can be cited. A more specific formation method of the adhesive layer will be described in detail later together with the formation methods of 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 coated by any known method. For example, the following methods can be used: air knife coater, blade coater, rod coater, gravure coater, roller coater. Cloth coater, roller knife coater, curtain coater, mold coater, knife coater, screen coater, Meyer rod 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 an adhesive layer is provided on a base material, for example, the adhesive composition is applied on the base material and dried if necessary, thereby laminating the adhesive layer on the base material. In addition, when an adhesive layer is provided on the base material, for example, the adhesive composition can be applied on the release film and dried if necessary, thereby forming an adhesive layer on the release film in advance, so that the adhesive layer The exposed surface is bonded to one surface of the base material, thereby laminating an adhesive layer on the base material. The release film in this case may be removed at any time point during the manufacturing process or use of the protective film-forming composite sheet.

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℃且以10秒至5分鐘之條件進行乾燥。The drying conditions of the adhesive composition are not particularly limited. When the adhesive composition contains a solvent described below, it is preferable to perform heat drying. Furthermore, the adhesive composition containing a solvent is preferably dried at 70°C to 130°C for 10 seconds to 5 minutes.

於黏著劑層為能量線硬化性之情形時，作為含有能量線硬化性黏著劑之黏著劑組成物、亦即能量線硬化性的黏著劑組成物，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, examples of the adhesive composition containing the energy ray curable adhesive, that is, the energy ray curable adhesive composition, include the following adhesive compositions: 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), which contains an energy-ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of a non-energy-ray-curable adhesive resin (I-1a) ( Hereinafter, sometimes 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 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，這些結構單元的組合及比率可任意選擇。[Adhesive resin (I-1a)] The adhesive resin (I-1a) is preferably an acrylic resin. Examples of the acrylic resin include an acrylic polymer having at least a structural unit derived from an alkyl (meth)acrylate. The acrylic resin may have only one type of structural unit, or may have two or more types. In the case of two or more types, the combination and ratio of these structural units may be selected arbitrarily.

作為前述(甲基)丙烯酸烷基酯，例如可列舉構成烷基酯之烷基的碳數為1至20之(甲基)丙烯酸烷基酯，前述烷基較佳為直鏈狀或支鏈狀。 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 (meth)acrylic acid alkyl ester include (meth)acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester has a carbon number of 1 to 20. The alkyl group is preferably linear or branched. status. More specifically, the (meth)acrylic acid alkyl esters include: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid isopropyl acrylate Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate Hexyl (meth)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, Myristyl (meth)acrylate (Myristyl (meth)acrylate), Pentadecyl (meth)acrylate, Tendecyl (meth)acrylate Hexalkyl ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), (meth)acrylate Nonadecyl acrylate, eicosanyl (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 order to improve the adhesive force of the adhesive layer, the acrylic polymer preferably has a structural unit derived from an alkyl (meth)acrylate having a carbon number of 4 or more in the alkyl group. In addition, in order to further improve the adhesive force of the adhesive layer, the carbon number of the alkyl group is preferably 4 to 12, and more preferably 4 to 8. In addition, the (meth)acrylic acid alkyl ester having a carbon number of 4 or more in the alkyl group is preferably an acrylic acid alkyl ester.

前述丙烯酸系聚合物較佳為除源自(甲基)丙烯酸烷基酯之結構單元以外，進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 acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from alkyl (meth)acrylate. Examples of the functional group-containing monomer include monomers that become a starting point for crosslinking by reacting with the crosslinking agent described below, or monomers that react with the unsaturated group-containing compound described below. The unsaturated group reaction can introduce unsaturated groups into the side chains 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, an epoxy group, and the like. That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amine group-containing monomer, an epoxy group-containing monomer, and the like.

作為前述含羥基之單體，例如可列舉：(甲基)丙烯酸羥基甲酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等(甲基)丙烯酸羥基烷基酯；乙烯醇、烯丙醇等非(甲基)丙烯酸系不飽和醇(不具有(甲基)丙烯醯基骨架之不飽和醇)等。Examples of the hydroxyl-containing monomer include: (meth)acrylic acid hydroxymethyl ester, (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester, (meth)acrylic acid 3- Hydroxyalkyl (meth)acrylate, such as hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols such as allyl alcohol (unsaturated alcohols that do not have a (meth)acrylyl 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 carboxyl group-containing monomer include: (meth)acrylic acid, crotonic acid and other ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond); 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. base) carboxyalkyl acrylate, etc.

含官能基之單體較佳為含羥基之單體、含羧基之單體，更佳為含羥基之單體。The functional group-containing monomer is preferably a hydroxyl 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，這些單體的組合及比率可任意選擇。The functional group-containing monomer constituting the acrylic polymer may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these monomers may be selected arbitrarily.

前述丙烯酸系聚合物中，源自含官能基之單體之結構單元的含量相對於結構單元的總量，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 acrylic polymer, the content of structural units derived from functional group-containing monomers is preferably 1 to 35 mass%, more preferably 2 to 32 mass%, relative to the total amount of structural units. Particularly 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 acrylic polymer may further have structural units derived from other monomers in addition to structural units derived from alkyl (meth)acrylate 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 other monomer include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide, and the like.

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

前述丙烯酸系聚合物可用作上述之非能量線硬化性的黏著性樹脂(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 acrylic polymer can be used as the non-energy ray curable adhesive resin (I-1a). On the other hand, a compound obtained by reacting a functional group in the acrylic polymer with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group (energy ray polymerizable group) can be used as the energy ray curing agent. 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，這些黏著性樹脂(I-1a)的組合及比率可任意選擇。The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be only one type, or may be two or more types. In the case of two or more types, these adhesive resins (I-1a) ) combinations and ratios can be selected arbitrarily.

黏著劑組成物(I-1)中，黏著性樹脂(I-1a)的含量相對於黏著劑組成物(I-1)的總質量之比例較佳為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 content of the adhesive resin (I-1a) relative to the total mass of the adhesive composition (I-1) is preferably 5 mass% to 99 mass%, more preferably The content is 10 mass% to 95 mass%, particularly preferably 15 mass% to 90 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 curing compound] Examples of the 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 irradiation with energy rays. Among the energy ray curable compounds, examples of monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate and other poly(meth)acrylates; (meth)acrylic acid aminomethyl 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. Since the molecular weight is relatively large and the storage elastic modulus of the adhesive layer is not easily reduced, the energy ray curable compound is preferably (meth)acrylic urethane or (meth)acrylic urethane. Ester oligomers.

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，這些能量線硬化性化合物的組合及比率可任意選擇。The adhesive composition (I-1) may contain only one type of energy ray curable compound, or may contain two or more types. In the case of two or more types, the combination and ratio of these energy ray curable compounds You can choose whatever you want.

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 adhesive composition (I-1), the content of the energy ray curable compound relative to the total mass of the adhesive composition (I-1) is preferably 1 mass % to 95 mass %, more preferably 5% by mass to 90% by mass, particularly preferably 10% by 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。[Cross-linking agent] When the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from alkyl (meth)acrylate is used as the adhesive resin (I-1a), The adhesive composition (I-1) preferably further contains a cross-linking 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。For example, the crosslinking agent reacts with the functional group to crosslink the adhesive resins (I-1a). Examples of the cross-linking agent include isocyanate-based cross-linking agents (cross-linking agents having an isocyanate group) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; Epoxy cross-linking agents (cross-linking agents with glycidyl group) such as ethylene glycol glycidyl ether; aziridines such as hexa[1-(2-methyl)-aziridinyl]triphosphonyltriazine It is a cross-linking agent (a cross-linking agent with an aziridine group); metal chelates such as aluminum chelates are a cross-linking agent (a cross-linking agent with a metal chelate structure); isocyanurate is a cross-linking agent Agent (cross-linking agent with isocyanuric acid skeleton), etc. The cross-linking agent is preferably an isocyanate-based cross-linking agent in terms of improving the cohesion of the adhesive and improving the adhesion of the adhesive layer and being easy to obtain.

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，這些交聯劑的組合及比率可任意選擇。The adhesive composition (I-1) may contain only one type of cross-linking agent or two or more types. In the case of two or more types, the combination and ratio of these cross-linking agents can be selected arbitrarily.

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

[光聚合起始劑] 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. Even if the adhesive composition (I-1) containing a photopolymerization initiator is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction proceeds sufficiently.

作為前述光聚合起始劑，例如可列舉：安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚、安息香苯甲酸、安息香苯甲酸甲酯、安息香二甲基縮酮等安息香化合物；苯乙酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等苯乙酮化合物；雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦等醯基氧化膦化合物；苄基苯基硫醚、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, benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. ; Acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one and other phenylethanes Ketone compounds; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and other hydroxyphosphine oxide compounds; benzyl Phylphenyl sulfide, tetramethylthiuram monosulfide and other sulfide compounds; 1-hydroxycyclohexyl phenyl ketone and other α-ketol compounds; azo bisisobutyronitrile and other azo compounds; titanocene and other dioxins Titanocene compounds; thioxanthone and other thioxanthone compounds; peroxide compounds; diethyl and other diketone compounds; benzil; diphenyl; benzophenone; 2,4-diethylthioxanthone ; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2-chloroanthraquinone, etc. In addition, as the photopolymerization initiator, for example, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines, etc. 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，這些光聚合起始劑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 may be two or more types. In the case of two or more types, the combination and ratio of these photopolymerization initiators may be Take your pick.

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, and more preferably 0.03 to 20 parts by mass relative to 100 parts by mass of the energy ray curable compound. 10 parts by mass, 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 ingredients within a range that does not impair the effects of the present invention. Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and adhesion-imparting agents. Well-known additives such as reaction retardants, cross-linking 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之與黏著劑層相鄰之層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 delaying agent refers to, for example, a substance used to inhibit the action of a catalyst mixed into the adhesive composition (I-1), causing the adhesive composition (I-1) during storage to undergo unintended processes. components of the cross-linking reaction. Examples of the reaction retardant include compounds that form chelate complexes by chelating the catalyst with respect to the catalyst. More specifically, examples include compounds having two or more carbonyl groups (-C(=O)) in one molecule. -) compounds. In addition, the interlayer transfer inhibitor refers to a component for inhibiting the transfer of components contained in the layer adjacent to the adhesive layer such as a protective film forming film to the adhesive layer, for example. Examples of the interlayer transfer inhibitor include the same components as the transfer inhibitor. For example, when the transfer inhibitor is the epoxy resin in the film for forming a protective film, the same type of 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，這些其他添加劑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 may be two or more types. In the case of two or more types, the combination and ratio of these other additives may be selected arbitrarily.

黏著劑組成物(I-1)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 types 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 also contain a solvent. By containing a solvent, the adhesive composition (I-1) improves its coating suitability for the surface to be coated.

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, etc.

作為前述溶劑，例如可將製造黏著性樹脂(I-1a)時所使用之溶劑不自黏著性樹脂(I-1a)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 manufacturing 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 it can be used in the adhesive composition (I-1). When producing the adhesive composition (I-1), a solvent that is the same or different from the solvent used when producing the adhesive resin (I-1a) is additionally added.

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

黏著劑組成物(I-1)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 can be adjusted appropriately.

[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 adhesive composition (I-2) contains the energy ray curable adhesive resin (I-1a) in which an unsaturated group is introduced into the side chain of the non-energy ray curable adhesive resin (I-1a). 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 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-beam 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, in addition to the aforementioned energy-beam polymerizable unsaturated group, further has the ability to bond with the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a). The base compound. Examples of the energy-beam polymerizable unsaturated group include (meth)acrylyl, vinyl (ethylidene), allyl (2-propenyl), and the like, with (meth)acrylyl being preferred. . Examples of the group that can be bonded to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amine group, and a carboxyl group or an epoxy group. hydroxyl and amine groups, etc.

作為前述含不飽和基之化合物，例如可列舉：異氰酸(甲基)丙烯醯氧基乙酯、(甲基)丙烯醯基異氰酸酯、(甲基)丙烯酸縮水甘油酯等。Examples of the unsaturated group-containing compound include (meth)acryloxyethyl isocyanate, (meth)acrylyl 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，這些黏著性樹脂(I-2a)的組合及比率可任意選擇。The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be only one type, or may be two or more types. In the case of two or more types, these adhesive resins (I-2a) ) combinations and ratios can be selected arbitrarily.

黏著劑組成物(I-2)中，黏著性樹脂(I-2a)的含量相對於黏著劑組成物(I-2)的總質量之比例較佳為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 content of the adhesive resin (I-2a) relative to the total mass of the adhesive composition (I-2) is preferably 5 mass% to 99 mass%, more preferably The content is 10 mass% to 95 mass%, particularly preferably 10 mass% to 90 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。[Cross-linking agent] For example, when the 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 cross-linking 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，這些交聯劑的組合及比率可任意選擇。Examples of the cross-linking agent in the adhesive composition (I-2) include the same compounds as the cross-linking agents in the adhesive composition (I-1). The adhesive composition (I-2) may contain only one type of cross-linking agent or two or more types. In the case of two or more types, the combination and ratio of these cross-linking agents can be selected arbitrarily.

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

[光聚合起始劑] 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，這些光聚合起始劑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 may be two or more types. In the case of two or more types, the combination and ratio of these photopolymerization initiators may be Take your pick.

黏著劑組成物(I-2)中，光聚合起始劑的含量相對於黏著性樹脂(I-2a)的含量100質量份，較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, and more preferably 0.03 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a). parts by mass to 10 parts by mass, 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，這些其他添加劑及溶劑的組合及比率可任意選擇。 黏著劑組成物(I-2)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 ingredients 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 the adhesive composition (I-1). Examples of the 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 may be two or more types. In the case of two or more types, the combination and ratio of these other additives and solvents may be arbitrary. select. The contents of other additives and solvents in the adhesive composition (I-2) are 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 content of the adhesive resin (I-2a) relative to the total mass of the adhesive composition (I-3) is preferably 5 mass% to 99 mass%, more preferably The content is 10 mass% to 95 mass%, particularly preferably 15 mass% to 90 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，這些能量線硬化性化合物的組合及比率可任意選擇。[Energy ray curing compound] Examples of the energy ray curable compound contained in the adhesive composition (I-3) include monomers and oligomers that have an energy ray polymerizable unsaturated group and can be cured by irradiation with energy rays. The same compound as the energy ray curable compound contained in the adhesive composition (I-1). The adhesive composition (I-3) may contain only one type of energy ray curable compound, or may contain two or more types. In the case of two or more types, the combination and ratio of these energy ray curable compounds You can choose whatever you want.

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 adhesive composition (I-3), the content of the energy ray curable compound is preferably 0.01 to 300 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a), 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，這些光聚合起始劑的組合及比率可任意選擇。Examples of the photopolymerization initiator in the adhesive composition (I-3) include the same compounds as the photopolymerization initiator in the adhesive composition (I-1). The photopolymerization initiator contained in the adhesive composition (I-3) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these photopolymerization initiators may be Take your pick.

黏著劑組成物(I-3)中，光聚合起始劑的含量相對於黏著性樹脂(I-2a)及前述能量線硬化性化合物的總含量100質量份，較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。In the adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total content of the adhesive resin (I-2a) and the aforementioned energy ray curable compound. Parts by mass, more preferably 0.03 to 10 parts by mass, even more preferably 0.05 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，這些其他添加劑及溶劑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 ingredients 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 the adhesive composition (I-1). Examples of the 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 may be two or more types. In the case of two or more types, the combination and ratio of these other additives and solvents may be arbitrary. select. The contents of other additives and solvents in the adhesive composition (I-3) are 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] 至此為止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 compositions other than adhesive composition (I-1) to adhesive composition (I-3)] Up to this point, the adhesive composition (I-1), the adhesive composition (I-2), and the adhesive composition (I-3) have been mainly described. However, as for the components contained in these adhesive compositions, The compound can be similarly used for all adhesive compositions other than these three types of adhesive compositions (referred to as "adhesive composition (I-1) to adhesive composition (I-3) in this specification"). 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 the non-energy ray curable adhesive composition include acrylic resin, urethane resin, rubber resin, polysiloxy resin, epoxy resin, polyvinyl ether, and polycarbonate. The adhesive composition (I-4) of non-energy ray curable adhesive resin (I-1a) such as ester resin and the like is preferably an adhesive composition containing an acrylic resin.

黏著劑組成物(I-1)至黏著劑組成物(I-3)以外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 compositions other than the adhesive composition (I-1) to the adhesive composition (I-3) preferably contain one or more cross-linking agents, and the content of the cross-linking agent can be set to The same applies to the adhesive composition (I-1) described above.

[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，這些黏著性樹脂(I-1a)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). The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be only one type, or may be two or more types. In the case of two or more types, these adhesive resins (I-1a) ) combinations and ratios can be selected arbitrarily.

黏著劑組成物(I-4)中，黏著性樹脂(I-1a)的含量相對於黏著劑組成物(I-4)的總質量之比例較佳為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 content of the adhesive resin (I-1a) relative to the total mass of the adhesive composition (I-4) is preferably 5 mass% to 99 mass%, more preferably The content is 10 mass% to 95 mass%, particularly preferably 15 mass% to 90 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。[Cross-linking agent] When the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from alkyl (meth)acrylate is used as the adhesive resin (I-1a), The adhesive composition (I-4) preferably further contains a cross-linking 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，這些交聯劑的組合及比率可任意選擇。Examples of the crosslinking agent in the adhesive composition (I-4) include the same compounds as the crosslinking agent in the adhesive composition (I-1). The adhesive composition (I-4) may contain only one type of cross-linking agent, or may contain two or more types. In the case of two or more types, the combination and ratio of these cross-linking agents can be selected arbitrarily.

前述黏著劑組成物(I-4)中，交聯劑的含量相對於黏著性樹脂(I-1a)的含量100質量份，較佳為0.01質量份至50質量份，更佳為0.1質量份至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 cross-linking agent is preferably 0.01 to 50 parts by mass, and more preferably 0.1 parts by mass relative to 100 parts by mass of the adhesive resin (I-1a). to 47 parts by mass, 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，這些其他添加劑及溶劑的組合及比率可任意選擇。 黏著劑組成物(I-4)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 ingredients 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 the adhesive composition (I-1). Examples of the 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 may be two or more types. In the case of two or more types, the combination and ratio of these other additives and solvents may be arbitrary. select. The contents of other additives and solvents in the adhesive composition (I-4) are 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之支撐片剝離，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 below 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 film for forming a protective film is cured by irradiating energy rays. If the adhesive layer and the protective film-forming film are cured at the same time, the cured product of the protective film-forming film and the adhesive layer may adhere to the interface of these layers to such an extent that they cannot be peeled off. In this case, it is difficult to peel off the cured material having the protective film-forming film on the inner surface, that is, the semiconductor wafer with the protective film (that is, the semiconductor wafer with the protective film) from the support sheet of the cured material having the adhesive layer. Normally pick up semiconductor wafers with protective films. If the adhesive layer is non-energy ray hardenable, this 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 is explained when the adhesive layer is non-energy ray hardenable. However, even if the layer of the support sheet that is in direct contact with the protective film forming film is a layer other than the adhesive layer, as long as the layer is not The hardening property of energy rays 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)等之黏著劑組成物(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℃。[Production method of adhesive composition] Adhesive composition (I-1) to adhesive composition (I-3), or adhesive composition (I-4), etc. Adhesive composition (I-1) to adhesive composition (I-3) ) are obtained by blending the above-mentioned adhesive and optional components other than the above-mentioned adhesive, etc. to form each component of the adhesive composition. The order in which each component is added is not particularly limited, and two or more components may be added at the same time. When using a solvent, it can be used by mixing the solvent with any preparation ingredient other than the solvent and diluting the preparation ingredients in advance; or by not diluting any preparation ingredient other than the solvent in advance. Solvents are mixed with these formulation ingredients. The method of mixing each component during preparation is not particularly limited, and can be appropriately selected from the following known methods: mixing by rotating a stirrer or stirring blade, mixing with a mixer, and mixing by applying ultrasonic waves. methods, etc. The temperature and time when adding and mixing each component are not particularly limited as long as the components are not deteriorated and can 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。○Antistatic layer on the back The aforementioned backside antistatic layer is in the form of a sheet or film and contains an antistatic agent. The back surface antistatic layer may contain resin in addition to the 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，這些多層可相互相同亦可不同，這些多層的組合並無特別限定。The backside antistatic layer can be composed of one layer (single layer), or it can be composed of two or more layers. When it is composed of multiple layers, these multiple layers can be the same or different from each other. The combination of these multiple 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, for example, it may also be 100 nm or less. A backside antistatic layer with a thickness of 200 nm or less can maintain sufficient antistatic capability and reduce the amount of antistatic agent used. Therefore, the cost of a composite sheet for forming a protective film having such a backside antistatic layer can be reduced. Furthermore, when the thickness of the back antistatic layer is 100 nm or less, in addition to the above-mentioned effects, the following effect can be obtained: the variation in characteristics of the protective film forming composite sheet due to the provision of the back antistatic layer can be suppressed to Minimum. Examples of the aforementioned characteristics include scalability. 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 the layers constituting the back antistatic layer. .

背面抗靜電層的厚度較佳為10nm以上，例如可為20nm以上、30nm以上、40nm以上、以及65nm以上之任一者。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 10 nm or more, and may be any one of 20 nm or more, 30 nm or more, 40 nm or more, and 65 nm or more, for example. A backside antistatic layer with a thickness 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10nm至200nm，例如可為20nm至200nm、30nm至200nm、40nm至180nm、以及65nm至100nm之任一者。但這些為背面抗靜電層的厚度的一例。The thickness of the back antistatic layer can be appropriately adjusted to a range set by any combination of the above-mentioned preferred lower limit values and upper limit values. For example, in one embodiment, the thickness of the back antistatic layer is preferably 10 nm to 200 nm, for example, it may be any one of 20 nm to 200 nm, 30 nm to 200 nm, 40 nm to 180 nm, and 65 nm to 100 nm. 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 also 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 transmits energy rays. For example, in order to optically inspect the protective film-forming film in the protective film-forming composite sheet 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)中的在常溫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 backside antistatic layer can be formed using the antistatic composition (VI-1) containing the aforementioned antistatic agent. For example, the antistatic composition (VI-1) is applied to the surface to be formed of the back antistatic layer and dried if necessary, thereby forming the back antistatic layer at the target location. The content ratio of components that do not vaporize at room temperature in the antistatic composition (VI-1) is generally the same as the content ratio of the above-mentioned components in the back antistatic layer. A more specific method of forming the back antistatic layer will be described in detail later along with methods 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, for example, the same method as in the case of the above-mentioned adhesive composition may be used.

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。When providing a back antistatic layer on a base material, for example, the antistatic composition (VI-1) is applied to the base material and dried if necessary, thereby laminating the back antistatic layer on the base material. In addition, when providing a back antistatic layer on a base material, for example, the antistatic composition (VI-1) can be applied on the release film and dried if necessary, thereby forming a back antistatic layer on the release film in advance. The electrostatic layer laminates the back antistatic layer on the base material by bonding the exposed surface of the back antistatic layer to one surface of the base material. The release film in this case may be removed at any time point during the manufacturing process or use of the protective film-forming composite sheet.

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℃且以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. When the antistatic composition (VI-1) contains the solvent described below, it is preferable to perform heat drying. Furthermore, the antistatic composition (VI-1) containing a solvent is preferably dried at 40°C to 130°C for 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 antistatic agent may be a known compound such as a conductive compound, and is not particularly limited. The 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 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-伸乙二氧基噻吩)/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)/polystyrenesulfonate (herein, sometimes 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，這些抗靜電劑的組合及比率可任意選擇。The antistatic composition (VI-1) may contain only one type of antistatic agent or two or more types. In the case of two or more types, the combination and ratio of these antistatic agents can be selected arbitrarily.

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 except the solvent (that is, the content of the antistatic agent in the back antistatic layer relative to the content of the back antistatic layer The ratio of the total mass) may be, for example, any one of 0.1% to 30% by mass and 0.5% to 15% by mass. When the ratio is equal to or higher than the lower limit, the effect of suppressing peeling charging of the protective film forming composite sheet becomes higher, and as a result, the effect of suppressing the mixing of foreign matter between the protective film forming film and the semiconductor wafer becomes higher. When the ratio is equal to or less than the 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 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。Preferable examples of the resin include resins that function as binder resins.

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。More specific examples of the resin include acrylic resins and the like, and energy ray-curable acrylic resins are preferred. Examples of the acrylic resin in the antistatic composition (VI-1) and the back surface antistatic layer include the same resin 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 surface antistatic layer include the same resin 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，這些樹脂的組合及比率可任意選擇。The above-mentioned resins contained in the antistatic composition (VI-1) and the back antistatic layer may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these resins can be selected arbitrarily. .

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 components except the solvent (that is, the content of the aforementioned resin in the back antistatic layer to the total mass of the back antistatic layer The proportion) may be, for example, any one of 30 mass% to 99.9 mass%, 35 mass% to 98 mass%, 60 mass% to 98 mass%, and 85 mass% to 98 mass%. When the ratio is equal to or higher than the lower limit, the strength of the backside antistatic layer becomes higher. When the aforementioned ratio is equal to or less than 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，這些能量線硬化性化合物及光聚合起始劑的組合及比率可任意選擇。 抗靜電組成物(VI-1)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 energy-ray-curable resin, it may also contain an energy-ray-curable compound. In addition, when the antistatic composition (VI-1) contains the energy-beam curable resin, a photopolymerization initiator may be included in order to efficiently carry out the polymerization reaction of the resin. Examples of the energy ray curable compound and photopolymerization initiator contained in the antistatic composition (VI-1) include the energy ray curable compound and photopolymerization initiator contained in the adhesive composition (I-1), respectively. The same compound as the polymerization initiator. The energy ray curing compound and the photopolymerization initiator contained in the antistatic composition (VI-1) may be only one type, or may be two or more types. In the case of two or more types, these energy ray curing compounds The combination and ratio of the chemical compound and the photopolymerization initiator can be selected arbitrarily. The contents of the energy ray curable compound and the photopolymerization initiator in the antistatic composition (VI-1) are not particularly limited, and may be appropriately selected depending on the types of the 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(乙二醇單乙醚)、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，這些其他添加劑及溶劑的組合及比率可任意選擇。 抗靜電組成物(VI-1)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 ingredients within a range that does not impair the effects of the present invention. In addition, the antistatic composition (VI-1) may also contain a solvent for the same purpose as the above-mentioned adhesive composition (I-1). Examples of the aforementioned other additives and solvents contained in the antistatic composition (VI-1) include the same additives (except for the antistatic agent) and solvents contained in the above-mentioned adhesive composition (I-1). 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 compounds, other alcohols such as ethanol; 2-methoxyethanol (ethylene glycol monomethyl ether), 2-ethoxy Alkoxy alcohols such as ethanol (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 may be two or more types. In the case of two or more types, the combination and ratio of these other additives and solvents may be arbitrary. select. The contents of other additives and solvents in the antistatic composition (VI-1) are 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。[Production method of antistatic composition (VI-1)] The antistatic composition (VI-1) can be obtained by blending each component constituting the antistatic composition (VI-1) such as the aforementioned antistatic agent and, if necessary, components other than the aforementioned antistatic agent. The antistatic composition (VI-1) can be produced by the same method as the above-mentioned adhesive composition except that the ingredients are different.

○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 antistatic base material is in the form of a sheet or film, has antistatic properties, and has the same function as the base material. In the 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 antistatic layer described above, and may be disposed in place 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，這些多層可相互相同亦可不同，這些多層的組合並無特別限定。The antistatic base material can be composed of one layer (single layer), or it can be composed of two or more layers. When it is composed of multiple layers, these multiple layers can be the same or different from each other. There is no particular combination of these multiple 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 base material may be, for example, the same as the thickness of the base material described above. When the thickness of the antistatic base material is within this range, the flexibility of the protective film forming composite sheet and the adhesion to the semiconductor wafer or the semiconductor wafer are further improved. Here, the "thickness of the antistatic base material" means the thickness of the entire antistatic base material. For example, the thickness of the antistatic base material composed of multiple layers means the entire thickness of the antistatic base material. The total thickness of the layers.

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 base material 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, it is preferable that the back surface antistatic layer transmits energy rays. For example, in order to optically inspect the protective film-forming film in the protective film-forming composite sheet 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 base material and the layer provided on the antistatic base material (such as an adhesive layer, an intermediate layer or a film for forming a protective film), the surface of the antistatic base material may also be sandblasted. , solvent treatment and other concave and convex treatments; 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, etc. In addition, the antistatic substrate surface 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)中的在常溫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 aforementioned antistatic agent and resin. The content ratio of components that do not vaporize at normal temperature in the antistatic composition (VI-2) is generally the same as the content ratio of the above-mentioned 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, the same method as that used for molding the resin composition when manufacturing the base material may be used.

[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，這些抗靜電劑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 agents contained in the back surface antistatic layer. The antistatic composition (VI-2) may contain only one type of antistatic agent, or may contain two or more types. In the case of two or more types, the combination and ratio of these antistatic agents can be selected arbitrarily.

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 content of the antistatic agent relative to the total content of the antistatic agent and resin is preferably 7.5% by mass or more, more preferably 8.5% by mass. above. When the ratio is equal to or higher than the lower limit, the effect of suppressing peeling charging of the protective film forming composite sheet becomes higher, and as a result, the effect of suppressing the mixing of foreign matter 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，就抗靜電劑的互溶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 base material, the upper limit of the ratio of the content of the antistatic agent to the total content of the antistatic agent and resin is not particularly limited. For example, in order to achieve better mutual solubility of the antistatic agent, the proportion is preferably 20 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 content ratio of the aforementioned antistatic agent can be appropriately adjusted to be within a range set by any combination of the above-mentioned preferred lower limit values and upper limit values. For example, in one embodiment, the aforementioned proportion is preferably 7.5 mass% to 20 mass%, more preferably 8.5 mass% to 20 mass%. However, these are examples of the aforementioned proportions.

[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 those contained in the base material. The above-mentioned resins contained in the antistatic composition (VI-2) and the antistatic base material may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily. .

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 resin to the total content of all components except the solvent (that is, the content of the resin in the antistatic base material to the amount of the resin in the antistatic base material) The ratio of the total mass) is preferably 30 mass% to 99.9 mass%, more preferably 35 mass% to 98 mass%, further preferably 60 mass% to 98 mass%, particularly preferably 85 mass% to 98 mass%. When the ratio is equal to or higher than the lower limit, the strength of the antistatic base material becomes higher. When the ratio is equal to or less than the upper limit, the content of the antistatic agent in 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，這些光聚合起始劑的組合及比率可任意選擇。 抗靜電組成物(VI-2)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-beam curable resin, a photopolymerization initiator may be included in order to efficiently carry out the polymerization reaction of the resin. 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 may be two or more types. In the case of two or more types, the combination and ratio of these photopolymerization initiators may be Take your pick. The content of the photopolymerization initiator in the antistatic composition (VI-2) is not particularly limited and may be appropriately selected depending on the type of the 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，這些抗靜電劑及樹脂的組合及比率可任意選擇。 抗靜電組成物(VI-2)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, contacts that do not meet any of these ingredients. Various well-known additives such as media, softeners (plasticizers), etc. Examples of the aforementioned additives contained in the antistatic composition (VI-2) include the same compounds as the other additives contained in the above-mentioned adhesive composition (I-1) (excluding the antistatic agent). In addition, in order to improve the fluidity of the antistatic composition (VI-2), a solvent may be contained. Examples of the solvent contained in the antistatic composition (VI-2) include the same compounds as the solvent contained in the above-mentioned adhesive composition (I-1). The antistatic agent and resin contained in the antistatic composition (VI-2) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these antistatic agents and resins You can choose whatever you want. The contents of the additives and the solvent in the antistatic composition (VI-2) are not particularly limited, and may be appropriately selected according to the types of the additives and solvents.

[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。[Production method of antistatic composition (VI-2)] The antistatic composition (VI-2) is obtained by blending the above-mentioned antistatic agent, the above-mentioned resin, and optionally other components other than these to form each component of the antistatic composition (VI-2). The antistatic composition (VI-2) can be produced by the same method as the above-mentioned adhesive composition except that the ingredients are different.

○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可相互相同亦可不同。○Surface antistatic layer The arrangement position of the surface antistatic layer in the protective film-forming composite sheet is different from that of the back surface antistatic layer, but the structure of the surface antistatic layer itself is the same as that of the back surface antistatic layer. For example, the surface antistatic layer can be formed using the antistatic composition (VI-1) by the same method as the formation method of the backside antistatic layer described above. Therefore, detailed description of the surface antistatic layer is omitted. When the composite sheet for forming a protective film is provided with both a surface antistatic layer and a backside antistatic layer, these surface antistatic layers and backside antistatic layers may be the same as 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 is in the form of a sheet or film. As described above, a preferable intermediate layer may include a peelability-improving layer having one side subjected to peeling treatment. Examples of the peelability improving layer include a multi-layered layer including a resin layer and a peeling treatment layer formed on the resin layer. In the composite sheet for protective film formation, the peelability improving layer is arranged so that the peeling treatment layer of the peelability improving layer faces the film side for 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 resin layer in the peelability improving layer can be produced by molding a resin composition containing resin. Furthermore, the peelability improving layer can be produced by subjecting one side of the resin layer to a peeling process.

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 resin layer can be performed, for example, by using various known peeling agents: alkyd-based, polysiloxane-based, fluorine-based, unsaturated polyester-based, polyolefin-based or wax-based release agents. In terms of heat resistance, the release agent is preferably an alkyd-based, polysiloxane-based or fluorine-based 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 that is a constituent material of the resin layer is not particularly limited as long as it is appropriately selected depending on the purpose. Examples of preferred resins include polyethylene terephthalate (PET; polyethylene terephthalate), polyethylene naphthalate (PEN; polyethylene naphthalate), and 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，這些多層可相互相同亦可不同，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, regardless of whether it is a peelability improving layer or not, may be composed of one layer (single layer), or may 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 peelability improving layer, both the resin layer and the peeling treatment layer may be composed of one layer (single layer) or may be composed 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 can be appropriately adjusted according to the type of the intermediate layer and is not particularly limited. For example, the thickness of the peelability improving 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-improving layer is equal to or greater than the aforementioned lower limit, the effect of the releasability-improving layer becomes more significant, and the effect of suppressing damage such as cutting of the releasability-improving layer becomes even higher. By having the thickness of the releasability improving layer below the above-mentioned upper limit, when a semiconductor wafer with a protective film or a semiconductor wafer with a film for forming a protective film is picked up as will be described later, the force that lifts up the wafers can be easily transmitted to the wafers, so that it is possible to Make picking up easier.

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 middle layer can be transparent or opaque, and can also be colored according to the purpose. For example, when the film for forming a protective film has energy ray curability, the intermediate layer preferably transmits energy rays. 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熱硬化而成為保護膜。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 protective film formation The film for protective film formation becomes a protective film by thermal curing. This 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 forming a protective film is soft and can be easily attached to an object to be attached.

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 "film for protective film formation" means a film before curing, and the term "protective film" means a film obtained by curing the film for protective film formation. In addition, in this specification, even after the protective film-forming film is cured, as long as the laminated structure of the supporting sheet and the cured product of the protective film-forming film (in other words, the supporting 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。於保護膜形成用膜不具有硬化性之情形時，視為於如後述般藉由保護膜形成用膜將保護膜形成用複合片貼附於半導體晶圓之階段，完成由保護膜形成用膜形成了保護膜。The film for forming a protective film may be, for example, either thermosetting or energy ray curable, may have both thermosetting properties and energy ray curable properties, or may not have both thermosetting properties and energy ray curable properties. . When the film for protective film formation does not have curability, it is considered that the film for protective film formation is completed at the stage when the composite sheet for protective film formation is attached to the semiconductor wafer via the film for protective film formation as described below. A protective film is formed.

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，這些多層可相互相同亦可不同，這些多層的組合並無特別限定。The film for forming a protective film may be composed of one layer (single layer) or two layers regardless of whether it has curability or not, and in the case of curability, whether it is thermosetting or energy ray curable. Made up of multiple layers above. 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-forming film, it is preferable whether the protective film-forming film has curability or not, and in the case of curability, whether the protective film-forming film is thermosetting or energy ray curable. It is 1 μm to 100 μm, more preferably 3 μm to 80 μm, particularly preferably 5 μm to 60 μm. When the thickness of the protective film-forming film is not less than the aforementioned lower limit, a protective film with higher protective capability can be formed. In addition, when the thickness of the protective film-forming film is equal to or less than the aforementioned upper limit, excessive thickness can be avoided. Here, the "thickness of the protective film-forming film" means the thickness of the entire protective film-forming film. For example, the thickness of the protective film-forming film composed of multiple layers means the entire thickness of the protective film-forming film. The total thickness of the layers.

[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在常溫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 protective film formation] The protective film-forming film can be formed using a protective film-forming composition containing a constituent material of the protective film-forming film. For example, the protective film-forming film can be formed by applying the protective film-forming composition to a surface to be formed of the protective film-forming film and drying it if necessary. The content ratio of components that do not vaporize at normal temperature in the protective film-forming composition is generally the same as the content ratio of the aforementioned components in the protective film-forming film. The film for forming a thermosetting protective film can be formed using a composition for forming a thermosetting protective film, and the film for forming an energy ray curable protective film can be formed using a composition for forming an energy ray curable protective film. In addition, in this specification, when the film for protective film formation has both thermal curability and energy ray curability, the contribution of thermal curing of the protective film forming film to the formation of the protective film is greater than that of energy ray curing. When contributing, the protective film-forming film is regarded as thermosetting. On the contrary, when the contribution of the energy ray curing of the protective film forming film to the formation of the protective film is greater than the contribution of thermal curing, the protective film forming film is regarded as energy ray curable.

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 protective film forming composition can be applied by the same method as the above-mentioned application of the adhesive composition.

關於保護膜形成用組成物的乾燥條件，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℃且以10秒至5分鐘之條件進行加熱乾燥。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。Regarding the drying conditions of the protective film-forming composition, regardless of whether the protective film-forming film has curability or not, and in the case of curability, regardless of whether the protective film-forming film is thermosetting or energy ray curable, No special restrictions. However, when the composition for forming a protective film contains a solvent described below, it is preferable to perform heating and drying. Furthermore, the protective film forming composition containing a solvent is preferably heated and dried at 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 thermosetting protective film formation Regarding the curing conditions when affixing a thermosetting protective film-forming film to the inner surface of a semiconductor wafer and thermally curing it to form a protective film, the protective film must have a degree of curing sufficient to fully exert the function of the protective film. , is not particularly limited and may be appropriately selected according to the type of film for forming a thermosetting protective film. For example, the heating temperature during thermal curing of the thermosetting protective film-forming film is preferably 100°C to 200°C, more preferably 110°C to 180°C, and particularly preferably 120°C to 170°C. Moreover, the heating time during the thermal hardening is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours, and even more preferably 1 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。Preferred examples of a film for forming a thermosetting protective film include a film containing a polymer component (A) and a thermosetting component (B). The polymer component (A) is a component formed by polymerization reaction as a polymerizable compound. In addition, the thermosetting component (B) is a component that can perform a curing (polymerization) reaction using heat as a trigger for 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。[Thermosetting protective film forming composition (III-1)] As a preferred composition for forming a thermosetting protective film, for example, the composition for forming a thermosetting protective film (III-1) containing the aforementioned polymer component (A) and the thermosetting component (B) can be cited. In the specification, it may be simply referred to as "composition (III-1)"), etc.

[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，這些聚合物成分(A)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 thermosetting protective film-forming 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 may be two or more types. In the case of two or more types, these polymer components The combination and ratio of ingredients (A) can be selected 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。Examples of the polymer component (A) include acrylic resin, polyester, urethane resin, acrylic urethane resin, silicone resin, rubber resin, and phenoxy resin. Thermosetting polyimide, etc., preferably 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。Examples of the acrylic resin in the polymer component (A) include known acrylic polymers. 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 over time during storage) is improved. In addition, when the weight average molecular weight of the acrylic resin is equal to or less than the aforementioned upper limit, the film for thermosetting protective film formation becomes easy to follow the uneven surface of the adherend, and can further suppress interference between the adherend and the thermosetting protective film. Voids etc. are generated between the film forming films. In addition, in this specification, the weight average molecular weight refers to the polystyrene-converted value measured by gel permeation chromatography (GPC; Gel Permeation Chromatography) 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 equal to or higher than the aforementioned lower limit, for example, the adhesive force between the cured product of the protective film-forming film and the support sheet is suppressed, and the peelability of the support sheet is moderately improved. In addition, when the Tg of the acrylic resin is equal to or less than the aforementioned upper limit, the adhesive force between the thermosetting protective film-forming 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。Examples of the acrylic resin include polymers of one or more (meth)acrylic acid esters selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N- Copolymers of two or more monomers such as hydroxymethylacrylamide, 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 same applies to terms similar to (meth)acrylic acid. For example, the concept of "(meth)acrylyl" includes both "acrylyl" and "methacrylyl", 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: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid isopropyl acrylate Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate Hexyl (meth)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, Myristyl (meth)acrylate (Myristyl (meth)acrylate), Pentadecyl (meth)acrylate, Tendecyl (meth)acrylate Hexaalkyl ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. constitute alkyl esters The alkyl group is a (meth)acrylic acid alkyl ester with a chain structure of 1 to 18 carbon atoms; (meth)acrylic acid cycloalkanes such as (meth)acrylic acid isobornyl ester, (meth)acrylic acid dicyclopentyl ester, etc. (meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate; (meth)acrylic acid cycloalkyl esters such as (meth)dicyclopentenyl acrylate; (meth)acrylic acid dicyclopentene (meth)acrylic acid cycloalkenyloxyalkyl esters such as oxyethyl ester; (meth)acrylimide; (meth)acrylic acid glycidyl ester and other glycidyl group-containing (meth)acrylates; 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; N-methylaminoethyl (meth)acrylate and other substituted amines Based on (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 a group 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-羥甲基丙烯醯胺等之中的1種或2種以上之單體進行共聚而成之丙烯酸系樹脂。For example, the acrylic resin may be one selected from the group consisting of (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, etc., in addition to the aforementioned (meth)acrylate. Acrylic resin formed 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，這些單體的組合及比率可任意選擇。The monomer constituting the acrylic resin may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these monomers can be selected arbitrarily.

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。Acrylic resins may also have functional groups capable of bonding with other compounds, such as vinyl groups, (meth)acrylyl groups, amine groups, hydroxyl groups, carboxyl groups, and isocyanate groups. The aforementioned functional group of the acrylic resin may be bonded to other compounds via the cross-linking agent (F) described below, or may be directly bonded to other compounds without the cross-linking agent (F). Since the acrylic resin is bonded to other compounds via the functional groups, the reliability of the package obtained using the protective film-forming composite sheet 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 the acrylic resin may be used alone instead of the acrylic resin (hereinafter, sometimes simply referred to as "thermoplastic resin"), or may be used in combination with the acrylic resin. By using the aforementioned thermoplastic resin, the peelability of the resin film self-supporting sheet may be improved, or the thermosetting protective film-forming film may become easier to follow the uneven surface of the adherend, thereby further suppressing the bonding between the adherend and thermosetting. There are gaps between the protective film forming films.

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 thermoplastic resin is preferably -30°C to 150°C, more preferably -20°C to 120°C.

作為前述熱塑性樹脂，例如可列舉：聚酯、聚胺基甲酸酯、苯氧基樹脂、聚丁烯、聚丁二烯、聚苯乙烯等。Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, and the like.

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 thermosetting protective film-forming film may be only one type, or may be 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 except the solvent (that is, the thermosetting protective film formation The content of the polymer component (A) in the film relative to the total mass of the film for forming a thermosetting protective film) is preferably 5 to 85 mass %, more preferably 5 to 80 mass %. , for example, any one of 5 mass% to 65 mass%, 5 mass% to 50 mass%, and 5 mass% to 35 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 a component that corresponds to 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，這些熱硬化性成分(B)的組合及比率可任意選擇。[Thermosetting ingredient (B)] The thermosetting component (B) is a component for hardening the thermosetting protective film forming film. The thermosetting component (B) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or may be two or more types. In the case of two or more types, these thermosetting components (B) The combination and ratio of the hardening component (B) 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 thermosetting resin, thermosetting polyimide, polyurethane, unsaturated polyester, polysiloxane resin, etc., and preferred ones are Epoxy 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，這些環氧系熱硬化性樹脂的組合及比率可任意選擇。(Epoxy thermosetting resin) The epoxy thermosetting resin is composed of an epoxy resin (B1) and a 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 may be two or more types. In the case of two or more types, these epoxy thermosetting resins may be used. The combination and ratio of oxygen-based thermosetting resins 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. Examples include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, and o-cresol novolak 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 and other 2-functional or higher epoxy resins 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，與丙烯酸系樹脂之互溶性較高。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 miscibility with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the resin film-attached semiconductor wafer obtained using the 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(甲基)丙烯酸的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：在構成環氧樹脂之芳香環等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。Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a part of the epoxy groups of a polyfunctional epoxy resin is converted into a group having an unsaturated hydrocarbon group. Such a compound is obtained, for example, by addition reaction of (meth)acrylic acid or a derivative of (meth)acrylic acid and an epoxy group. Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring constituting the epoxy resin. The unsaturated hydrocarbon group is a polymerizable unsaturated group. Specific examples of the unsaturated hydrocarbon group include: ethylidene (vinyl), 2-propenyl (allyl), (meth)acrylyl, (Meth)acrylamide group and the like, preferably acrylyl 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 is preferably 300 to 30,000 in terms of the curability of the thermosetting protective film-forming film and the strength and heat resistance of the cured resin film. , preferably 300 to 10,000, particularly preferably 300 to 3,000. The epoxy equivalent of the epoxy resin (B1) is preferably 100g/eq to 1000g/eq, more preferably 150g/eq to 950g/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，這些環氧樹脂(B1)的組合及比率可任意選擇。One type of epoxy resin (B1) can be used alone, or two or more types can be used in combination. When two or more types are used in combination, the combination and ratio of these epoxy resins (B1) 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 thermal hardener (B2) functions as a hardener for the epoxy resin (B1). Examples of the thermosetting agent (B2) include compounds having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, an acidic group and the like, and preferably a phenolic hydroxyl group, an alcoholic hydroxyl group, an acidic group and an anhydride group. The group is preferably a phenolic hydroxyl group or an amine group.

熱硬化劑(B2)中，作為具有酚性羥基之酚系硬化劑，例如可列舉：多官能酚樹脂、聯苯酚、酚醛清漆型酚樹脂、二環戊二烯型酚樹脂、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：雙氰胺等。Examples of the phenolic curing agent having a phenolic hydroxyl group among the thermal curing agents (B2) include polyfunctional phenol resins, biphenol, novolak-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol resins. Phenol resin, etc. Among the thermal curing agents (B2), examples of the amine-based curing agent having an amino group include dicyandiamide and the like.

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、在酚樹脂的芳香環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 thermal hardener (B2) may have an unsaturated hydrocarbon group. Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include a compound in which a part of the hydroxyl groups of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a group having an unsaturated hydrocarbon group directly bonded to the aromatic ring of the phenol resin. Compounds formed, etc. The aforementioned unsaturated hydrocarbon group in the thermal hardener (B2) is the same as the aforementioned unsaturated hydrocarbon group in the 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 a phenolic hardener is used as the thermal hardener (B2), in order to improve the peelability of the protective film self-supporting sheet, the thermal hardener (B2) is preferably a phenol with a high softening point or glass transition temperature. 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 thermal hardener (B2), the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, aralkyl type phenol resin, etc. is preferably 300 to 30,000, more preferably 300 to 30,000. The best value is 400 to 10,000, especially the best value is 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, but is preferably 60 to 500, for example.

熱硬化劑(B2)可單獨使用1種，亦可併用2種以上，於併用2種以上之情形時，這些熱硬化劑(B2)的組合及比率可任意選擇。One type of thermosetting agent (B2) can be used alone, or two or more types can be used in combination. When two or more types are used in combination, the combination and ratio of these thermosetting agents (B2) 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 to 200 parts by mass, for example, 1 to 100 parts by mass, 1 to 50 parts by mass, 1 to 25 parts by mass, and 1 to 10 parts by mass By. When the aforementioned content of the thermosetting agent (B2) is equal to or more than the aforementioned lower limit, the film for forming a thermosetting protective film becomes more easily cured. When the content of the thermosetting agent (B2) is equal to or less than the upper limit, the moisture absorption rate of the thermosetting protective film forming film is reduced, and the reliability of the package obtained using the protective film forming 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 component (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, further preferably 30 parts by mass to 150 parts by mass, for example, 35 parts by mass to 100 parts by mass, and any one from 40 parts by mass to 80 parts by mass. When the aforementioned content of the thermosetting component (B) is in such a range, for example, the adhesive force between the cured product of the protective film-forming film and the support sheet is suppressed, and the peelability 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。[Harding accelerator (C)] The composition (III-1) and the film for forming a thermosetting protective film may contain a curing accelerator (C). The hardening accelerator (C) is a component for adjusting the hardening speed of the composition (III-1). Preferred hardening accelerators (C) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethylimidazole (imidazole in which more than one hydrogen atom is replaced by a group other than a hydrogen atom); organic phosphines such as tributylphosphine, diphenylphosphine and triphenylphosphine (one or more hydrogen atoms substituted with a group other than hydrogen atom) Phosphines in which hydrogen atoms are substituted by organic groups); tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate.

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，這些硬化促進劑(C)的組合及比率可任意選擇。The curing accelerator (C) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or may be two or more types. In the case of two or more types, these curing accelerators (C) The combination and ratio of agents (C) can be selected 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抑制效果變高。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。When a hardening accelerator (C) is used, the content of the hardening accelerator (C) in the composition (III-1) and the film for forming a thermosetting protective film is 100% relative to the content of the thermosetting component (B). Parts by mass, preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass. When the aforementioned content of the hardening accelerator (C) is equal to or higher than the aforementioned lower limit, more significant effects brought about by the use of the hardening accelerator (C) can be obtained. When the content of the hardening accelerator (C) is equal to or less than the aforementioned upper limit, for example, a highly polar hardening accelerator (C) can be exposed to the substrate in the thermosetting protective film-forming film under conditions of high temperature and high humidity. Then the interface side moves and the segregation suppressing effect becomes higher. As a result, the reliability of the protective film-attached semiconductor wafer obtained using the protective film forming composite sheet 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，使該熱膨脹係數最適於保護膜之形成對象物，藉此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). Since the thermosetting protective film-forming film contains the filler (D), the thermal expansion coefficient of the protective film obtained by curing the thermosetting protective film-forming film can be easily adjusted so that the thermal expansion coefficient is optimal for the object to be formed of the protective film. The reliability of the protective film-attached semiconductor wafer obtained by using the composite sheet for forming a protective film is thereby further improved. In addition, when the thermosetting protective film-forming film contains the filler (D), the moisture absorption rate of the protective film can also be reduced or the heat dissipation property 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 filler (D) may be either an organic filler or an inorganic filler, and an inorganic filler is preferred. Preferable inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium dioxide, titanium dioxide, silicon carbide, boron nitride, etc.; these inorganic fillers are formed into spherical shapes. Beads; surface modifications of these inorganic filler materials; single crystal fibers of these inorganic filler materials; glass fibers, etc. Among these, the inorganic filler material is preferably silica or alumina, and 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，這些填充材料(D)的組合及比率可任意選擇。The filler material (D) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or may be two or more types. In the case of two or more types, these filler materials (D) The combination and ratio of D) can be selected 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 the composition (III-1), the ratio of the content of the filler (D) to the total content of all components except the solvent (that is, the ratio of the content of the filler (D) in the film for forming a thermosetting protective film to The ratio to the total mass of the film for forming the thermosetting protective film) is preferably 5% to 80% by mass, more preferably 10% to 70% by mass, for example, 20% to 65% by mass, 30% by mass % to 65 mass%, and any one of 40 mass% to 65 mass%. By keeping the aforementioned ratio within this range, it becomes easier to adjust the thermal expansion coefficient of the protective film.

[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 thermosetting protective film-forming film to the adherend can be improved. In addition, by using the coupling agent (E), the cured product of the thermosetting protective film-forming film has improved water resistance without impairing the heat 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), the thermosetting component (B), etc., and is more preferably a silane coupling agent. Preferred silane coupling agents include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyl Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethyl Oxysilane, 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, vinyltriethyloxysilane, imidazolesilane, 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，這些偶合劑(E)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 may be two or more types. In the case of two or more types, these coupling agents (E) The combination and ratio of E) can be selected 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，能夠更顯著地獲得由使用偶合劑(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 a coupling agent (E) is used, the content of the coupling agent (E) in the composition (III-1) and the thermosetting protective film-forming film is relative to the polymer component (A) and the thermosetting component ( The total content of B) is preferably 0.03 to 20 parts by mass per 100 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass. When the content of the coupling agent (E) is equal to or higher than the 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. The effect brought about by using the coupling agent (E) can be obtained more significantly. In addition, when the aforementioned content of the coupling agent (E) is equal to or less 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)] When using the above-mentioned acrylic resin as the polymer component (A) and having functional groups capable of bonding to other compounds, such as vinyl groups, (meth)acrylyl groups, amine groups, hydroxyl groups, carboxyl groups, isocyanate groups, etc. , the composition (III-1) and the film for forming a thermosetting protective film may also contain a crosslinking agent (F). The cross-linking agent (F) is a component for cross-linking the aforementioned functional group in the polymer component (A) by bonding it to other compounds. By cross-linking in this way, the film for forming a thermosetting protective film can be adjusted. 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。Examples of the cross-linking agent (F) include organic polyisocyanate compounds, organic polyimine compounds, metal chelate-based cross-linking agents (cross-linking agents having a metal chelate structure), and aziridine-based cross-linking agents. Agent (cross-linking agent with aziridine group), etc.

作為前述有機多元異氰酸酯化合物，例如可列舉：芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物及脂環族多元異氰酸酯化合物(以下，有時將這些化合物統一簡稱為「芳香族多元異氰酸酯化合物等」)；前述芳香族多元異氰酸酯化合物等的三聚物、異氰脲酸酯體及加合物；使前述芳香族多元異氰酸酯化合物等與多元醇化合物反應而獲得之末端異氰酸酯胺基甲酸酯預聚物等。前述「加合物」意指前述芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物或脂環族多元異氰酸酯化合物，與乙二醇、丙二醇、新戊二醇、三羥甲基丙烷或蓖麻油等含低分子活性氫化合物之反應物。作為前述加合物的示例，可列舉如後述之三羥甲基丙烷之苯二甲基二異氰酸酯加成物等。另外，所謂「末端異氰酸酯胺基甲酸酯預聚物」，意指具有胺基甲酸酯鍵、並且於分子的末端部具有異氰酸酯基之預聚物。Examples of the organic polyisocyanate compound include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyisocyanate compounds, etc."); Trimers, isocyanurates and adducts of the aforementioned aromatic polyisocyanate compounds, etc.; terminal isocyanate urethane prepolymers, etc. obtained by reacting the aforementioned aromatic polyisocyanate compounds, etc. with polyol compounds. . The aforementioned "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, etc. Reactant of low molecular weight active hydrogen compounds. Examples of the adduct include a xylylene diisocyanate adduct of trimethylolpropane, which will be described later. In addition, the "terminated isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the terminal portion of the molecule.

作為前述有機多元異氰酸酯化合物，更具體而言，例如可列舉：2,4-甲苯二異氰酸酯；2,6-甲苯二異氰酸酯；1,3-苯二甲基二異氰酸酯；1,4-二甲苯二異氰酸酯；二苯基甲烷-4,4'-二異氰酸酯；二苯基甲烷-2,4'-二異氰酸酯；3-甲基二苯基甲烷二異氰酸酯；六亞甲基二異氰酸酯；異佛爾酮二異氰酸酯；二環己基甲烷-4,4'-二異氰酸酯；二環己基甲烷-2,4'-二異氰酸酯；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。More specific examples of the organic polyisocyanate compound include: 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylylenedimethyldiisocyanate; 1,4-xylylenediisocyanate Isocyanates; 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 added to all or part of the hydroxyl groups of polyols such as trimethylolpropane, Any one or two or more compounds of hexamethylene diisocyanate and xylylene diisocyanate; lysine diisocyanate, etc.

作為前述有機多元亞胺化合物，例如可列舉：N,N'-二苯基甲烷-4,4'-雙(1-氮丙啶甲醯胺)、三羥甲基丙烷-三-β-氮丙啶基丙酸酯、四羥甲基甲烷-三-β-氮丙啶基丙酸酯、N,N'-甲苯-2,4-雙(1-氮丙啶甲醯胺)三伸乙基三聚氰胺等。Examples of the organic polyimine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinemethane), trimethylolpropane-tris-β-nitrogen Propiridylpropionate, tetramethylolmethane-tris-β-aziridinylpropionate, N,N'-toluene-2,4-bis(1-aziridinylcarboxamide)triethylene Based on melamine, etc.

於使用有機多元異氰酸酯化合物作為交聯劑(F)之情形時，作為聚合物成分(A)，較佳為使用含羥基之聚合物。於交聯劑(F)具有異氰酸酯基，聚合物成分(A)具有羥基之情形時，藉由交聯劑(F)與聚合物成分(A)之反應，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 cross-linking agent (F), it is preferred to use a hydroxyl-containing polymer as the polymer component (A). When the cross-linking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the cross-linked structure can be easily introduced through the reaction between the cross-linking agent (F) and the polymer component (A). Films for forming thermosetting protective films.

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，這些交聯劑(F)的組合及比率可任意選擇。The cross-linking agent (F) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or may be two or more types. In the case of two or more types, these cross-linking agents (F) The combination and ratio of agents (F) can be selected 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質量份至10質量份，尤佳為0.5質量份至5質量份。藉由交聯劑(F)的前述含量為前述下限值以上，能夠更顯著地獲得由使用交聯劑(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)。When a cross-linking agent (F) is used, the content of the cross-linking agent (F) in the composition (III-1) is preferably 0.01 to 0.01 parts by mass relative to 100 parts by mass of the polymer component (A). 20 parts by mass, more preferably 0.1 to 10 parts by mass, particularly preferably 0.5 to 5 parts by mass. When the content of the cross-linking agent (F) is equal to or higher than the lower limit, the effect of using the cross-linking agent (F) can be more significantly obtained. In addition, when the content of the cross-linking agent (F) is equal to or less than the upper limit, use of an excessive amount of the cross-linking agent (F) can be suppressed.

[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). Since the film for forming a thermosetting protective film contains an energy ray curable resin (G), its characteristics can be changed by irradiating energy rays.

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。Energy ray curable resin (G) is obtained by polymerizing (hardening) an energy ray curable compound. Examples of the energy ray curable compound include compounds having at least one polymerizable double bond in the molecule, and preferably are acrylate compounds having a (meth)acrylyl group.

作為前述丙烯酸酯系化合物，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯等含鏈狀脂肪族骨架之(甲基)丙烯酸酯；二(甲基)丙烯酸二環戊酯等含環狀脂肪族骨架之(甲基)丙烯酸酯；聚乙二醇二(甲基)丙烯酸酯等聚伸烷基二醇(甲基)丙烯酸酯；寡酯(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲酸酯低聚物；環氧改質(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 compound include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate. hydroxy) acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di (Meth)acrylates and other (meth)acrylates containing a chain aliphatic skeleton; (meth)acrylates containing a cyclic aliphatic skeleton such as dicyclopentyl di(meth)acrylate; polyethylene glycol Polyalkylene glycol (meth)acrylate such as di(meth)acrylate; oligoester (meth)acrylate; (meth)acrylic urethane oligomer; epoxy modified (meth)acrylate (meth)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 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，這些能量線硬化性化合物的組合及比率可任意選擇。The energy ray curable compound used for polymerization may be only one type or two or more types. In the case of two or more types, the combination and ratio of these energy ray curable compounds can be selected arbitrarily.

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，這些能量線硬化性樹脂(G)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 may be two or more types. In the case of two or more types, these The combination and ratio of energy ray curable resin (G) can be selected arbitrarily.

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%。When an energy ray curable resin (G) is used, the ratio of the content of the energy ray curable resin (G) in the composition (III-1) to the total mass of the composition (III-1) is preferably 1 mass% to 95 mass%, more preferably 5 mass% to 90 mass%, particularly preferably 10 mass% to 85 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 the energy ray curable resin (G), in order to efficiently carry out the polymerization reaction of the energy ray curable resin (G), they 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、安息香乙醚、安息香異丙醚、安息香異丁醚、安息香苯甲酸、安息香苯甲酸甲酯、安息香二甲基縮酮等安息香化合物；苯乙酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等苯乙酮化合物；雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦等醯基氧化膦化合物；苄基苯基硫醚、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, benzoic acid, and benzoin benzoic acid methyl ether. Benzoin compounds such as ester, benzoin dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-di Acetophenone compounds such as phenylethane-1-one; bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 2,4,6-trimethylbenzyldiphenyl Phosphine oxide compounds such as phosphine oxide; thioether compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketool compounds such as 1-hydroxycyclohexylphenyl ketone; azobisisobutyl Azo compounds such as nitriles; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diethyl; benzil; diphenyl; benzophenone ;2,4-diethylthioxanthone;1,2-diphenylmethane;2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone;2- Chloranthraquinone, etc. Examples of the photopolymerization initiator include quinone compounds such as 1-chloroanthraquinone and 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，這些光聚合起始劑(H)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 may be two or more types. In the case of two or more types, these The combination and ratio of the photopolymerization initiator (H) can be selected arbitrarily.

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。When a photopolymerization initiator (H) is used, the content of the photopolymerization initiator (H) in the composition (III-1) is smaller than 100 parts by mass of the energy ray curable resin (G). Preferably it is 0.1 part by mass to 20 parts by mass, more preferably 1 part by mass to 10 parts by mass, still more preferably 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。[Color(I)] The composition (III-1) and the film for forming a thermosetting protective film may contain the colorant (I). Examples of the colorant (I) include known colorants such as inorganic pigments, organic pigments, and organic dyes.

作為前述有機系顏料及有機系染料，例如可列舉：銨系色素、花青系色素、部花青系色素、克酮鎓(croconium)系色素、方酸鎓(squalilium)系色素、薁鎓系色素、聚次甲基系色素、萘醌系色素、吡喃鎓系色素、酞菁系色素、萘酞菁系色素、萘內醯胺系色素、偶氮系色素、縮合偶氮系色素、靛藍系色素、紫環酮(perinone)系色素、苝系色素、二噁嗪系色素、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 organic pigments and organic dyes include ammonium pigments, cyanine pigments, merocyanine pigments, croconium pigments, squalilium pigments, and azulium pigments. Pigments, polymethine pigments, naphthoquinone pigments, pyranium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphtholactam pigments, azo pigments, condensed azo pigments, indigo Pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, Thioindigo-based pigments, metal complex-based pigments (metal complex dyes), dithiol metal complex-based pigments, indoxyl-based pigments, triallylmethane-based pigments, anthraquinone-based pigments, naphthols pigments, methine azo pigments, benzimidazolone pigments, picanthrone pigments and 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 inorganic pigment include carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, and ITO (Indium Tin Oxide; indium tin oxide) pigments, ATO (Antimony Tin Oxide; antimony tin oxide) 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，這些著色劑(I)的組合及比率可任意選擇。The colorant (I) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or may be two or more types. In the case of two or more types, these coloring agents (I) The combination and ratio of I) can be selected 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看見。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，能夠更顯著地獲得由使用著色劑(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 the colorant (I) is used, the content of the colorant (I) in the film for thermosetting protective film formation may be appropriately adjusted depending on the purpose. For example, by adjusting the content of the colorant (I) in the thermosetting protective film-forming film and adjusting the light transmittance of the protective film, it is possible to adjust the printing visibility when laser printing is performed on the protective film. In addition, by adjusting the content of the colorant (I) in the thermosetting protective film-forming film, the designability of the protective film can be improved, or grinding marks on the inner surface of the semiconductor wafer can be made less visible. Taking these aspects into consideration, the ratio of the content of the colorant (I) to the total content of all components except the solvent in the composition (III-1) (that is, the colorant in the film for forming a thermosetting protective film) The content of (I) relative to the total mass of the film for forming a thermosetting protective film) is preferably 0.1 mass % to 10 mass %, more preferably 0.1 mass % to 7.5 mass %, particularly preferably 0.1 mass % to 5% by mass. When the ratio is equal to or higher than the lower limit, the effect of using the colorant (I) can be more significantly obtained. In addition, when the ratio is equal to or less than the upper limit, excessive decrease in the light transmittance of the thermosetting protective film-forming film can be suppressed.

[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 Additive(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 effects of the present invention. The general-purpose additive (J) can be a well-known additive, and can be selected arbitrarily according to the purpose, and is not particularly limited. Examples of preferred general-purpose additives (J) include plasticizers, antistatic agents, antioxidants, and getters. (gettering agent) etc.

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，這些通用添加劑(J)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 additive (J) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or may be two or more types. In the case of two or more types, these general additives (J) The combination and ratio of J) can be selected arbitrarily. The content of the general additive (J) in the composition (III-1) and the thermosetting protective film-forming film is not particularly limited and may be appropriately selected depending on 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，這些溶劑的組合及比率可任意選擇。[Solvent] The composition (III-1) preferably further contains a solvent. The composition (III-1) containing a solvent has good operability. The solvent is not particularly limited. Examples of preferred solvents include: hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), 1- Alcohols such as butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amide 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 may be two or more types. In the case of two or more types, the combination and ratio of these solvents can be selected arbitrarily.

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。From the viewpoint that the components contained in the composition (III-1) can be mixed more uniformly, the solvent contained in the composition (III-1) is preferably methyl ethyl ketone or the like.

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 in the composition (III-1) is not particularly limited, and may be appropriately selected depending on 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] A composition for forming a thermosetting protective film such as composition (III-1) is obtained by blending each component constituting the composition. The composition for forming a thermosetting protective film can be produced by the same method as the adhesive composition described above, except that the types of ingredients are different.

○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 an energy ray curable protective film Regarding the curing conditions when the film for forming an energy ray curable protective film is attached to the inner surface of a semiconductor wafer and subjected to energy ray curing to form a protective film, as long as the protective film becomes The degree of hardening to the extent that the function of the protective film can be fully exerted is not particularly limited, and may be appropriately selected according to the type of energy ray curable protective film forming film. For example, the illumination intensity of the energy ray during energy ray curing of the film for forming an energy ray curable protective film is preferably 120 mW/cm 2 to 280 mW/cm 2 . Furthermore, the light amount of the energy ray during the hardening 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 preferably a film containing an energy ray curable component (a) and a filler. 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 is uncured and has 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。[Energy ray curable protective film forming composition (IV-1)] Preferred energy ray curable protective film forming compositions include, for example, the energy ray curable protective film forming composition (IV-1) containing the energy ray curable component (a) (in this specification, is simply referred to 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，該成分亦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 curing component (a)] The energy ray curable component (a) is a component that is cured by irradiation with energy rays. This component is also used to impart film-forming properties, flexibility, etc. to the film for forming an energy ray curable protective film, and to form a hard material 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 polymer (a1) may be at least partially cross-linked by a cross-linking agent, or may not be cross-linked.

[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) having an energy ray curable group and a weight average molecular weight of 80,000 to 2,000,000] Examples of the polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80,000 to 2,000,000 include an acrylic resin (a1-1) obtained by an acrylic polymer (a1-1). a11) is formed by reacting an energy ray curable compound (a12), the acrylic polymer (a11) has a functional group capable of reacting with a group of other compounds, and the energy ray curable compound (a12) has the above Energy ray hardening groups such as functional group reaction groups and energy ray hardening 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 functional group capable of reacting with a group of other compounds include a hydroxyl group, a carboxyl group, an amino group, and a substituted amino group (one or two hydrogen atoms in the amine group are substituted with groups other than hydrogen atoms). base), epoxy group, etc. However, in terms of preventing corrosion of semiconductor wafers or circuits such as semiconductor wafers, the functional group is preferably a group other than a carboxyl group. 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 polymer with functional groups (a11) Examples of the acrylic polymer (a11) having the functional group include a polymer obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer not having the functional group. A polymer obtained by copolymerizing monomers other than acrylic monomers (non-acrylic monomers) in addition to these monomers. In addition, the acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known polymerization method may be used.

作為具有前述官能基之丙烯酸系單體，例如可列舉：含羥基之單體、含羧基之單體、含胺基之單體、含取代胺基之單體、含環氧基之單體等。Examples of acrylic monomers having the aforementioned functional groups include hydroxyl 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 hydroxyl-containing monomer include: (meth)acrylic acid hydroxymethyl ester, (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester, (meth)acrylic acid 3- Hydroxyalkyl (meth)acrylate, such as hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols such as allyl alcohol (unsaturated alcohols that do not have a (meth)acrylyl 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 carboxyl group-containing monomer include: (meth)acrylic acid, crotonic acid and other ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond); 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. base) carboxyalkyl acrylate, etc.

具有前述官能基之丙烯酸系單體較佳為含羥基之單體。The acrylic monomer having the aforementioned functional group is preferably a hydroxyl-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，這些丙烯酸系單體的組合及比率可任意選擇。The acrylic monomer having the above functional group that constitutes the acrylic polymer (a11) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these acrylic monomers You can choose whatever you want.

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 the acrylic monomer that does not have the above functional group include: (meth)acrylic acid methyl ester, (meth) ethyl acrylate, (meth) acrylic acid n-propyl ester, (meth) acrylic acid isopropyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-butyl (meth)acrylate, 3-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 methacrylate, myristyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate Alkanes constituting alkyl esters such as palmityl ((meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. The base is alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms, etc.

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的三級胺基之(甲基)丙烯酸酯等。Examples of the acrylic monomer that does not have the above functional group include: (meth)acrylic acid methoxymethyl ester, (meth)acrylic acid methoxyethyl ester, (meth)acrylic acid ethoxymethyl ester. (meth)acrylates containing alkoxyalkyl groups such as esters and ethoxyethyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate and the like having aromatic groups (meth)acrylate; non-crosslinked (meth)acrylamide and its derivatives; (meth)acrylic acid N,N-dimethylaminoethyl ester, (meth)acrylic acid N,N- Dimethylaminopropyl ester and other non-crosslinking tertiary amino (meth)acrylate.

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，這些丙烯酸系單體的組合及比率可任意選擇。The acrylic monomer that does not have the above-mentioned functional group constituting the acrylic polymer (a11) may be only one type, or may be two or more types. In the case of two or more types, the combination of these acrylic monomers and The ratio can be chosen arbitrarily.

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

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 acrylic polymer (a11), the ratio (content) of the structural units derived from the acrylic monomer having the functional group to the total amount of the structural units constituting the acrylic polymer (a11) is preferred. It is 0.1 mass % to 50 mass %, more preferably 1 mass % to 40 mass %, particularly preferably 3 mass % to 30 mass %. When the ratio is in this range, the energy ray curable group in the acrylic resin (a1-1) can be obtained by copolymerizing the acrylic polymer (a11) and the energy ray curable compound (a12). The content can be easily adjusted to a range in which the degree of hardening of the protective film is optimal.

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，這些丙烯酸系聚合物(a11)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 may be two or more types. In the case of two or more types, the acrylic polymer (a11) may be The combination and ratio can be chosen arbitrarily.

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 ratio of the acrylic resin (a1) in the film for forming an energy-ray curable protective film The content of -1) is preferably 1 to 70 mass%, more preferably 5 to 60 mass%, and even more preferably 10 to 50 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 energy ray curable compound (a12) preferably has one or more types selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group that can match the acrylic polymer (a11). The group for functional group reaction more preferably has an isocyanate group as the aforementioned group. When the energy ray curable compound (a12) has, for example, an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

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 groups contained in one molecule of the energy ray curable compound (a12) is not particularly limited, and can be appropriately selected in consideration of physical properties such as shrinkage rate required for the target protective film. For example, the energy ray curable compound (a12) preferably has 1 to 5 of the energy ray curable groups per 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-methacryloyloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and methacrylyl isocyanate. isocyanate, allyl isocyanate, 1,1-(bisacrylyloxymethyl)ethyl isocyanate; produced by the reaction of a diisocyanate compound or a polyisocyanate compound and hydroxyethyl (meth)acrylate Acrylyl monoisocyanate compound obtained; acrylyl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound, polyol compound and hydroxyethyl (meth)acrylate, etc. Among these, the energy ray curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.

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

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%。In the acrylic resin (a1-1), the ratio of the content of the energy ray curable group derived from the energy ray curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) Preferably it is 20 mol% to 120 mol%, more preferably 35 mol% to 100 mol%, even more 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 energy ray curable compound (a12) is a monofunctional (having one of the above groups in one molecule) compound, the upper limit of the proportion of the above content is 100 mol%, but in the case of the energy ray curable compound (a12), When the sclerosing compound (a12) is a polyfunctional (having two or more of the aforementioned groups in one molecule) compound, the upper limit of the aforementioned content ratio 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 term "weight average molecular weight" is as explained 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)可為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，且在與前述交聯劑反應之基中進行交聯而成，亦可為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而成。When at least part of the polymer (a1) is cross-linked by a cross-linking agent, the polymer (a1) may be any monomer constituting the acrylic polymer (a11) that does not meet the above description. In addition, a monomer having a group that reacts with a cross-linking agent is polymerized and cross-linked with a group that reacts with the cross-linking agent. It may also be obtained by polymerizing a monomer having a group that reacts with the cross-linking agent. It is formed by cross-linking in the functional group reaction group.

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，這些聚合物(a1)的組合及比率可任意選擇。The aforementioned polymer (a1) contained in the composition (IV-1) and the energy-beam curable protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, these polymers The combination and ratio of objects (a1) 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) having an energy ray hardening group and a molecular weight of 100 to 80,000) Examples of the energy ray curable group in the compound (a2) having an energy ray curable group and a molecular weight of 100 to 80,000 include a group containing an energy ray curable double bond. As the preferred energy ray curable group, Examples include (meth)acryl group, vinyl group, and the like.

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 compound (a2) is not particularly limited as long as it satisfies the above conditions, and examples thereof include: a low molecular weight compound having an energy ray curable group, an epoxy resin having an energy ray curable group, and a phenol resin having an energy ray curable group. wait.

前述化合物(a2)中，作為具有能量線硬化性基之低分子量化合物，例如可列舉多官能之單體或低聚物等，較佳為具有(甲基)丙烯醯基之丙烯酸酯系化合物。 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 an acrylate compound having a (meth)acrylyl group is preferred. Examples of the acrylate compound include 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, and propoxylated ethoxylate. Bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(methyl) ) acrylate, 2,2-bis[4-((meth)acryloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloxy) Ethoxy)phenyl]fluorine, 2,2-bis[4-((meth)acryloxypolypropoxy)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-di(meth)acryloxypropane and other 2-functional (methyl) ) Acrylate; tris(2-(meth)acryloxyethyl) isocyanurate, ε-caprolactone modified tris-(2-(meth)acryloxyethyl isocyanurate) ethoxylated glyceryl tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate ) acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate and other multifunctional (methacrylate) polyfunctional (meth)acrylate oligomers such as (meth)acrylic urethane oligomers, etc.

前述化合物(a2)中，作為具有能量線硬化性基之環氧樹脂、具有能量線硬化性基之酚樹脂，例如可使用「日本特開2013-194102號公報」之段落0043等所記載之樹脂。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 the epoxy resin having an energy ray curable group and the phenol resin having an energy ray curable group, for example, the resins described in paragraph 0043 of "Japanese Patent Application Publication No. 2013-194102" can be used. . This resin also corresponds to the resin constituting the thermosetting component described below, but in the present invention, it is regarded as the aforementioned compound (a2).

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，這些化合物(a2)的組合及比率可任意選擇。The aforementioned compound (a2) contained in the composition (IV-1) and the energy-beam curable protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, these compounds (a2) The combination and ratio of a2) can be selected 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 (b) without energy ray hardening group] When the composition (IV-1) and the energy-beam-curable protective film-forming film contain the aforementioned compound (a2) as the aforementioned energy-beam curable component (a), it is preferable to further include a compound that does not have energy-beam curability. Based polymer (b). The polymer (b) may be at least partially cross-linked by a cross-linking agent, or may not be cross-linked.

作為不具有能量線硬化性基之聚合物(b)，例如可列舉：丙烯酸系聚合物、苯氧基樹脂、胺基甲酸酯樹脂、聚酯、橡膠系樹脂、丙烯酸胺基甲酸酯樹脂等。 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-based resins, and acrylic urethane resins. wait. Among these, the polymer (b) is preferably an acrylic polymer (hereinafter, may be simply referred to as "acrylic polymer (b-1)").

丙烯酸系聚合物(b-1)可為公知的聚合物，例如可為1種丙烯酸系單體的均聚物，亦可為2種以上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, a copolymer of two or more acrylic monomers, or one Or a copolymer of two or more acrylic monomers and one or more monomers other than acrylic monomers (non-acrylic monomers).

作為構成丙烯酸系聚合物(b-1)之前述丙烯酸系單體，例如可列舉：(甲基)丙烯酸烷基酯、具有環狀骨架之(甲基)丙烯酸酯、含縮水甘油基之(甲基)丙烯酸酯、含羥基之(甲基)丙烯酸酯、含取代胺基之(甲基)丙烯酸酯等。此處，所謂「取代胺基」，如上文所說明。Examples of the acrylic monomer constituting the acrylic polymer (b-1) include: (meth)acrylic acid alkyl ester, (meth)acrylic acid ester having a cyclic skeleton, and glycidyl group-containing (meth)acrylic acid ester. (meth)acrylate, hydroxyl-containing (meth)acrylate, substituted amine-containing (meth)acrylate, etc. Here, the term "substituted amino group" is as explained 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。Examples of the alkyl (meth)acrylate include the acrylic monomer constituting the acrylic polymer (a11) described above that does not have the above-mentioned functional group (the alkyl group constituting the alkyl ester has a carbon number of (meth)acrylic acid alkyl ester, etc.) with a chain structure of 1 to 18.

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 the (meth)acrylate having a cyclic skeleton include (meth)acrylic acid cycloalkyl esters such as isobornyl methacrylate and dicyclopentyl (meth)acrylate; (meth)acrylic acid esters; )(meth)aralkyl acrylates such as benzyl acrylate; (meth)cycloalkyl acrylates such as dicyclopentenyl (meth)acrylate; dicyclopentenyloxyethyl (meth)acrylate, etc. ( Cyclalkenyloxyalkyl methacrylate, etc.

作為前述含縮水甘油基之(甲基)丙烯酸酯，例如可列舉(甲基)丙烯酸縮水甘油酯等。 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。Examples of the glycidyl group-containing (meth)acrylate include glycidyl (meth)acrylate. Examples of the hydroxyl-containing (meth)acrylate include: (meth)acrylic acid hydroxymethyl ester, (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester, (meth)acrylic acid 2-hydroxypropyl ) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Examples of the substituted amino group-containing (meth)acrylate include N-methylaminoethyl (meth)acrylate.

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 energy ray curable group include those obtained by reacting a reactive functional group in the polymer (b) with a cross-linking agent. of polymers. The reactive functional group may be appropriately selected depending on the type of cross-linking agent, etc., and is not particularly limited. For example, when the crosslinking agent is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxyl group, an amino group, and the like. Among these, a hydroxyl group that is highly reactive with an isocyanate group is preferred. In addition, when the cross-linking agent is an epoxy compound, examples of the reactive functional group include carboxyl group, amine group, amide group, etc. Among these, those with high reactivity with the epoxy group are preferred. carboxyl. However, in order to prevent 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：至少使具有前述反應性官能基之單體進行聚合而獲得之聚合物。於丙烯酸系聚合物(b-1)之情形時，作為構成該丙烯酸系聚合物(b-1)之單體所列舉之前述丙烯酸系單體及非丙烯酸系單體中的任一者或兩者，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。Examples of the polymer (b) having the reactive functional group and not having an energy ray curable group include polymers obtained by polymerizing at least a monomer having the reactive functional group. In the case of an acrylic polymer (b-1), any one or both of the aforementioned acrylic monomers and non-acrylic monomers may be used as monomers constituting the acrylic polymer (b-1). Alternatively, monomers having the aforementioned reactive functional groups may be used. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include a polymer obtained by polymerizing a hydroxyl-containing (meth)acrylate. In addition, examples thereof include those listed above. A polymer obtained by polymerizing a monomer in which one or more hydrogen atoms in the acrylic monomer or non-acrylic monomer are substituted by the 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 a reactive functional group, the proportion (content) of the structural units derived from the monomer having the reactive functional group relative to the total amount of the structural units constituting the polymer (b) is relatively high. Preferably, it is 1 mass % to 20 mass %, More preferably, it is 2 mass % to 10 mass %. When the aforementioned ratio is in this range, the degree of crosslinking in the aforementioned polymer (b) becomes a more optimal 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。From the viewpoint 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 1,500,000. Here, the term "weight average molecular weight" is as explained 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，這些聚合物(b)的組合及比率可任意選擇。The polymer (b) that does not have an energy ray curable group 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, or two types in this case. In the above case, the combination and ratio of these polymers (b) can be selected arbitrarily.

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)。Examples of the composition (IV-1) include a composition containing any one or both of the aforementioned polymer (a1) and the aforementioned compound (a2). Furthermore, when the composition (IV-1) contains the aforementioned compound (a2), it is also preferred to further contain the polymer (b) which does not have an energy ray curable group. In this case, it is also preferred to further contain The aforementioned (a1). Moreover, the composition (IV-1) may not contain the said compound (a2), but may contain the said polymer (a1) and the polymer (b) which does not have an energy ray curable group together.

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) without an energy ray curable group, in the composition (IV-1), the aforementioned The content of compound (a2) is preferably 10 to 400 parts by mass, more preferably 30 parts by mass, based on 100 parts by mass of the total content of the aforementioned polymer (a1) and the polymer (b) without an energy ray curable group. 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) without 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 energy ray curable component (a) and the polymer (b) without an energy ray curable group in the film for forming an energy ray curable protective film to the total mass of the film is preferably 5 mass% to 90 mass%, more preferably 10 mass% to 80 mass%, particularly preferably 20 mass% to 70 mass%. When 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。The composition (IV-1) may contain, in addition to the aforementioned energy ray curable component, a thermosetting component selected from the group consisting of a filler, a coupling agent, a crosslinking agent, a photopolymerization initiator, a coloring agent and 1 or 2 or more types in a group 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。Examples of the aforementioned thermosetting components, fillers, coupling agents, cross-linking agents, photopolymerization initiators, colorants and general additives in the composition (IV-1) include those in the composition (III-1). The thermosetting component (B), filler (D), coupling agent (E), cross-linking agent (F), photopolymerization initiator (H), colorant (I) and general additive (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提高對被接著體之接著力，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 energy ray curable component and the thermosetting component, the energy ray curable protective film forming film formed can improve the adhesion force to the adherend by heating. , the strength of the resin film formed from the energy ray curable protective film forming film is also improved. In addition, by using the composition (IV-1) containing the energy ray curable component and the colorant, the energy ray curable protective film forming film formed behaves the same as the thermosetting protective film forming film described above. It has the same effect as the case where the colorant (I) is contained.

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 component, filler, coupling agent, cross-linking agent, photopolymerization initiator, colorant and general additive may be used individually by one type, or two or more types may be used in combination. When two or more types are used together, the combination and ratio of these can be selected arbitrarily.

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 contents of the aforementioned thermosetting components, fillers, coupling agents, cross-linking agents, photopolymerization initiators, colorants and general additives in the composition (IV-1) can be appropriately adjusted according to the purpose and are 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)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 order to improve the operability 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 those in the composition (III-1). The composition (IV-1) may contain only one type of solvent or two or more types of solvents. The content of the solvent in the composition (IV-1) is not particularly limited, and may be appropriately selected depending on 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。[Production method of energy ray curable protective film forming composition] A composition for forming an energy ray curable protective film such as composition (IV-1) can be obtained by blending each component constituting the composition. The composition for forming an energy ray curable protective film can be produced by the same method as the adhesive composition described above, except that the types of ingredients are different.

◎剝離膜 前述剝離膜可作為於前述保護膜形成用複合片之保護膜形成用膜側的最表層所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。◎Peel-off film The release film may be an arbitrary component included in 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 which the release film is provided on the film for protective film formation, peeling charging of the composite sheet for protective film formation is suppressed when the release film is removed from the film for protective film formation.

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 release film may be a known film, and examples thereof include a film made of a resin film such as a polyethylene terephthalate film and one surface thereof subjected to a release treatment such as polysiloxane treatment. The said peeling film may have the same structure as the said peelability improving layer as an 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 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，例如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中之前述支撐片側的最表層的表面電阻率為1.0×1011 Ω/□以下；自於70℃加熱1分鐘後的前述保護膜形成用複合片，切取大小為10cm×20cm之試片，使前述試片中之前述支撐片側的最表層接觸於多孔台的表面，藉此將前述試片載置於前述多孔台上，使大小為6cm×10cm×2cm且質量為1kg之重物之大小為6cm×10cm之面接觸於前述試片中的保護膜形成用膜，將前述重物載置於前述保護膜形成用膜上，沿相對於前述試片之與前述多孔台之接觸面為平行的方向，使前述重物以10mm/min之速度移動，測定前述重物的即將開始移動前的荷重時，前述荷重的測定值為20N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-伸乙二氧基噻吩)/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。An example of an embodiment of the protective film-forming composite sheet is a protective film-forming composite sheet including a support sheet and a protective film-forming film formed on one side of the support sheet; and the protective film-forming film is formed on one side of the support sheet. The surface resistivity of the outermost layer on the supporting sheet side of the composite sheet is 1.0×10 11 Ω/□ or less; and the composite sheet for protective film formation heated at 70°C for 1 minute is used to cut out a 10cm×20cm sample. piece, so that the outermost surface layer of the aforementioned support piece side of the aforementioned test piece is in contact with the surface of the porous platform, thereby placing the aforementioned test piece on the aforementioned porous stage with a weight of 6 cm × 10 cm × 2 cm and a mass of 1 kg. A surface with a size of 6 cm × 10 cm is in contact with the protective film forming film in the aforementioned test piece, and the aforementioned heavy object is placed on the aforementioned protective film forming film along the contact surface with the aforementioned porous stage relative to the aforementioned test piece. In a parallel direction, the aforementioned weight is moved at a speed of 10 mm/min, and the load immediately before the movement of the aforementioned weight is measured, the measured value of the aforementioned load is 20N or less; the aforementioned support sheet is provided with a base material, and is formed on the aforementioned An antistatic layer on one or both sides of the base material, or the aforementioned support sheet has a base material with antistatic properties as an antistatic layer; the aforementioned antistatic layer contains a material selected from the group consisting of pyrimidinium salt, pyridinium salt, and piperidinium salt. , pyrrolidinium salt, imidazolium salt, morpholinium salt, sulfonium salt, phosphonium salt, ammonium salt, poly(3,4-ethylenedioxythiophene)/polystyrenesulfonate, polypyrrole and nanoparticles One or more types in the group composed of carbon tubes.

作為前述保護膜形成用複合片的一實施形態，例如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；前述保護膜形成用複合片中之前述支撐片側的最表層的表面電阻率為1.0×1011 Ω/□以下；自於70℃加熱1分鐘後的前述保護膜形成用複合片，切取大小為10cm×20cm之試片，使前述試片中之前述支撐片側的最表層接觸於多孔台的表面，藉此將前述試片載置於前述多孔台上，使大小為6cm×10cm×2cm且質量為1kg之重物中之大小為6cm×10cm之面接觸於前述試片中的保護膜形成用膜，將前述重物載置於前述保護膜形成用膜上，沿相對於前述試片之與前述多孔台之接觸面為平行的方向，使前述重物以10mm/min之速度移動，測定前述重物的即將開始移動前的荷重時，前述荷重的測定值為20N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-伸乙二氧基噻吩)/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抗靜電層的合計厚度為10nm至200nm。One embodiment of the protective film-forming composite sheet includes, for example, a protective film-forming composite sheet including a support sheet and a protective film-forming film formed on one side of the support sheet; The surface resistivity of the outermost layer on the side of the supporting sheet in the composite sheet is 1.0×10 11 Ω/□ or less; cut out a test piece of 10cm×20cm from the composite sheet for forming a protective film after heating at 70°C for 1 minute. , so that the outermost layer on the side of the support sheet in the aforementioned test piece is in contact with the surface of the porous stage, thereby placing the aforementioned test piece on the aforementioned porous stage in a weight of 6 cm × 10 cm × 2 cm and a mass of 1 kg. A surface with a size of 6 cm × 10 cm is in contact with the protective film forming film in the aforementioned test piece, and the aforementioned heavy object is placed on the aforementioned protective film forming film along the contact surface with the aforementioned porous stage relative to the aforementioned test piece. In a parallel direction, the aforementioned weight is moved at a speed of 10 mm/min, and the load immediately before the movement of the aforementioned weight is measured, the measured value of the aforementioned load is 20N or less; the aforementioned support sheet is provided with a base material, and is formed on the aforementioned An antistatic layer on one or both sides of the base material, or the aforementioned support sheet has a base material with antistatic properties as an antistatic layer; the aforementioned antistatic layer contains a material selected from the group consisting of pyrimidinium salt, pyridinium salt, and piperidinium salt. , pyrrolidinium salt, imidazolium salt, morpholinium salt, sulfonium salt, phosphonium salt, ammonium salt, poly(3,4-ethylenedioxythiophene)/polystyrenesulfonate, polypyrrole and nanoparticles One or more than two types of the group consisting of carbon tubes; the total thickness of the antistatic layer formed on one or both sides of the aforementioned substrate is 10 nm to 200 nm.

作為前述保護膜形成用複合片的一實施形態，例如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；前述保護膜形成用複合片中之前述支撐片側的最表層的表面電阻率為1.0×1011 Ω/□以下；自於70℃加熱1分鐘後的前述保護膜形成用複合片，切取大小為10cm×20cm之試片，使前述試片中之前述支撐片側的最表層接觸於多孔台的表面，藉此將前述試片載置於前述多孔台上，使大小為6cm×10cm×2cm且質量為1kg之重物之大小為6cm×10cm之面接觸於前述試片中的保護膜形成用膜，將前述重物載置於前述保護膜形成用膜上，沿相對於前述試片之與前述多孔台之接觸面為平行的方向，使前述重物以10mm/min之速度移動，測定前述重物的即將開始移動前的荷重時，前述荷重的測定值為20N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-伸乙二氧基噻吩)/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，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。One embodiment of the protective film-forming composite sheet includes, for example, a protective film-forming composite sheet including a support sheet and a protective film-forming film formed on one side of the support sheet; The surface resistivity of the outermost layer on the side of the supporting sheet in the composite sheet is 1.0×10 11 Ω/□ or less; cut out a test piece of 10cm×20cm from the composite sheet for forming a protective film after heating at 70°C for 1 minute. , so that the outermost layer on the side of the support sheet in the aforementioned test piece is in contact with the surface of the porous platform, thereby placing the aforementioned test piece on the aforementioned porous stage, with a weight of 6 cm × 10 cm × 2 cm and a mass of 1 kg. The surface of the protective film forming film with a size of 6cm×10cm is in contact with the aforementioned test piece. The aforementioned heavy object is placed on the aforementioned protective film forming film along the contact surface with the aforementioned porous stage relative to the aforementioned test piece. The aforementioned weight is moved in a parallel direction at a speed of 10 mm/min, and the load immediately before the movement of the aforementioned weight is measured, the measured value of the aforementioned load is 20N or less; the aforementioned support sheet is provided with a base material, and is formed on the aforementioned base material. An antistatic layer on one or both sides of the material, or the aforementioned support sheet has a base material with antistatic properties as an antistatic layer; the aforementioned antistatic layer contains a material selected from the group consisting of 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 nanocarbon One or more types in the group consisting of tubes; the aforementioned antistatic base material includes the aforementioned antistatic agent and resin, and in the aforementioned antistatic base material, the content of the aforementioned antistatic agent is relative to the aforementioned The total content ratio of the antistatic agent and resin 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。◇Production method of composite sheet for protective film formation The composite sheet for forming a protective film can be produced by laminating each of the above layers so as to have a corresponding positional relationship. Each layer is formed 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, when an adhesive layer is laminated on a base material or an antistatic base material when manufacturing a support sheet, the above-mentioned adhesive composition is applied on the base material or the antistatic base material, and if necessary, Just dry. This method can be applied to both the case where an adhesive layer is laminated on the uneven surface of the base material or the antistatic base material, and the case where the adhesive layer is laminated on the aforementioned smooth surface of the base material or the antistatic base material. situation. Furthermore, this method is particularly suitable for laminating an adhesive layer on the uneven surface. The reason is that when this method is applied, a high effect of suppressing the generation of voids between the uneven surface of the base material or the antistatic base material and the adhesive layer can be obtained.

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。The same is true for laminating a back antistatic layer or a surface antistatic layer on a base material or an antistatic base material when manufacturing the support sheet. In this case, except for using the antistatic composition (VI-1) instead of the adhesive composition, the same method as the above-mentioned method of laminating the adhesive layer can be used, on the base material or on the antistatic base material. Laminate a back antistatic layer or a 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 base material or an antistatic base material, the following method can be used instead of coating the adhesive composition on the base material or the antistatic base material as described above. method. That is, the adhesive layer can also be laminated on the base material or the antistatic base material by the following method: applying the adhesive composition on the release film and drying it if necessary, thereby preforming the adhesive layer on the release film The adhesive layer is used to bond the exposed surface of the adhesive layer to a surface of the base material or the antistatic base material. Furthermore, this method is particularly suitable for laminating an adhesive layer on the smooth surface. The reason is that when this method is applied, a high effect of suppressing the generation of gaps between the base material or the smooth surface of the antistatic base material and the adhesive layer can be obtained.

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。The same applies to the case where a release film is used to laminate a back antistatic layer or a surface antistatic layer on a base material or an antistatic base material when manufacturing a support sheet. 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 laminating an adhesive layer using a release film can be used to form antistatic properties on the base material or the adhesive layer. A back antistatic layer or surface antistatic layer is laminated on the base material.

至此已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。So far, the case where an adhesive layer, a back antistatic layer, or a surface antistatic layer is laminated on a base material or an antistatic base material has been cited as an example. However, the above method can also be applied to, for example, a base material or an antistatic base material. The case where an intermediate layer is laminated on the base material is the case where 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層之與接觸前述剝離膜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 film for forming a protective film is laminated on an adhesive layer that has been laminated on a base material or an antistatic base material, the composition for forming a protective film can be applied on the adhesive layer. Instead, the protective film forming film is directly formed. The composition used to form this layer can also be used as a layer other than the film for forming a protective film, and this 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 already laminated on the base material (hereinafter, referred to as the "first layer"), thereby forming a continuous 2-layer laminated structure. (In other words, a laminated structure of the first layer and the second layer), the method of applying a composition for forming the second layer on the first layer and drying it if necessary can be applied. However, it is preferable to form a continuous two-layer laminated structure by using a composition for forming the second layer, forming the second layer in advance on the release film, and combining the formed second layer with The exposed surface on the opposite side of the release film is bonded to the exposed surface of the first layer. At this time, the composition is preferably applied to the release-treated surface of the release film. The peeling film can be removed if necessary after forming the laminated structure. Here, the case where a protective film-forming film is laminated on the adhesive layer is given as an example. However, for example, the case where an intermediate layer is laminated on the adhesive layer, the case where a protective film-forming film is laminated on the intermediate layer, and the surface antistatic The target laminate structure can be selected arbitrarily, such as when an adhesive layer is laminated on top of each other.

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, the layers other than the base material constituting the composite sheet for forming a protective film can be laminated by a method of being formed in advance on the release film and then bonded to the surface of the target layer. Therefore, it is appropriate to select the layer using this step as needed. A composite sheet for forming a protective film may be produced.

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之與接觸剝離膜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 protective film formation is usually stored in a state in which a release film is bonded to the surface of the outermost layer (for example, the film for protective film formation) on the opposite side to the support sheet. Therefore, a protective film-forming composite sheet with a release film can be obtained by coating a protective film-forming composition or the like on the release film (preferably, the release-treated surface of the release film) to form The composition constituting the layer constituting the outermost layer is dried as necessary, thereby forming the layer constituting the outermost layer on the release film in advance, and using any of the above methods to expose the layer on the side opposite to the side contacting the release film. Laminate the remaining layers on the surface without removing the peel-off film and keep the bonded state intact.

◇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，例如可列舉以下之方法，具有：將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，製作由具備支撐片、設置於前述支撐片的一面(換言之為第1面)上之切斷後的前述保護膜或保護膜形成用膜、及設置於前述切斷後的保護膜或保護膜形成用膜之與前述支撐片側為相反側的面(本說明書中，有時稱為「第1面」)上之半導體晶片而成之積層體之步驟(以下，有時簡稱為「積層體製作步驟」)；以及將前述積層體中之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」)；進而，於前述積層體製作步驟與前述拾取步驟之間，具有將固定於台上之前述積層體自前述台扯離之步驟(以下，有時簡稱為「積層體扯離步驟」)；於前述積層體扯離步驟中，固定於台上之前述積層體於前述積層體之前述支撐片側的最表層的表面接觸於前述台，前述台之前述積層體的固定面為陶瓷製或不銹鋼製。 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、積層體製作步驟、積層體扯離步驟及拾取步驟。並且，依序進行前述積層體製作步驟、積層體扯離步驟及拾取步驟，但保護膜形成步驟可於貼附步驟後的任一階段進行。另外，於保護膜形成用膜不具有硬化性之情形時，不進行前述保護膜形成步驟。◇Semiconductor chip manufacturing method The composite sheet for forming a protective film can be used to manufacture semiconductor wafers. An example of a method for manufacturing a semiconductor wafer at this time is a method including a step of attaching the protective film-forming film in the protective film-forming composite sheet to the semiconductor wafer (hereinafter, sometimes simply referred to as " "Attachment step"); a step of curing the protective film-forming film attached to the semiconductor wafer to form a protective film (hereinafter, sometimes referred to as "protective film forming step"); dividing the semiconductor wafer, The protective film or protective film-forming film is cut to produce the cut protective film or protective film-forming film provided with a support sheet on one side (in other words, the first surface) of the support sheet, and The steps of forming a laminated body of semiconductor wafers on the side of the cut protective film or protective film-forming film opposite to the supporting sheet side (sometimes referred to as the "first side" in this specification) (hereinafter , sometimes referred to simply as the "laminate production step"); and the step of picking up the semiconductor wafer having the cut protective film or protective film forming film in the laminate from the supporting sheet (hereinafter, (sometimes referred to as "picking up step"); further, between the aforementioned laminated body production step and the aforementioned picking up step, there is a step of pulling off the aforementioned laminated body fixed on the table from the aforementioned table (hereinafter, sometimes referred to as "picking up step"); "Laminated body peeling off step"); In the aforementioned laminated body peeling off step, the surface of the outermost layer of the laminated body on the front side of the supporting sheet before being fixed on the table is in contact with the aforementioned table, and the front surface of the laminated body on the front of the aforementioned table is in contact with the aforementioned table. The fixing surface is made of ceramic or stainless steel. In the above manufacturing method, after the above attaching step, the above protective film forming step, the laminated body manufacturing step, the laminated body tearing off step and the picking up step are performed. In addition, the aforementioned laminated body production step, laminated body peeling step and picking up step are performed in sequence, but the protective film forming step can be performed at any stage after the attaching step. In addition, when the film for protective film formation does not have curability, the aforementioned protective film forming step is not performed.

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 which the protective film forming composite sheet is to be used is not particularly limited, but in order to make it easier to divide into semiconductor wafers described later, it is preferably 30 μm to 1000 μm, and more preferably 100 μm to 400 μm.

以下，一邊參照圖式，一邊對上述製造方法進行說明。圖14至圖17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為圖1所示之保護膜形成用複合片之情形時的製造方法作為示例而進行說明。Hereinafter, the above-mentioned manufacturing method will be described with reference to the drawings. 14 to 17 are cross-sectional views for schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. Here, a manufacturing method when the composite sheet for protective film formation is the composite sheet for protective film formation shown in FIG. 1 will be described as an example.

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：將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，製作具備支撐片、設置於前述支撐片的一面(第1面)上之切斷後的前述保護膜、及設置於前述切斷後的保護膜之與前述支撐片側為相反側的面(第1面)上之半導體晶片之積層體(以下，有時簡稱為「第1積層體」)之步驟(以下，有時簡稱為「第1積層體製作步驟」)；以及將前述第1積層體中之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)；進而，於前述第1積層體製作步驟與前述拾取步驟之間，具有將固定於台上之前述第1積層體自前述台扯離之步驟(以下，有時簡稱為「積層體扯離步驟」)；於前述積層體扯離步驟中，固定於台上之前述第1積層體於前述第1積層體之前述支撐片側的最表層的表面接觸於前述台，前述台之前述第1積層體的固定面為陶瓷製或不銹鋼製。 圖14至圖15係用於以示意方式說明此種製造方法(1)的一實施形態之剖視圖。The manufacturing method of this embodiment (sometimes referred to as "manufacturing method (1)" in this specification) includes the step of attaching the protective film forming film in the protective film forming composite sheet to the semiconductor wafer (attaching Attached step); the step of curing the protective film forming film attached to the semiconductor wafer to form a protective film (protective film forming step); dividing the semiconductor wafer, cutting the protective film, and producing a support sheet , the cut protective film provided on one side (first surface) of the support sheet, and the semiconductor wafer provided on the surface (first surface) of the cut protective film opposite to the support sheet side a step (hereinafter, sometimes referred to as a "first laminated body production step") of a laminated body (hereinafter, sometimes referred to as a "first laminated body"); The semiconductor wafer with the protective film is separated from the supporting sheet and picked up (picking up step); further, between the first laminated body production step and the picking up step, the first laminated body is fixed on the table. The step of pulling off the laminated body from the table (hereinafter, sometimes referred to as the "layered body peeling step"); in the step of pulling off the laminated body, the first laminated body before being fixed on the table is attached to the first laminated body. The surface of the outermost layer on the support sheet side is in contact with the table, and the fixed surface of the table before the first laminated body is made of ceramics or stainless steel. 14 to 15 are cross-sectional views for schematically explaining one embodiment of the manufacturing method (1).

製造方法(1)中，於使用圖1所示之保護膜形成用複合片101之情形時，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。In the manufacturing method (1), when the composite sheet 101 for protective film formation shown in FIG. 1 is used, as shown in FIG. 14A, the peeling film 15 is removed from the film 101 for protective film formation. In addition, here, for the sake of convenience, the composite sheet for forming a protective film after removing the release film 15 is also denoted by a symbol 101.

製造方法(1)的前述貼附步驟中，如圖14B所示，於半導體晶圓9的內面9b，貼附保護膜形成用複合片101中的保護膜形成用膜13。 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，貼附於半導體晶圓9。該情形時，例如亦可將保護膜形成用膜13於70℃加熱1分鐘後，立即貼附於半導體晶圓9。 此外，此處省略圖示半導體晶圓9中電路面上的凸塊等。In the aforementioned attaching step of the manufacturing method (1), as shown in FIG. 14B , the protective film forming film 13 in the protective film forming composite sheet 101 is attached to the inner surface 9 b of the semiconductor wafer 9 . In the attaching step, the protective film forming film 13 may be softened by heating and attached to the semiconductor wafer 9 . In this case, for example, the protective film forming film 13 may be heated at 70° C. for 1 minute and then immediately attached to the semiconductor wafer 9 . In addition, the bumps etc. on the circuit surface of the semiconductor wafer 9 are not shown here.

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 protective film forming step, the protective film forming film 13 attached to the semiconductor wafer 9 is cured to form a protective film 13' as shown in FIG. 14C. At this time, when the protective film forming film 13 is thermosetting, the protective film forming film 13 is heated to form the protective film 13'. When the protective film forming film 13 is energy ray curable, the protective film forming film 13 is irradiated with energy rays through the support sheet 10 to form the protective film 13'. In addition, the protective film forming composite sheet in which the protective film forming film 13 becomes the protective film 13' is denoted by reference numeral 101' 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 forming step, the curing conditions of the protective film forming film 13, that is, the heating temperature and heating time during thermal curing, and the illuminance and light amount of energy rays during energy ray curing are as described above.

製造方法(1)的保護膜形成步驟後，於前述第1積層體製作步驟中，分割半導體晶圓9，切斷保護膜13'，如圖14D所示，製作具備支撐片10、設置於支撐片10的第1面10a上之切斷後的保護膜130'、及設置於切斷後的保護膜130'的第1面130a'上之半導體晶片9'之第1積層體901。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)。第1積層體901中存在多個具備切斷後的保護膜130'之半導體晶片9'。After the protective film forming step of the manufacturing method (1), in the first laminated body manufacturing step, the semiconductor wafer 9 is divided and the protective film 13' is cut. As shown in FIG. 14D, a support sheet 10 is produced, which is provided on the support. The protective film 130' after cutting on the first surface 10a of the sheet 10, and the first laminated body 901 of the semiconductor wafer 9' provided on the first surface 130a' of the protective film 130' after cutting. At this time, the protective film 13' is cut (divided) at a position along the peripheral edge of the semiconductor wafer 9'. There are a plurality of semiconductor wafers 9' provided with cut protective films 130' in the first laminated body 901.

前述第1積層體製作步驟中，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；以聚焦到設定於半導體晶圓9的內部之焦點之方式照射雷射光，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 first laminated body manufacturing step, the method of dividing the semiconductor wafer 9 and cutting the protective film 13' may be a known method. Examples of such a method include: dividing (cutting) the semiconductor wafer 9 together with the protective film 13' using a dicing blade; and irradiating laser light so as to focus on a focal point set inside the semiconductor wafer 9 , a modified layer is formed inside the semiconductor wafer 9, and then the semiconductor wafer 9 with the modified layer formed and the protective film 13' attached to the inner surface 9b is placed along the protective film 13 together with the protective film 13'. The protective film 13' is expanded in the surface direction, the protective film 13' is cut, and the semiconductor wafer 9 is divided into parts of the modified layer.

前述第1積層體製作步驟中，可將貼附於半導體晶圓9之保護膜形成用複合片101'固定於台7來進行製作第1積層體901。此處，符號7a表示台7用以將固定對象物(此處為保護膜形成用複合片101')予以固定之面、亦即固定面。固定於台7上之第1積層體901於該第1積層體901中的背面抗靜電層17的第2面17b接觸於台7。台7的固定面7a與保護膜形成用複合片101'中的背面抗靜電層17的第2面相互密接。 台7的固定面7a為陶瓷製或不銹鋼製。In the aforementioned first laminated body production step, the protective film forming composite sheet 101 ′ attached to the semiconductor wafer 9 is fixed to the stage 7 to produce the first laminated body 901 . Here, the symbol 7a represents the surface of the base 7 for fixing the object to be fixed (here, the composite sheet 101' for forming a protective film), that is, the fixing surface. The first laminated body 901 fixed on the table 7 is in contact with the table 7 with the second surface 17 b of the back antistatic layer 17 in the first laminated body 901 . The fixed surface 7a of the table 7 and the second surface of the back antistatic layer 17 in the protective film forming composite sheet 101' are in close contact with each other. The fixed surface 7a of the table 7 is made of ceramic or stainless steel.

作為台7，例如可列舉以下之台(亦即吸附台)：具有於該台7的厚度方向貫通之空隙部，藉由將台7之與固定對象物接觸之側、亦即固定面7a側的相反側予以減壓，能夠將前述固定對象物吸附而固定於台7上。 此外，於圖14以後的圖中，作為台，僅表示台之固定對象物的固定部位，省略其他構成的圖示。Examples of the table 7 include a table (i.e., an adsorption table) having a gap portion penetrating the table 7 in the thickness direction. By reducing the pressure on the opposite side, the fixed object can be adsorbed and fixed on the table 7 . In addition, in the figures after FIG. 14 , as the table, only the fixing part of the fixed object of the table is shown, and the illustration of other components is omitted.

台7的固定面7a中，如上文所說明，較佳為凹凸差為5μm以下。In the fixed surface 7a of the table 7, as explained above, it is preferable that the unevenness difference is 5 μm or less.

製造方法(1)的第1積層體製作步驟後，在前述拾取步驟之前，於前述積層體扯離步驟中，如圖15A所示，將固定於台7上之第1積層體901自台7扯離。此時，例如於使用吸附台作為台7之情形時，藉由解除減壓，能夠解除第1積層體901於台7上的固定狀態。 藉由保護膜形成用複合片101'中的背面抗靜電層17的第2面17b滿足上述之表面電阻率及靜摩擦力之條件，於積層體扯離步驟中，因帶電所致之半導體晶片9'中的電路的破壞得到抑制。After the first laminated body production step of the manufacturing method (1) and before the aforementioned picking-up step, in the aforementioned laminated body separation step, as shown in FIG. 15A , the first laminated body 901 fixed on the table 7 is removed from the table 7 Pull away. At this time, for example, when a suction stage is used as the stage 7, the fixed state of the first laminated body 901 on the stage 7 can be released by releasing the pressure reduction. Since the second surface 17b of the backside antistatic layer 17 in the protective film-forming composite sheet 101' satisfies the above-mentioned conditions of surface resistivity and static friction, the semiconductor wafer 9 due to charging during the laminate separation step 'The damage to the circuit in the circuit is suppressed.

進行前述積層體扯離步驟之原因在於，在第1積層體製作步驟之後，至少為了進行拾取步驟，而必須搬運第1積層體901。作為此種必須搬運第1積層體901之步驟，拾取步驟以外的其他步驟亦可能會符合。作為前述其他步驟，可列舉以下所示之步驟。The reason why the aforementioned laminated body separation step is performed is that after the first laminated body production step, at least the first laminated body 901 must be transported for at least the picking up step. As such a step that requires transporting the first laminated body 901, other steps other than the picking up step may be applicable. Examples of the aforementioned other steps include the steps shown below.

例如，進行上述之半導體晶圓9之分割、及保護膜13'之切斷時(亦即進行切割時)，有時會產生來自半導體晶圓9或保護膜13'之切削屑，該切削屑附著於第1積層體901。於本實施形態的第1積層體製作步驟與拾取步驟之間，作為前述其他步驟，可進行將第1積層體901用水洗淨，將該切削屑沖洗而去除之步驟(以下，有時簡稱為「洗淨步驟」)。For example, when the semiconductor wafer 9 is divided and the protective film 13' is cut (that is, when dicing is performed), cutting chips may be generated from the semiconductor wafer 9 or the protective film 13'. Adhered to the first laminated body 901. Between the first laminated body production step and the picking-up step in this embodiment, as the above-mentioned other steps, a step of washing the first laminated body 901 with water and rinsing and removing the cutting chips (hereinafter, sometimes referred to as "Cleaning Steps").

前述洗淨步驟中，如圖15B所示，將所搬運之第1積層體901固定於台6上，將該狀態的第1積層體901用水洗淨。亦即，該情形時的台6係洗淨用台。 洗淨步驟中，作為洗淨用台之台6亦可將相對於該台6的固定面6a正交之方向設為旋轉軸的軸向而能夠旋轉。於使用此種台6之情形時，亦可一邊使台6旋轉，一邊將第1積層體901用水洗淨。能夠旋轉之台6除如此能夠旋轉之方面以外，可與上述之台7相同。例如，台6可為以下之台(亦即吸附台)：具有於該台6的厚度方向貫通之空隙部，藉由將台6之與固定對象物接觸之側、亦即固定面6a側的相反側予以減壓，能夠將前述固定對象物吸附而固定於台6上。In the aforementioned washing step, as shown in FIG. 15B , the conveyed first laminated body 901 is fixed on the table 6 , and the first laminated body 901 in this state is washed with water. That is, the table 6 in this case is a washing table. In the washing step, the table 6 serving as the washing table may be rotatable by setting the direction orthogonal to the fixed surface 6 a of the table 6 as the axial direction of the rotation axis. When the table 6 is used, the first laminated body 901 can be washed with water while the table 6 is rotated. The rotatable stage 6 may be the same as the above-mentioned stage 7 except for the aspect of being rotatable. For example, the table 6 can be a table (that is, an adsorption table) having a gap portion penetrating the table 6 in the thickness direction. By reducing the pressure on the opposite side, the fixed object can be adsorbed and fixed on the table 6 .

前述洗淨步驟中，與第1積層體製作步驟之情形同樣地，固定於台6上之第1積層體901於該第1積層體901中的背面抗靜電層17的第2面17b接觸於台6。台6的固定面6a與保護膜形成用複合片101'中的背面抗靜電層17的第2面相互密接。In the aforementioned cleaning step, similarly to the first laminated body production step, the first laminated body 901 fixed on the stage 6 is in contact with the second surface 17b of the back antistatic layer 17 in the first laminated body 901. Taiwan 6. The fixed surface 6a of the table 6 and the second surface of the back antistatic layer 17 in the protective film forming composite sheet 101' are in close contact with each other.

於進行前述洗淨步驟之情形時，洗淨步驟後，在前述拾取步驟之前，如圖15C所示，再次進行積層體扯離步驟，將固定於台6上之第1積層體901自台6扯離。此時，例如於使用吸附台作為台6之情形時，藉由解除減壓，能夠解除第1積層體901於台6上的固定狀態。 本步驟中，藉由保護膜形成用複合片101'中的背面抗靜電層17的第2面17b滿足上述之表面電阻率及靜摩擦力之條件，因帶電所致之半導體晶片9'中的電路的破壞亦得到抑制。When performing the aforementioned washing step, after the washing step and before the aforementioned picking-up step, as shown in FIG. 15C , the laminated body pulling-off step is performed again, and the first laminated body 901 fixed on the stage 6 is removed from the stage 6 Pull away. At this time, for example, when a suction stage is used as the stage 6, the fixed state of the first laminated body 901 on the stage 6 can be released by releasing the pressure reduction. In this step, because the second surface 17b of the backside antistatic layer 17 in the protective film forming composite sheet 101' satisfies the above conditions of surface resistivity and static friction, the circuit in the semiconductor chip 9' is charged due to damage has also been suppressed.

於進行前述洗淨步驟之情形時，於本實施形態的第1積層體製作步驟與拾取步驟之間，作為前述其他步驟，可進行使洗淨後的第1積層體901乾燥，將前續步驟的洗淨時所附著之水去除之步驟(以下，有時簡稱為「乾燥步驟」)。於必須在與洗淨步驟不同的場所進行前述乾燥步驟之情形時，必須搬運洗淨步驟後的第1積層體901。When performing the aforementioned washing step, between the first laminated body production step and the picking-up step in this embodiment, as the aforementioned other step, the washed first laminated body 901 may be dried, and the preceding steps may be performed. The step of removing the water attached during washing (hereinafter sometimes referred to as the "drying step"). When the drying step must be performed in a different place from the washing step, the first laminated body 901 after the washing step must be transported.

前述乾燥步驟中，如圖15B所示，亦將第1積層體901固定於台6上，使該狀態的第1積層體901乾燥。亦即，該情形時的台6係乾燥用台。此外，本實施形態中，於乾燥步驟中，可繼續使用洗淨步驟所使用之台6，亦可與洗淨步驟所使用之台不同地另行使用台6。於乾燥步驟中，與洗淨步驟所使用之台不同地另行使用台6之情形時，乾燥步驟所使用之台6的種類與洗淨步驟所使用之台6的種類可相同亦可不同。 乾燥步驟中的第1積層體901於台6上之固定方法與前述洗淨步驟的固定方法相同。In the aforementioned drying step, as shown in FIG. 15B , the first laminated body 901 is also fixed on the table 6 and the first laminated body 901 in this state is dried. That is, the table 6 in this case is a drying table. In addition, in this embodiment, in the drying step, the stage 6 used in the washing step can be continued to be used, or a stage 6 different from the stage used in the washing step can be used. In the drying step, when a table 6 is used separately from the table used in the washing step, the type of table 6 used in the drying step and the type of table 6 used in the washing step may be the same or different. The method of fixing the first laminated body 901 on the stage 6 in the drying step is the same as the fixing method in the aforementioned washing step.

於進行前述乾燥步驟之情形時，乾燥步驟後，與上述之洗淨步驟後之情形同樣地，在前述拾取步驟之前，如圖15C所示，再次進行積層體扯離步驟，將固定於台6上之第1積層體901自台6扯離。至少後述拾取步驟必須於與前述乾燥步驟不同的場所進行，本實施形態中，必須搬運乾燥步驟後的第1積層體901。 本步驟中，藉由保護膜形成用複合片101'中的背面抗靜電層17的第2面17b滿足上述之表面電阻率及靜摩擦力之條件，因帶電所致之半導體晶片9'中的電路的破壞亦得到抑制。In the case of performing the aforementioned drying step, after the drying step, in the same manner as after the aforementioned washing step, before the aforementioned picking-up step, as shown in FIG. 15C , the laminate separation step is performed again, and the laminate is fixed on the stage 6 The first layered body 901 is separated from the platform 6. At least the picking-up step described later must be performed in a different place from the drying step. In this embodiment, the first laminated body 901 after the drying step must be transported. In this step, because the second surface 17b of the backside antistatic layer 17 in the protective film forming composite sheet 101' satisfies the above conditions of surface resistivity and static friction, the circuit in the semiconductor chip 9' is charged due to damage has also been suppressed.

製造方法(1)的前述其他步驟後，於前述拾取步驟中，如圖15D所示，將所搬運之第1積層體901中之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(vacuum collet)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中，電路的破壞得到了抑制。After the aforementioned other steps of the manufacturing method (1), in the aforementioned picking-up step, as shown in FIG. 15D , the semiconductor wafer 9' having the cut protective film 130' in the conveyed first laminated body 901 is self-supporting. 10Tear it away and pick it up. Here, the pickup direction is indicated by an arrow I, and this situation is also the same in subsequent figures. As the peeling mechanism 8 for peeling off the semiconductor wafer 9' together with the protective film 130' from the supporting sheet 10, a vacuum collet or the like can be used. Through the above steps, the target semiconductor wafer 9' is obtained as a semiconductor wafer with a protective film. In the protective film-attached semiconductor wafer obtained by the manufacturing method (1), damage to the circuit is suppressed.

作為製造方法(1)的一例，可列舉依序具有前述貼附步驟、保護膜形成步驟、第1積層體製作步驟、積層體扯離步驟、洗淨步驟、積層體扯離步驟、乾燥步驟、積層體扯離步驟及拾取步驟之方法。An example of the manufacturing method (1) includes the above-mentioned attaching step, the protective film forming step, the first laminated body production step, the laminated body peeling step, the washing step, the laminated body peeling step, and the drying step, in this order. The method of peeling off and picking up the layered body.

製造方法(1)中，於保護膜形成步驟後進行積層體製作步驟(亦即第1積層體製作步驟)，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積層體製作步驟，於積層體製作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)」)。In the manufacturing method (1), the laminated body manufacturing step (that is, the first laminated body manufacturing step) is performed after the protective film forming step. In the manufacturing method of the semiconductor wafer of this embodiment, the protective film forming step may not be performed. In the laminated body production step, a protective film forming step is performed after the laminated body production step (this embodiment may be referred to as "manufacturing method (2)").

亦即，本實施形態的製造方法(製造方法(2))具有：將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，製作具備支撐片、設置於前述支撐片的一面(第1面)上之切斷後的前述保護膜形成用膜、及設置於前述切斷後的保護膜形成用膜之與前述支撐片側為相反側的面(本說明書中，有時稱為「第1面」)上之半導體晶片之積層體(以下，有時簡稱為「第2積層體」)之步驟(以下，有時簡稱為「第2積層體製作步驟」)；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，獲得具備支撐片、設置於前述支撐片的第1面上之切斷後(已切斷)的前述保護膜、及設置於前述切斷後的保護膜的第1面上之半導體晶片之第1積層體之步驟(保護膜形成步驟)；以及將前述第1積層體中之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)；進而，於前述第2積層體製作步驟與前述拾取步驟之間，具有將固定於台上之前述第2積層體或第1積層體自前述台扯離之步驟(以下，有時簡稱為「積層體扯離步驟」)；於前述積層體扯離步驟中，固定於台上之前述第2積層體或第1積層體於該積層體之前述支撐片側的最表層的表面接觸於前述台，前述台之前述第2積層體或第1積層體的固定面為陶瓷製或不銹鋼製。 圖16係用於以示意方式說明此種製造方法(2)的一實施形態之剖視圖。That is, the manufacturing method (manufacturing method (2)) of this embodiment includes: a step of attaching the protective film-forming film in the protective film-forming composite sheet to a semiconductor wafer (attachment step); and dividing the semiconductor wafer. wafer, cutting the protective film forming film, and producing a supporting sheet, the cut protective film forming film provided on one side (first surface) of the supporting sheet, and the protective film provided after cutting The laminated body of semiconductor wafers (hereinafter, sometimes referred to as the "second laminated body") on the side of the film for formation opposite to the side of the supporting sheet (hereinafter, sometimes referred to as the "first side") Step (hereinafter, sometimes simply referred to as the "second laminated body production step"); hardening the protective film forming film (protective film forming film after cutting) attached to the semiconductor wafer to form a protective film, A first laminated body including a support sheet, the cut (cut) protective film provided on the first surface of the support sheet, and the semiconductor wafer provided on the first surface of the cut protective film is obtained. a step (protective film forming step); and a step of picking up the semiconductor wafer having the cut protective film in the first laminated body from the supporting sheet (picking up step); and further, in the second step Between the laminated body production step and the aforementioned picking-up step, there is a step of peeling off the second laminated body or the first laminated body fixed on the table from the aforementioned table (hereinafter, sometimes referred to as the "laminated body peeling step") ; In the step of pulling off the laminated body, the surface of the outermost layer of the second laminated body or the first laminated body fixed on the table on the front support sheet side of the laminated body is in contact with the aforementioned table, and the aforementioned second laminated body is in front of the table The body or the fixing surface of the first laminated body is made of ceramic or stainless steel. FIG. 16 is a cross-sectional view schematically illustrating an embodiment of the manufacturing method (2).

製造方法(2)中，於使用圖1所示之保護膜形成用複合片101之情形時，如圖16A所示，亦與製造方法(1)之情形同樣地，自保護膜形成用膜101移除剝離膜15。In the manufacturing method (2), when the composite sheet 101 for protective film formation shown in FIG. 1 is used, as shown in FIG. 16A , similarly to the case of the manufacturing method (1), the self-protective film forming film 101 Remove the release film 15.

製造方法(2)的前述貼附步驟亦可如圖16B所示，利用與製造方法(1)的貼附步驟相同的方法(如圖14B所示)進行。The aforementioned attaching step of the manufacturing method (2) can also be performed using the same method as the attaching step of the manufacturing method (1) as shown in FIG. 16B (as shown in FIG. 14B).

製造方法(2)的貼附步驟後，於前述第2積層體製作步驟中，分割半導體晶圓9，切斷保護膜形成用膜13，如圖16C所示，製作具備支撐片10、設置於支撐片10的第1面10a上之切斷後的保護膜形成用膜130、及設置於切斷後的保護膜形成用膜130的第1面130a上之半導體晶片9'之第2積層體902。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)。第2積層體902中存在多個具備切斷後的保護膜形成用膜130之半導體晶片9'。After the attaching step of the manufacturing method (2), in the second laminated body manufacturing step mentioned above, the semiconductor wafer 9 is divided, and the protective film forming film 13 is cut. As shown in FIG. 16C, a supporting sheet 10 is produced, which is placed on The cut protective film forming film 130 is on the first surface 10 a of the support sheet 10 , and the second laminate 902 of the semiconductor wafer 9 ′ is provided on the first surface 130 a of 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'. In the second laminated body 902, there are a plurality of semiconductor wafers 9' provided with the cut protective film forming films 130.

製造方法(2)的第2積層體製作步驟後，於前述保護膜形成步驟中，使切斷後的保護膜形成用膜130硬化，如圖16D所示，於半導體晶片9'形成保護膜130'。藉此，獲得具備支撐片10、設置於支撐片10的第1面10a上之切斷後的保護膜130'、及設置於切斷後的保護膜130'的第1面130a'上之半導體晶片9'之第1積層體901。 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。製造方法(2)的保護膜形成步驟所獲得之第1積層體901與製造方法(1)的第1積層體製作步驟所獲得之第1積層體901相同。 藉由進行本步驟，獲得製造方法(1)的第1積層體製作步驟結束後、亦即與圖14D相同狀態的附保護膜之半導體晶片。After the second laminated body production step of the manufacturing method (2), in the protective film forming step, the cut protective film forming film 130 is cured to form a protective film 130' on the semiconductor wafer 9' as shown in FIG. 16D. . Thereby, the semiconductor wafer 9 is obtained including the support sheet 10, the cut protective film 130' provided on the first surface 10a of the support sheet 10, and the cut protective film 130' provided on the first surface 130a'. 'The first layered body 901. 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). The first laminated body 901 obtained in the protective film forming step of the manufacturing method (2) is the same as the first laminated body 901 obtained in the first laminated body manufacturing step of the manufacturing method (1). By performing this step, a semiconductor wafer with a protective film in the same state as in FIG. 14D is obtained after the first laminated body production step of the manufacturing method (1) is completed.

製造方法(2)的第2積層體製作步驟後，在前述拾取步驟之前，前述積層體扯離步驟中，將固定於台上之第1積層體或第2積層體自前述台扯離。After the second laminated body production step of the manufacturing method (2) and before the aforementioned picking-up step, in the aforementioned laminated body pulling-off step, the first laminated body or the second laminated body fixed on the table is pulled away from the aforementioned table.

例如，於前述第2積層體製作步驟後，為了進行保護膜形成步驟，必須搬運第2積層體902。另外，於前述第2積層體製作步驟後，可進行：將來自半導體晶圓9或保護膜形成用膜13且附著於第2積層體902之切削屑自第2積層體902沖洗而去除之步驟(亦即洗淨步驟)；使利用前述洗淨步驟洗淨後的第2積層體902乾燥而將洗淨時所附著之水去除之步驟(亦即乾燥步驟)，在這些步驟之前，亦必須搬運第2積層體902。這些洗淨步驟及乾燥步驟、以及各步驟間的第2積層體902之搬運除使用第2積層體902代替第1積層體901之方面以外，可利用與製造方法(1)之情形相同的方法進行。 在此種第2積層體902之搬運之前，將第2積層體902自前述台扯離時，可將與於製造方法(1)中，如圖15C所示，將固定於台6上之第1積層體901自台6扯離之情形相同的方法應用於第2積層體902。並且，該情形時，亦與製造方法(1)之情形同樣地，藉由保護膜形成用複合片101中的背面抗靜電層17的第2面17b滿足上述之表面電阻率及靜摩擦力之條件，因帶電所致之半導體晶片9'中的電路的破壞得到抑制。For example, in order to perform the protective film forming step after the above-mentioned second laminated body production step, the second laminated body 902 must be transported. In addition, after the above-mentioned second laminated body production step, a step of rinsing and removing cutting chips from the semiconductor wafer 9 or the protective film forming film 13 and adhering to the second laminated body 902 may be performed. (i.e., the washing step); the step of drying the second laminated body 902 washed by the aforementioned washing step to remove the water attached during washing (i.e., the drying step). Before these steps, it is also necessary to The second laminated body 902 is transported. These washing steps, drying steps, and the transportation of the second laminated body 902 between each step can be performed in the same manner as in the manufacturing method (1), except that the second laminated body 902 is used instead of the first laminated body 901. conduct. Before transporting the second laminated body 902, when the second laminated body 902 is pulled away from the aforementioned table, the second laminated body 902 can be fixed on the table 6 in the manufacturing method (1) as shown in FIG. 15C. The same method as when the first laminated body 901 is separated from the stage 6 is applied to the second laminated body 902. In addition, in this case, as in the case of the manufacturing method (1), the second surface 17b of the back antistatic layer 17 in the protective film forming composite sheet 101 satisfies the above-mentioned conditions of surface resistivity and static friction. , damage to the circuit in the semiconductor chip 9' caused by charging is suppressed.

另一方面，例如於保護膜形成步驟後，為了進行前述拾取步驟，必須搬運第1積層體901。此時的第1積層體901之搬運可利用與製造方法(1)之情形相同的方法進行。並且，將第1積層體901自前述台扯離時，應用與於製造方法(1)中，如圖15C所示，將固定於台6上之第1積層體901自台6扯離之情形相同的方法即可。該情形時，亦與製造方法(1)之情形同樣地，藉由保護膜形成用複合片101'中的背面抗靜電層17的第2面17b滿足上述之表面電阻率及靜摩擦力之條件，因帶電所致之半導體晶片9'中的電路的破壞得到抑制。On the other hand, for example, after the protective film forming step, the first laminated body 901 must be transported in order to perform the aforementioned pickup step. At this time, the first laminated body 901 can be transported by the same method as in the case of the manufacturing method (1). Moreover, when the first laminated body 901 is pulled away from the aforementioned table, it is applied to the manufacturing method (1). As shown in FIG. 15C, the first laminated body 901 fixed on the table 6 is pulled away from the table 6. Just the same method. In this case, similarly to the case of the manufacturing method (1), the second surface 17b of the back antistatic layer 17 in the protective film forming composite sheet 101' satisfies the above-mentioned surface resistivity and static friction conditions, Damage to the circuit in the semiconductor chip 9' due to electrification is suppressed.

製造方法(2)的前述拾取步驟中，如圖16E所示，將第1積層體901中之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15D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中，電路的破壞亦得到了抑制。In the aforementioned pickup step of the manufacturing method (2), as shown in FIG. 16E , the semiconductor wafer 9' having the cut protective film 130' in the first laminated body 901 is pulled away from the supporting sheet 10 and picked up. The picking-up step in the manufacturing method (2) can be performed using the same method as the picking-up step in the manufacturing method (1) (as shown in FIG. 15D ). Through the above steps, the target semiconductor wafer 9' is obtained as a semiconductor wafer with a protective film. In the semiconductor wafer with a protective film obtained by the manufacturing method (2), damage to the circuit is also suppressed.

作為製造方法(2)的一例，可列舉依序具有貼附步驟、第2積層體製作步驟、積層體扯離步驟、洗淨步驟、積層體扯離步驟、乾燥步驟、積層體扯離步驟、保護膜形成步驟、積層體扯離步驟及拾取步驟之方法。An example of the manufacturing method (2) includes an attaching step, a second laminated body production step, a laminated body peeling step, a washing step, a laminated body peeling step, a drying step, and a laminated body peeling step in this order. The protective film forming step, the laminate separation step and the method of picking up the step.

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：將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，製作具備支撐片、設置於前述支撐片的一面(第1面)上之切斷後的前述保護膜形成用膜、及設置於前述切斷後的保護膜形成用膜之與前述支撐片側為相反側的面(第1面)上之半導體晶片之積層體(第2積層體)之步驟(第2積層體製作步驟)；將前述第2積層體中之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，獲得具備切斷後(已切斷)的前述保護膜之半導體晶片之步驟(保護膜形成步驟)；進而，於前述第2積層體製作步驟與前述拾取步驟之間，具有將固定於台上之前述第2積層體自前述台扯離之步驟(以下，有時簡稱為「積層體扯離步驟」)；於前述積層體扯離步驟中，固定於台上之前述第2積層體於該第2積層體之前述支撐片側的最表層的表面接觸於前述台，前述台之前述第2積層體的固定面為陶瓷製或不銹鋼製。 圖17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 pickup step is performed after the protective film forming step. However, in the manufacturing method of the semiconductor wafer of this embodiment, the protective film forming step may not be performed and the pickup step may be performed. Then, a protective film forming step is performed (this embodiment may be referred to as "manufacturing method (3)"). That is, the manufacturing method (manufacturing method (3)) of this embodiment includes: a step of attaching the protective film-forming film in the protective film-forming composite sheet to a semiconductor wafer (attachment step); and dividing the semiconductor wafer. wafer, cutting the protective film forming film, and producing a supporting sheet, the cut protective film forming film provided on one side (first surface) of the supporting sheet, and the protective film provided after cutting The step of forming a laminated body (second laminated body) of semiconductor wafers on the side of the film opposite to the side of the supporting sheet (the first side) (second laminated body production step); The step of picking up the semiconductor wafer provided with the cut protective film-forming film from the supporting sheet (picking up step); and the step of attaching the protective film-forming film to the semiconductor wafer (cutting and The picked-up protective film forming film) is cured to form a protective film, and a semiconductor wafer having the protective film after cutting (cut) is obtained (protective film forming step); further, in the second laminated body production step Between the aforementioned picking-up step, there is a step of peeling off the second laminated body fixed on the table from the aforementioned table (hereinafter, sometimes referred to as the “laminated body peeling off step”); in the aforementioned laminated body peeling off step Before the second laminated body is fixed on the table, the surface of the outermost layer of the second laminated body on the side of the supporting piece is in contact with the table. The fixing surface of the second laminated body on the front side of the table is made of ceramic or stainless steel. FIG. 17 is a cross-sectional view schematically illustrating an embodiment of a manufacturing method of such a semiconductor wafer.

製造方法(3)中，於使用圖1所示之保護膜形成用複合片101之情形時，如圖17A所示，亦與製造方法(1)之情形同樣地，自保護膜形成用膜101移除剝離膜15。In the manufacturing method (3), when the composite sheet 101 for protective film formation shown in FIG. 1 is used, as shown in FIG. 17A , the self-protective film forming film 101 is also similar to the case of the manufacturing method (1). Remove the release film 15.

製造方法(3)的前述貼附步驟及第2積層體製作步驟可分別如圖17B至圖17C所示，利用與製造方法(2)的貼附步驟及第2積層體製作步驟相同的方法(如圖15B至圖15C所示)進行。The aforementioned attaching step and the second laminated body manufacturing step of the manufacturing method (3) can be performed as shown in Figures 17B to 17C respectively, using the same method as the attaching step and the second laminated body manufacturing step of the manufacturing method (2) ( (as shown in Figure 15B to Figure 15C).

製造方法(3)的第2積層體製作步驟後，在前述拾取步驟之前，於前述積層體扯離步驟中，將固定於台上之第2積層體自前述台扯離。After the second laminated body production step of the manufacturing method (3) and before the aforementioned picking-up step, in the aforementioned laminated body pulling-off step, the second laminated body fixed on the table is pulled away from the aforementioned table.

例如，於前述第2積層體製作步驟後，為了進行前述拾取步驟，必須搬運第2積層體902。另外，於前述第2積層體製作步驟後，可進行：將來自半導體晶圓9或保護膜形成用膜13且附著於第2積層體902之切削屑自第2積層體902沖洗而去除之步驟(亦即洗淨步驟)；使利用前述洗淨步驟洗淨後的第2積層體902乾燥而將洗淨時所附著之水去除之步驟(亦即乾燥步驟)，在這些步驟之前，亦必須搬運第2積層體902。這些洗淨步驟及乾燥步驟、以及各步驟間的第2積層體902之搬運除使用第2積層體902代替第1積層體901之方面以外，可利用與製造方法(1)之情形相同的方法進行。 在此種第2積層體902之搬運之前，將第2積層體902自前述台扯離時，可將與於製造方法(1)中，如圖15C所示，將固定於台6上之第1積層體901自台6扯離之情形相同的方法應用於第2積層體902。並且，該情形時，亦與製造方法(1)之情形同樣地，藉由保護膜形成用複合片101中的背面抗靜電層17的第2面17b滿足上述之表面電阻率及靜摩擦力之條件，因帶電所致之半導體晶片9'中的電路的破壞得到抑制。For example, after the second laminated body production step, in order to perform the picking step, the second laminated body 902 must be transported. In addition, after the above-mentioned second laminated body production step, a step of rinsing and removing cutting chips from the semiconductor wafer 9 or the protective film forming film 13 and adhering to the second laminated body 902 may be performed. (that is, the washing step); the step of drying the second laminated body 902 washed by the aforementioned washing step to remove the water attached during washing (that is, the drying step). Before these steps, it is also necessary to The second laminated body 902 is transported. These washing steps, drying steps, and the transportation of the second laminated body 902 between each step can be performed in the same manner as in the manufacturing method (1), except that the second laminated body 902 is used instead of the first laminated body 901. conduct. Before transporting the second laminated body 902, when the second laminated body 902 is pulled away from the aforementioned table, the second laminated body 902 can be fixed on the table 6 in the manufacturing method (1) as shown in FIG. 15C. The same method as when the first laminated body 901 is separated from the stage 6 is applied to the second laminated body 902. In this case, as in the case of the manufacturing method (1), the second surface 17b of the back antistatic layer 17 in the protective film forming composite sheet 101 satisfies the above-mentioned conditions of surface resistivity and static friction. , damage to the circuit in the semiconductor chip 9' caused by charging is suppressed.

製造方法(3)的前述拾取步驟中，如圖17D所示，將第2積層體902中之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15D及圖16E所示)進行。In the aforementioned pickup step of the manufacturing method (3), as shown in FIG. 17D , the semiconductor wafer 9 ′ provided with the cut protective film forming film 130 in the second laminated body 902 is pulled away from the supporting sheet 10 and picked up. The picking-up step in the manufacturing method (3) can be performed using the same method as the picking-up steps in the manufacturing methods (1) and (2) (as shown in FIG. 15D and FIG. 16E ).

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17E所示，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中，電路的破壞亦得到了抑制。In the aforementioned protective film forming step of the manufacturing method (3), the picked up protective film forming film 130 is cured to form a protective film 130' as shown in FIG. 17E. 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 steps in the manufacturing methods (1) and (2). When the protective film-forming film 13 is energy ray curable, the protective film forming step in the manufacturing method (3) does not require irradiation of energy rays to the protective film-forming film 130 through the support sheet 10. In addition to this aspect, it can be utilized The same method as the protective film formation step in the manufacturing methods (1) and (2) is performed. Through the above steps, the target semiconductor wafer 9' is obtained as a semiconductor wafer with a protective film. In the semiconductor wafer with a protective film obtained by the manufacturing method (3), damage to the circuit is also suppressed.

作為製造方法(3)的一例，可列舉依序具有貼附步驟、第2積層體製作步驟、積層體扯離步驟、洗淨步驟、積層體扯離步驟、乾燥步驟、積層體扯離步驟、拾取步驟及保護膜形成步驟之方法。An example of the manufacturing method (3) includes an attaching step, a second laminated body production step, a laminated body peeling step, a washing step, a laminated body peeling step, a drying step, and a laminated body peeling step, in this order. The method of picking up step and protective film forming step.

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，前述第1積層體製作步驟或第2積層體製作步驟中，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 explained 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 first laminated body manufacturing step or the second laminated body manufacturing step, the step of forming the modified layer inside the semiconductor wafer 9 only needs to be before the step of dividing the semiconductor wafer 9 at the location of the modified layer. stage, it can be carried out at any stage, for example, it can be carried out at any stage before the attaching step, between the attaching step and the protective film forming step.

至此已對使用圖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。So far, the method of manufacturing a semiconductor wafer using the protective film forming composite sheet 101 shown in FIG. 1 has been described. However, the method of manufacturing a semiconductor wafer of the present invention is not limited to this. For example, the manufacturing method of the 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 Figures 11 to 13, the protective film forming composite sheet 401 and the protective film forming composite sheet 501, etc. The protective film formation shown in Figure 1 Semiconductor wafers can be manufactured in the same manner using composite sheets for forming protective films other than the composite sheet 101 . In this way, when the composite sheet for protective film formation of another embodiment is used, as long as the addition, change, deletion, etc. of steps in the above-mentioned manufacturing method are appropriately performed to manufacture a semiconductor wafer based on the difference in the structure of these sheets, that is, 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進行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]◇Manufacturing method of semiconductor device After obtaining a semiconductor wafer with a protective film through the above-mentioned manufacturing method, the semiconductor wafer is flip-chip connected to the circuit surface of the substrate by a known method, and then a semiconductor package is produced. By using the semiconductor package, it is possible to The target semiconductor device (illustration omitted) is manufactured. [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 through specific examples. However, the present invention is not limited to the Examples shown below at all.

[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 following shows antistatic compositions used in Examples or Comparative Examples. 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」)[Raw materials for manufacturing compositions for forming protective films] The raw materials used for manufacturing 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 made from (weight average molecular weight 400000, glass transition temperature -1℃) [Thermosetting ingredient (B)] ・Epoxy resin (B1) (B1)-1: Bisphenol A type epoxy resin ("jER1055" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 800g/eq to 900g/eq) (B1)-2: Bisphenol A type epoxy resin ("BPA328" manufactured by Nippon Shokubai Co., Ltd., epoxy equivalent 235g/eq) (B1)-3: Dicyclopentadiene-type epoxy resin ("Epiclon HP-7200HH" manufactured by DIC Corporation, epoxy equivalent 274g/eq to 286g/eq) ・Thermal hardener (B2) (B2)-1: Dicyandiamide (heat-active latent epoxy resin hardener, "DICY7" manufactured by Mitsubishi Chemical Corporation, active hydrogen content 21g/eq) [Harding 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, a silica filler surface-modified with an epoxy compound, average particle size 500nm) [Color(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] [Manufacture of composite sheet for protective film formation] [Production of thermosetting protective film forming composition (III-1)] 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), thermal hardener (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 further diluted with methyl ethyl ketone so that the total concentration of these components became 55 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。[Manufacture of film for protective film formation] A release film ("SP-PET381031" manufactured by Lintec Co., Ltd., thickness 38 μm) made of polyethylene terephthalate and subjected to release treatment by polysiloxane treatment on one side. The thermosetting protective film-forming composition (III-1) obtained above was applied to the peeling-treated surface and dried at 100° C. for 2 minutes to produce a thermosetting protective film-forming film with a thickness of 40 μm.

[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 the base material, prepare the following polypropylene base material (thickness 80 μm). The surface roughness Ra of one side is 0.2 μm, and the surface roughness Ra of the other side is less than this value. In this way, one side has an uneven surface and the other side has a smooth surface. . The antistatic composition (VI-1)-1 is coated on the uneven surface of the polypropylene base material using a rod coater and dried at 100° C. for 2 minutes, thereby forming a thickness on the base material. 75nm backside 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。[Production of adhesive composition (I-4)] A non-energy ray curable adhesive composition (I-4) containing an acrylic polymer (100 parts by mass) and bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation) was prepared. "JER828") (based on the amount of the above-mentioned epoxy resin as 30 parts by mass), and a trifunctional xylylene diisocyanate-based cross-linking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (based on the above-mentioned cross-linking The amount of the agent is 35 parts by mass), and further contains methyl ethyl ketone as a solvent, and the total concentration of the acrylic polymer, epoxy resin and cross-linking agent is 35 mass %. The weight average of the acrylic polymer copolymerized 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之黏著劑層的露出面(換言之，黏著劑層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之基材的露出面(換言之，基材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積層而構成之附剝離膜之支撐片。[Manufacture of support sheet] The same release film ("SP-PET381031" manufactured by Lintec Co., Ltd., thickness 38 μm) as the release film used in the above-mentioned production of the protective film-forming film was used, and the resultant obtained above was applied to the release-treated surface of the release film. 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), the base material and the back surface obtained above are antistatic. The exposed surface of the base material in the laminate of the layers (in other words, the surface of the base material opposite to the back antistatic layer side) is bonded together. Thereby, a support sheet with a release film is produced, in which the back antistatic layer, the base material, the adhesive layer and the release film are sequentially laminated in the thickness direction of these layers.

[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之保護膜形成用膜的露出面(換言之，保護膜形成用膜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。[Manufacture of composite sheet for protective film formation] From the support sheet obtained above, remove the release film. Then, the exposed surface of the newly formed adhesive layer in the support sheet (in other words, the surface of the adhesive layer opposite to the base material side), the release film and the protective film forming film obtained above are laminated. The exposed surface of the protective film forming film (in other words, the surface of the protective film forming film opposite to the peeling film side) is bonded. In this way, the back antistatic layer (thickness 75 nm), the base material (thickness 80 μm), the adhesive layer (thickness 5 μm), the protective film forming film (thickness 40 μm), and the peeling film (thickness 38 μm) were obtained in this order. A composite sheet for forming a protective film composed of stacked layers in the thickness direction. In this protective film-forming composite sheet, 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 a circle with a diameter of 270 mm, and the protective film-forming film and peel The planar shape of the film laminate was a circle with a diameter of 210 mm, and these two circles were made concentric. Next, the peeling film is removed, and the peripheral edge of the protective film forming film on the exposed surface of the protective film forming film (in other words, the surface of the protective film forming film opposite to the adhesive layer side, or the first surface) In the area near the bottom, an adhesive layer for the jig is provided. Then, the same release film ("SP-PET381031" manufactured by Lintec Corporation) as the release film removed previously was bonded to the first surface of the protective film forming film and the first surface of the jig adhesive layer. Thickness 38μm). Through the above steps, a composite sheet for protective film formation with a release film is produced. The composite sheet has the structure shown in FIG. 1 and the size of the protective film forming film is slightly smaller than the size of the support sheet. Table 1 shows each layer constituting the composite sheet for protective film formation. When "-" is written in the layer column, it means that the composite sheet for forming a protective film does not have this layer.

[保護膜形成用複合片之評價] [保護膜形成用膜進行熱硬化前的保護膜形成用複合片的表面電阻率之測定] 使用表面電阻率計(Advantest公司製造的「R12704 Resistivity chamber」)，不使上述所獲得之保護膜形成用複合片中的保護膜形成用膜熱硬化，而將施加電壓設為100V，於該片中的背面抗靜電層之與基材側為相反側的露出面，測定表面電阻率。結果示於表1中的「保護膜形成用複合片熱硬化前的表面電阻率(Ω/□)」一欄。[Evaluation of composite sheet for protective film formation] [Measurement of the surface resistivity of the protective film-forming composite sheet before the protective film-forming film is thermally cured] Using a surface resistivity meter ("R12704 Resistivity chamber" manufactured by Advantest Co., Ltd.), the protective film-forming film in the protective film-forming composite sheet obtained above was not thermally cured, but the applied voltage was set to 100V. Measure the surface resistivity of the exposed surface of the back antistatic layer opposite to the substrate side. The results are shown in the column "Surface resistivity (Ω/□) of the composite sheet for protective film formation before thermosetting" in Table 1.

[保護膜形成用膜進行熱硬化後的保護膜形成用複合片的表面電阻率之測定] 使用測定了上述熱硬化前的表面電阻率之保護膜形成用複合片，使該複合片中的保護膜形成用膜於130℃熱硬化2小時。繼而，利用與上述相同的方法測定該熱硬化後的保護膜形成用複合片中的背面抗靜電層的表面電阻率。結果示於表1中的「保護膜形成用複合片熱硬化後的表面電阻率(Ω/□)」一欄。[Measurement of the surface resistivity of the protective film-forming composite sheet after the protective film-forming film was thermally cured] The composite sheet for protective film formation whose surface resistivity before thermal curing was measured was used, and the film for protective film formation in the composite sheet was thermally cured at 130° C. for 2 hours. Next, the surface resistivity of the back surface antistatic layer in the thermally cured composite sheet for forming a protective film was measured using the same method as described above. The results are shown in the column "Surface resistivity of the composite sheet for protective film formation after thermal curing (Ω/□)" in Table 1.

[保護膜形成用複合片的靜摩擦力之測定] 將上述所獲得之保護膜形成用複合片於70℃加熱1分鐘。繼而，藉由使用該加熱後的片，參照圖18進行說明之方法，測定背面抗靜電層的靜摩擦力。更具體而言，如下所述。 亦即，自上述之加熱後的保護膜形成用複合片，切取大小為10cm×20cm之試片。 將切割裝置中的8吋多孔台(DISCO公司製造的「MOKFRA05Z」) 載置於萬能材料試驗機(A&D公司製造的「RTG-1225」)，將前述試片載置於該多孔台上。此時，使試片中的背面抗靜電層接觸於多孔台的表面。 繼而，於該狀態的試片中的保護膜形成用膜的露出面，載置大小為6cm×10cm×2cm且質量為1kg之金屬重物。此時，使金屬重物之大小為6cm×10cm之面接觸於保護膜形成用膜。 繼而，沿相對於試片之與前述多孔台之接觸面為平行的方向，使前述重物以10mm/min之速度移動，測定此時的前述重物的即將開始移動前的荷重(峰值試驗力)，採用該測定值作為靜摩擦力。結果示於表1中的「保護膜形成用複合片的靜摩擦力」一欄。[Measurement of static friction force of composite sheet for protective film formation] The composite sheet for protective film formation obtained above was heated at 70° C. for 1 minute. Then, by using this heated sheet, the static friction force of the back antistatic layer was measured by the method described with reference to FIG. 18 . More specifically, as described below. That is, a test piece with a size of 10 cm×20 cm was cut out from the heated composite sheet for protective film formation. The 8-inch porous table ("MOKFRA05Z" manufactured by DISCO) in the cutting device was placed on the universal material testing machine ("RTG-1225" manufactured by A&D), and the aforementioned test piece was placed on the porous table. At this time, the back antistatic layer in the test piece was brought into contact with the surface of the porous stage. Next, a metal weight having a size of 6 cm×10 cm×2 cm and a mass of 1 kg was placed on the exposed surface of the protective film forming film of the test piece in this state. At this time, the surface of the metal weight having a size of 6 cm×10 cm was brought into contact with the protective film forming film. Then, move the weight at a speed of 10 mm/min in a direction parallel to the contact surface of the test piece with the porous platform, and measure the load (peak test force) immediately before the weight starts to move. ), and use this measured value as the static friction force. The results are shown in the column "Static friction force of composite sheet for protective film formation" in Table 1.

[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 total light transmittance of support sheet] For the support sheet obtained above, the total light transmittance (%) was measured using a spectrophotometer ("UV-VIS-NIR SPECTROPHOTOMETER UV-3600" manufactured by Shimadzu Corporation) in accordance with JIS K 7375:2008. 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] The scratch resistance of the backside antistatic layer in the support sheet obtained above was evaluated by the following method. That is, a flat abrasion testing machine "PA-2A" manufactured by Daiei Scientific Seiki Manufacturing Co., Ltd. was used, and the pressing surface of the head of the testing machine was covered with flannel cloth. The pressing surface is flat, and the area of the pressing surface is 2cm×2cm. As flannel cloth, use flannel cloth with a thickness within the range explained above. The pressing surface of the head covered with flannel cloth is pressed against the surface of the back antistatic layer. In this state, a load of 125g/ cm2 is applied to the back antistatic layer by the head while pressing. The head is moved back and forth 10 times in a straight line distance of 10cm, thereby applying a load of 125g/ cm2 through the flannel cloth while rubbing the antistatic layer on the back. Then, an area of 2 cm × 2 cm on the friction surface of the back antistatic layer was visually observed, and the case where no scratches were confirmed was judged as "A", and the case where scratches were confirmed was judged as "B", and the antistatic layer was evaluated. scratch resistance. The results are shown in the column "Scratch resistance of antistatic layer or substrate" in Table 1.

[半導體晶片之製造] 使用上述所獲得之保護膜形成用複合片，採用製造方法(1)，製造附保護膜之半導體晶片。此時，藉由依序進行前述貼附步驟、保護膜形成步驟、第1積層體製作步驟、積層體扯離步驟、洗淨步驟、積層體扯離步驟、乾燥步驟、積層體扯離步驟及拾取步驟，而製造附保護膜之半導體晶片。各步驟的更詳細的條件如下所示。[Manufacturing of semiconductor chips] Using the composite sheet for forming a protective film obtained above, a semiconductor wafer with a protective film is produced using the production method (1). At this time, by sequentially performing the aforementioned attaching step, protective film forming step, first laminated body production step, laminated body peeling step, washing step, laminated body peeling step, drying step, laminated body peeling step and picking up Steps to manufacture a semiconductor wafer with a protective film. More detailed conditions for each step are shown below.

亦即，前述貼附步驟中，作為半導體晶圓，使用8吋矽鏡面晶圓(厚度350μm)，對該晶圓之鏡面之面(內面)，藉由於70℃加熱1分鐘之保護膜形成用膜，貼附保護膜形成用複合片。That is, in the aforementioned attaching step, an 8-inch silicon mirror wafer (thickness 350 μm) is used as the semiconductor wafer, and the mirror surface (inner surface) of the wafer is formed with a protective film heated at 70°C for 1 minute. Use film to attach a protective film forming composite sheet.

前述保護膜形成步驟中，使保護膜形成用膜於130℃熱硬化2小時。In the aforementioned protective film forming step, the film for forming a protective film is thermally cured at 130° C. for 2 hours.

前述第1積層體製作步驟中，藉由使用切割裝置(Disco公司製造的「DFD6362」)進行切割，而分割矽鏡面晶圓，獲得大小為5mm×5mm之矽晶片。此時的切割係將切割刀片的移動速度設為50mm/sec、切割刀片的轉速設為30000rpm而進行。另外，此時同時保護膜亦被切斷。In the aforementioned first laminated body production step, the silicon mirror wafer is divided by cutting using a cutting device ("DFD6362" manufactured by Disco Corporation) to obtain silicon wafers with a size of 5 mm×5 mm. The cutting at this time was performed by setting the moving speed of the cutting blade to 50 mm/sec and the rotation speed of the cutting blade to 30,000 rpm. In addition, the protective film is also cut off at this time.

前述第1積層體製作步驟及其後的積層體扯離步驟中，使用台之第1積層體的固定面為陶瓷製且凹凸差為5μm以下之吸附台作為台。前述洗淨步驟及其後的積層體扯離步驟、以及前述乾燥步驟及其後的積層體扯離步驟之任一者中，均使用與第1積層體製作步驟及其後的積層體扯離步驟之情形同一種的吸附台。In the above-mentioned first laminated body production step and the subsequent laminated body separation step, an adsorption table whose fixed surface of the first laminated body is made of ceramic and has an unevenness of 5 μm or less is used as the table. In any of the aforementioned washing step and the subsequent laminated body separation step, and the aforementioned drying step and the subsequent laminated body separation step, the same as the first laminated body production step and the subsequent laminated body separation step are used. The steps are the same for the adsorption table.

前述乾燥步驟中，使洗淨後的第1積層體於室溫下進行送風乾燥。In the aforementioned drying step, the washed first laminated body is air-dried at room temperature.

前述拾取步驟中，使用拾取-黏晶裝置(Canon Machinery公司製造的「BESTEM D-02」)，於常溫，將乾燥後的第1積層體予以固定後，於該第1積層體與固定該第1積層體之環狀框架之間，新產生3mm之高低差。然後，以該狀態，自第1積層體之背面抗靜電層側施加力而頂起第1積層體，藉此將內面具備切斷後的保護膜之矽晶片(附保護膜之半導體晶片)自前述支撐片扯離而進行拾取。此時，作為頂起部，使用1個突起(頂銷)，將該頂起部的頂起高度設為0.6mm、頂起速度設為20mm/s、頂起保持時間設為30毫秒，頂起前述附保護膜之矽晶片。 藉由以上步驟，獲得大小為5mm×5mm且厚度為350μm之矽晶片作為半導體晶片。該半導體晶片的內面所具備之保護膜的大小與該半導體晶片的大小同等。In the aforementioned pick-up step, a pick-up and die-bonding device ("BESTEM D-02" manufactured by Canon Machinery Co., Ltd.) is used to fix the dried first laminated body at normal temperature, and then fix the first laminated body to the first laminated body. 1. A new height difference of 3 mm is created between the ring-shaped frames of the laminated body. Then, in this state, force is applied from the back antistatic layer side of the first laminated body to lift the first laminated body, whereby the silicon wafer (semiconductor wafer with protective film) having the cut protective film on its inner surface is removed from the first laminated body. The aforementioned supporting piece is pulled away to be picked up. At this time, a protrusion (ejector pin) is used as the jacking part, and the jacking height of the jacking part is set to 0.6mm, the jacking speed is set to 20mm/s, and the jacking holding time is set to 30 milliseconds. Start with the aforementioned silicon wafer with a protective film. Through the above steps, a silicon wafer with a size of 5 mm×5 mm and a thickness of 350 μm was obtained as a semiconductor wafer. The size of the protective film provided on the inner surface of the semiconductor wafer is equal to the size of the semiconductor wafer.

[半導體晶片之評價] [半導體晶片中的電路的破壞抑制性之評價] 利用以下所示之方法評價上述所獲得之附保護膜之半導體晶片中有無電路的破壞。 亦即，使用基板(WALTS公司製造的「WLP(s)400P-2」，3cm□)，使附保護膜之半導體晶片的凸塊形成面接觸於該基板，從而將該附保護膜之半導體晶片接合。前述基板於該基板的電路面中4邊的周緣部附近的區域，沿著邊具有多個電極。附保護膜之半導體晶片配置於前述基板的電路面的中央部，且使附保護膜之半導體晶片位於沿著前述基板的相向的2邊的周緣部配置之電極間。 繼而，使沿著前述基板的相向的2邊中的1邊配置之1個電極、及沿著其餘1邊配置之1個電極之兩者分別接觸測試機(日置電機公司製造的「Card HiTester 3244-60」)的端子各1根，以該狀態，進行利用前述測試機之導通試驗。進而，作為相向的2個電極，依序選擇其他組合，反復進行該導通試驗。並且，於利用測試機獲得之電阻的測定值無明確變化之情形時，判斷半導體晶片中的電路未遭破壞，而判定為「A」。相對於此，於利用測試機獲得之電阻的測定值有明確變化之情形時，判斷半導體晶片中的電路遭破壞，而判定為「B」。 結果示於表1中的「半導體晶片中的電路的破壞抑制性」一欄。[Evaluation of semiconductor chips] [Evaluation of damage suppression properties of circuits in semiconductor wafers] The presence or absence of circuit damage in the semiconductor wafer with a protective film obtained above was evaluated by the method shown below. That is, a substrate ("WLP (s) 400P-2" manufactured by WALTS Corporation, 3 cm□) is used, and the bump formation surface of the semiconductor wafer with a protective film is brought into contact with the substrate, so that the semiconductor wafer with a protective film is Engagement. The substrate has a plurality of electrodes along the sides in areas near the peripheral portions of four sides of the circuit surface of the substrate. The semiconductor wafer with a protective film is disposed in the center of the circuit surface of the substrate, and the semiconductor wafer with a protective film is positioned between electrodes disposed along the peripheral portions of two opposing sides of the substrate. Then, one electrode arranged along one of the two opposing sides of the substrate and one electrode arranged along the other side were brought into contact with a tester ("Card HiTester 3244 manufactured by Hioki Electric Co., Ltd." -60"), conduct a continuity test using the above-mentioned testing machine in this state. Furthermore, as two electrodes facing each other, other combinations are sequentially selected, and the conduction test is repeated. Furthermore, when there is no clear change in the resistance measurement value obtained by the tester, it is judged that the circuit in the semiconductor chip is not damaged, and the judgment is "A". On the other hand, when there is a clear change in the resistance measurement value obtained by the tester, it is judged that the circuit in the semiconductor chip is damaged, and the judgment is "B". The results are shown in the column "Destruction suppression properties of circuits in semiconductor wafers" in Table 1.

[保護膜形成用複合片之製造及評價、半導體晶片之製造及評價] [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，變更該組成物的塗佈量，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，皆利用與實施例1之情形相同的方法來製造及評價保護膜形成用複合片，製造及評價半導體晶片。本實施例所製造之保護膜形成用複合片係以下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 sheets for protective film formation, production and evaluation of semiconductor wafers] [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 composition, and dry at 50° C. for 1 minute to form a film on the substrate. The back surface antistatic layer having a thickness of 170 nm was used to produce and evaluate a protective film forming composite sheet and a semiconductor wafer in the same manner as in Example 1 except for these points. The composite sheet for forming a protective film produced in this example is a composite sheet for forming a protective film with a peeling film as follows: a back antistatic layer (thickness: 170 nm), a base material (thickness: 80 μm), and an adhesive layer (thickness: 5 μm) , a protective film forming film (thickness 40 μm) and a peeling film (thickness 38 μm) are laminated in order in the thickness direction of these layers, and the structure is as shown in Figure 1 and the size of the protective film forming film is larger than the size of the support sheet Slightly smaller. 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，皆利用與實施例2之情形相同的方法來製造及評價保護膜形成用複合片，製造及評價半導體晶片。本實施例所製造之保護膜形成用複合片係以下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 antistatic composition (VI-1)-2 was changed, and the thickness of the backside antistatic layer was set to 50 nm instead of 170 nm. Except for these aspects, the same method as in Example 2 was used to produce and Composite sheets for protective film formation were evaluated, and semiconductor wafers were produced and evaluated. The composite sheet for forming a protective film produced in this example is a composite sheet for forming a protective film with a release film as follows: a back antistatic layer (thickness 50 nm), a base material (thickness 80 μm), and an adhesive layer (thickness 5 μm). , a protective film forming film (thickness 40 μm) and a peeling film (thickness 38 μm) are laminated in order in the thickness direction of these layers, and the structure is as shown in Figure 1 and the size of the protective film forming film is larger than the size of the support sheet Slightly smaller. 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] [Manufacture of composite sheet for protective film formation] [Manufacture of antistatic substrate] A composition containing an acrylic urethane resin and a photopolymerization initiator, and the content of the photopolymerization initiator relative to the content of the acrylic urethane resin is 3% by mass, is prepared as an antistatic agent The phosphonium-based ionic liquid (an ionic liquid composed of a phosphonium salt) is stirred to obtain an energy ray-curable antistatic composition (VI-2). At this time, the ratio of the content of the antistatic agent to the total content of the antistatic agent and acrylic urethane resin in the antistatic composition (VI-2) was set to 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 Corporation) using an injection mold (fountain die). Lumirror T60 PET 50 T-60 Toray", 50μm thick product), forming a coating film with a thickness of 80μm. Then, an ultraviolet irradiation device ("ECS-401GX" manufactured by EYEGRAPHICS) was used, a high-pressure mercury lamp ("H04-L41" manufactured by EYEGRAPHICS) was used, 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 light amount was set to 175 mJ/cm 2 , and the coating film was irradiated with ultraviolet rays. Next, a release film ("SP-PET3801" manufactured by Lindec Corporation, thickness 38 μm) was used, and the release-treated surface of the release film was bonded to the ultraviolet irradiated coating film. Then, the same ultraviolet irradiation device and high-pressure mercury lamp as above were used, the height of the lamp was set to 150mm, the illumination intensity of the light with a wavelength of 365nm was set to 271mW/cm 2 , and the light amount was set to 600mJ/cm 2 , and the above-mentioned film was removed through the aforementioned peeling film. The coating film (more specifically, the acrylic urethane resin) is cured by ultraviolet rays by irradiating the coating film twice with ultraviolet rays. Then, from the ultraviolet cured coating film, the aforementioned process film and peeling film were removed to obtain an antistatic substrate containing polyacrylic urethane and phosphonium-based ionic liquid and having a thickness of 80 μm. In the obtained antistatic base material, the content of the antistatic agent was 9% by mass relative to the total content of the antistatic agent and polyacrylic urethane. This value is shown in the column "Antistatic agent (content ratio (mass %))" in Table 1.

[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積層而構成的附剝離膜之支撐片。[Manufacture 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 the release film ("SP-PET381031" manufactured by Lintec Corporation, thickness 38 μm). Next, 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) was placed with one side of the antistatic base material obtained above. Fit. Thereby, a support sheet with a release film is produced, in which an antistatic base material, an adhesive layer, and a release film are sequentially laminated in the thickness direction of these layers.

[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，皆利用與實施例1之情形相同的方法來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。[Manufacture of composite sheet for protective film formation] The support sheet having the antistatic base material obtained above was used instead of the aforementioned support sheet having the back antistatic layer and the base material. Except for this point, the same method as in Example 1 was used to produce a release film-attached film. Composite sheet for forming a protective film. The composite sheet for forming a protective film with a release film is composed of an antistatic base material (thickness 80 μm), an adhesive layer (thickness 5 μm), a film for forming a protective film (thickness 40 μm), and a release film ( Thickness: 38 μm), these layers are laminated sequentially in the thickness direction, and further includes an adhesive layer for a jig. In this composite sheet for forming a protective film with a peeling film, the planar shape of the laminate of the antistatic base material and the adhesive layer (in other words, the supporting sheet) is a circle with a diameter of 270 mm, and the film for forming a protective film and the peeling film are The planar shape of the film laminate is a circle with a diameter of 210 mm, and these two circles are concentric. The composite sheet for forming a protective film with a release film has a structure as shown in FIG. 6 , and the size of the film for forming a protective film is slightly smaller than the size of the supporting 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。保護膜形成用複合片的表面電阻率及靜摩擦力均於抗靜電性基材中進行測定，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 protective film formation] The composite sheet for protective film formation obtained above was evaluated in the same manner as in Example 1. The surface resistivity and static friction of the protective film-forming composite sheet were measured on the antistatic base material, and the scratch resistance was evaluated on the antistatic base material. The results are shown in Table 1.

[半導體晶片之製造及評價] 使用上述所獲得之保護膜形成用複合片，除該方面以外，皆利用與實施例1之情形相同的方法來製造及評價半導體晶片。結果示於表1。[Manufacturing and Evaluation of Semiconductor Chips] Using the composite sheet for protective film formation obtained above, a semiconductor wafer was produced and evaluated by the same method as in Example 1 except for this point. The results are shown in Table 1.

[保護膜形成用複合片之製造及評價、半導體晶片之製造及評價] [實施例5] 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，皆利用與實施例2之情形相同的方法來製造及評價保護膜形成用複合片，製造及評價半導體晶片。本實施例所製造之保護膜形成用複合片係以下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。[Production and evaluation of composite sheets for protective film formation, production and evaluation of semiconductor wafers] [Example 5] The coating amount of the antistatic composition (VI-1)-2 was changed, and the thickness of the backside antistatic layer was set to 15 nm instead of 170 nm. Except for these aspects, the same method as in Example 2 was used to produce and Composite sheets for protective film formation were evaluated, and semiconductor wafers were produced and evaluated. The composite sheet for forming a protective film produced in this example is a composite sheet for forming a protective film with a release film as follows: a back antistatic layer (thickness: 15 nm), a base material (thickness: 80 μm), and an adhesive layer (thickness: 5 μm) , a film for forming a protective film (thickness 40 μm) and a peeling film (thickness 38 μm) are laminated in order in the thickness direction of these layers, and further has an adhesive layer for a jig, and has the structure shown in Figure 1 and the protective film The size of the forming film is slightly smaller than the size of the supporting sheet. The results are shown in Table 1.

[比較例1] 不形成背面抗靜電層，除該方面以外，皆利用與實施例1之情形相同的方法來製造及評價保護膜形成用複合片，製造及評價半導體晶片。本比較例所製造之保護膜形成用複合片係以下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，保護膜形成用複合片的表面電阻率及靜摩擦力均於基材中進行測定，耐擦傷性之評價係對基材進行。 結果示於表1。[Comparative example 1] Except for not forming the backside antistatic layer, the composite sheet for protective film formation was manufactured and evaluated in the same manner as in Example 1, and the semiconductor wafer was manufactured and evaluated. The composite sheet for forming a protective film produced in this comparative example is a composite sheet for forming a protective film with a release film as follows: a base material (thickness 80 μm), an adhesive layer (thickness 5 μm), and a film for forming a protective film (thickness 40 μm). ) and a release film (thickness: 38 μm) are laminated sequentially in the thickness direction of these layers, and further has an adhesive layer for the jig, and does not have a back antistatic layer in Figure 1, and the size of the protective film forming film Slightly smaller than the size of the support piece. In addition, in this comparative example, the surface resistivity and static friction force of the protective film-forming composite sheet were measured on the base material, and the scratch resistance was evaluated on the base material. The results are shown in Table 1.

[比較例2] 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，皆利用與實施例4之情形相同的方法來製造及評價保護膜形成用複合片，製造及評價半導體晶片。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。 本比較例所製造之保護膜形成用複合片係以下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 2] A base material in which the content of the antistatic agent was reduced was used as the antistatic base material. Except for this point, the composite sheet for forming a protective film was produced and evaluated by the same method as in Example 4, and a semiconductor wafer was produced and evaluated. . In the obtained antistatic base material, the content of the antistatic agent was 3% by mass relative to the total content of the antistatic agent and polyacrylic urethane. This value is shown in the column "proportion of antistatic agent content" in Table 1. The composite sheet for forming a protective film produced in this comparative example is a composite sheet for forming a protective film with a release film as follows: an antistatic base material (thickness 80 μm), an adhesive layer (thickness 5 μm), and a film for forming a protective film. (thickness: 40 μm) and a peeling film (thickness: 38 μm) are laminated sequentially in the thickness direction of these layers, and further includes a jig adhesive layer. The structure is shown in Figure 6 and the size of the protective film forming film is relatively large. The size of the support piece is slightly smaller. 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 實施例5 比較例1 比較例2 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 (nm) 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(含量之比率(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熱硬化前的表面電阻率(Ω/□) 2.1×105 2.8×108 4.1×108 3.5×1010 4.0×108 5.0×1015 1.5×1011 保護膜形成用複合片的熱硬化後的表面電阻率(Ω/□) 1.3×106 1.7×109 5.3×109 9.2×1010 5.0×109 5.6×1015 8.4×1011 保護膜形成用複合片的靜摩擦力(N) 12 16 14 18 12 11 18 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 A B A 半導體晶片中的電路的破壞抑制性 A A A A A B B [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1 Comparative example 2 Composition of composite sheet for protective film formation Film for protective film formation Hardening Thermal hardening Thickness(μm) 40 adhesive layer Hardening Non-energy line hardenability Thickness(μm) 5 base material Main material polypropylene - polypropylene - Thickness(μm) 80 - 80 - antistatic layer Back antistatic layer Main material Polypyrrole PEDOT/PSS - PEDOT/PSS - - Thickness(nm) 75 170 50 - 15 - - Antistatic substrate Main material - - - polyacrylic urethane - - polyacrylic urethane Thickness(μm) - - - 80 - - 80 Antistatic agent (content ratio (mass %)) - - - Phosphonium ionic liquid(9) - - Phosphonium ionic liquid(3) Evaluation results Surface resistivity of composite sheet for protective film formation before thermal curing (Ω/□) 2.1×10 5 2.8×10 8 4.1×10 8 3.5×10 10 4.0×10 8 5.0×10 15 1.5×10 11 Surface resistivity of composite sheet for protective film formation after thermal curing (Ω/□) 1.3×10 6 1.7×10 9 5.3×10 9 9.2×10 10 5.0×10 9 5.6×10 15 8.4×10 11 Static friction force of composite sheet for protective film formation (N) 12 16 14 18 12 11 18 Total light transmittance of the support sheet (%) 80 91 91 91 92 92 93 Scratch resistance of antistatic layer or substrate A A A A A B A Damage suppression of circuits in semiconductor wafers A A A A A B B

由上述結果可明確，實施例1至實施例5的保護膜形成用複合片中，背面抗靜電層或抗靜電性基材的表面電阻率於使保護膜形成用膜熱硬化前為2.1×105 Ω/□至3.5×1010 Ω/□，於使保護膜形成用膜熱硬化後為1.3×106 Ω/□至9.2×1010 Ω/□，這些保護膜形成用複合片於平常時抗靜電性優異。並且，使用這些保護膜形成用複合片所獲得之半導體晶片中，電路未遭破壞。這些保護膜形成用複合片中，背面抗靜電層或抗靜電性基材的靜摩擦力為12N至18N，將固定於台上之前述積層體(亦即，第1積層體或第2積層體)自台上的固定面扯離時，前述積層體的帶電抑制效果高。From the above results, it is clear that in the protective film-forming composite sheets of Examples 1 to 5, the surface resistivity of the back antistatic layer or the antistatic base material before the protective film-forming film is thermally cured is 2.1×10 5 Ω/□ to 3.5×10 10 Ω/□, and 1.3×10 6 Ω/□ to 9.2×10 10 Ω/□ after the protective film-forming film is thermally cured. These protective film-forming composite sheets are normally used Excellent antistatic properties. Furthermore, circuits in the semiconductor wafers obtained using these protective film-forming composite sheets were not damaged. In these protective film-forming composite sheets, the static friction force of the back antistatic layer or the antistatic base material is 12N to 18N, and the above-mentioned laminated body (that is, the first laminated body or the second laminated body) is fixed on the table. The laminated body has a high charge suppression effect when it is pulled away from the fixed surface on the table.

實施例1至實施例5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92%)，這些複合片具有較佳的光學特性。The total light transmittance of the support sheet in the protective film forming composite sheets of Examples 1 to 5 is above 80% (80% to 92%), and these composite sheets have better optical properties.

實施例1至實施例3、實施例5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 backside antistatic layer in the composite sheet for protective film formation in Examples 1 to 3 and Example 5, and the antistatic base material in the composite sheet for protective film formation in Example 4 all have high scratch resistance. The protective film-forming films of these composite sheets have good inspection properties.

相對於此，比較例1的保護膜形成用複合片中，基材的表面電阻率於使保護膜形成用膜熱硬化前為5.0×1015 Ω/□，於使保護膜形成用膜熱硬化後為5.6×1015 Ω/□，該保護膜形成用複合片於平常時抗靜電性差。並且，使用該保護膜形成用複合片所獲得之半導體晶片中，電路遭破壞。該保護膜形成用複合片中，基材的靜摩擦力為11N，但由於該片的抗靜電性低，故而將固定於台上之積層體自台上的固定面扯離時，前述積層體的帶電抑制效果低。On the other hand, in the protective film-forming composite sheet of Comparative Example 1, the surface resistivity of the base material was 5.0×10 15 Ω/□ before the protective film-forming film was thermally cured. The final value is 5.6×10 15 Ω/□. The composite sheet for forming a protective film has poor antistatic properties under normal conditions. Furthermore, in the semiconductor wafer obtained using the composite sheet for forming a protective film, the circuit was damaged. In this protective film-forming composite sheet, the static friction force of the base material is 11N. However, since the antistatic property of this sheet is low, when the laminated body fixed on the table is pulled away from the fixed surface of the table, the laminated body's friction force is 11N. The charging suppression effect is low.

比較例2的保護膜形成用複合片中，抗靜電性基材的表面電阻率於使保護膜形成用膜熱硬化前為1.5×1011 Ω/□，於使保護膜形成用膜熱硬化後為8.4×1011 Ω/□，該保護膜形成用複合片於平常時抗靜電性差。並且，使用該保護膜形成用複合片所獲得之半導體晶片中，電路遭破壞。該保護膜形成用複合片中，基材的靜摩擦力為18N，但由於該片的抗靜電性低，故而將固定於台上之積層體自台上的固定面扯離時，前述積層體的帶電抑制效果低。In the protective film-forming composite sheet of Comparative Example 2, the surface resistivity of the antistatic base material was 1.5×10 11 Ω/□ before the protective film-forming film was thermally cured, and after the protective film-forming film was thermally cured. It is 8.4×10 11 Ω/□, and the composite sheet for forming a protective film has poor antistatic properties under normal conditions. Furthermore, in the semiconductor wafer obtained using the composite sheet for forming a protective film, the circuit was damaged. In this protective film-forming composite sheet, the static friction force of the base material is 18N. However, since the antistatic property of this sheet is low, when the laminated body fixed on the table is pulled away from the fixed surface of the table, the laminated body's friction force is The charging suppression effect is low.

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 scratch resistance of the base material in the protective film-forming composite sheet of Comparative Example 1 was low, and the protective film-forming film of this composite sheet had poor inspection properties. [Industrial Availability]

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

1:試片 1a:試片之與支撐片側為相反側的最表層的表面(露出面) 1b:試片之支撐片側的最表層的露出面(表面) 4:多孔台 4a:多孔台的表面 5:重物 5b:重物之與試片之接觸面 6,7:台 6a,7a:台的固定面 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 17b:背面抗靜電層的第2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 19b:表面抗靜電層的第2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 130a:切斷後的保護膜形成用膜的第1面 130':切斷後的保護膜 130a':切斷後的保護膜的第1面 901:第1積層體 902:第2積層體 I:拾取方向 II:重物的移動方向1: test piece 1a: The outermost surface (exposed surface) of the test piece on the side opposite to the supporting piece 1b: The exposed surface (surface) of the outermost layer of the support piece side of the test piece 4:Porous table 4a: Surface of porous table 5:Heavy objects 5b: The contact surface between the weight and the test piece 6,7: Taiwan 6a,7a: Fixed surface of the table 8: Break away from the organization 9:Semiconductor wafer 9b: Inner surface of 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 piece 11:Substrate 11a:Side 1 of the substrate 11b:Side 2 of the substrate 11': Antistatic base material 11a': The first side of the antistatic substrate 11b': The second side of the antistatic substrate 12: Adhesive layer 12a: Side 1 of adhesive layer 13,23: Film for protective film formation 13a, 23a: The first side of the protective film forming film 13':Protective film 15: Peel off film 16: Adhesive layer for fixtures 16a: The first side of the adhesive layer for the jig 16c: Side of the adhesive layer for the jig 17: Antistatic layer on the back 17a: The first side of the back antistatic layer 17b: The second side of the antistatic layer on the back 18:Middle layer 18a: Side 1 of the middle layer 18b: Side 2 of the middle layer 18c: Side of middle layer 19: Surface antistatic layer 19a: The first side of the surface antistatic layer 19b: The second side of the surface antistatic layer 23b: The second side of the protective film forming film 23c: Side surface of protective film forming film 101,101',102,103,104,105,201,202,203,204,205,301,401,501: Composite sheet for protective film formation 130: Film for forming protective film after cutting 130a: The first side of the cut protective film forming film 130':Protective film after cutting 130a': The first side of the protective film after cutting 901: 1st layered body 902:Second layered body I: Picking direction II: The direction of movement of the heavy object

[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至中途為止的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至中途為止的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至中途為止的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至中途為止的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繼圖14之後的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繼圖14之後的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繼圖14之後的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繼圖14之後的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。 [圖17A]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17B]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17C]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17D]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17E]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18]係以示意方式表示測定使用保護膜形成用複合片所獲得之試片的靜摩擦力時的試片的配置形態的一例之側視圖。[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] 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] 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 the composite sheet for forming a protective film according to one embodiment of the present invention. [Fig. 6] 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] Fig. 7 is a cross-sectional view schematically showing the composite sheet for forming a protective film according to one embodiment of the present invention. [Fig. 8] Fig. 8 is a cross-sectional view schematically showing the composite sheet for forming a protective film according to one embodiment of the present invention. [Fig. 9] 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] 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] 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] 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] 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 the method of manufacturing a semiconductor wafer according to one embodiment of the present invention up to the middle point. [Fig. 14B] is a cross-sectional view for schematically explaining the method of manufacturing a semiconductor wafer according to one embodiment of the present invention up to the middle point. [Fig. 14C] is a cross-sectional view for schematically explaining the method of manufacturing a semiconductor wafer according to one embodiment of the present invention up to the middle point. [Fig. 14D] is a cross-sectional view for schematically explaining the method of manufacturing a semiconductor wafer according to one embodiment of the present invention up to the middle point. [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 following Fig. 14. [Fig. [Fig. 15B] is a cross-sectional view for schematically explaining a method for manufacturing a semiconductor wafer according to an embodiment of the present invention following Fig. 14. [Fig. [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 following Fig. 14. [Fig. [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 following Fig. 14. [Fig. [Fig. 16A] is a cross-sectional view schematically illustrating a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [Fig. 16B] is a cross-sectional view schematically illustrating a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [Fig. 16C] is a cross-sectional view schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [Fig. 16D] is a cross-sectional view schematically illustrating a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [Fig. 16E] is a cross-sectional view schematically illustrating a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [Fig. 17A] is a cross-sectional view schematically illustrating a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [Fig. 17B] is a cross-sectional view schematically illustrating a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [Fig. 17C] is a cross-sectional view schematically illustrating a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [Fig. 17D] is a cross-sectional view schematically explaining a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [Fig. 17E] is a cross-sectional view schematically illustrating a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [Fig. 18] Fig. 18 is a side view schematically showing an example of the arrangement form of the test piece when measuring the static friction force of the test piece obtained using the protective film forming composite sheet.

10:支撐片 10:Support piece

10a:支撐片的第1面 10a:Side 1 of the support piece

11:基材 11:Substrate

11a:基材的第1面 11a:Side 1 of the substrate

11b:基材的第2面 11b:Side 2 of the substrate

12:黏著劑層 12: Adhesive layer

12a:黏著劑層的第1面 12a: Side 1 of adhesive layer

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

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

15:剝離膜 15: Peel off film

16:治具用接著劑層 16: Adhesive layer for fixtures

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

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

17b:背面抗靜電層的第2面 17b: The second side of the antistatic layer on the back

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

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中之前述支撐片側的最表層的表面電阻率為1.0×1011Ω/□以下；自於70℃加熱1分鐘後的前述保護膜形成用複合片，切取大小為10cm×20cm之試片，使前述試片中之前述支撐片側的最表層接觸於多孔台的表面，藉此將前述試片載置於前述多孔台上，使大小為6cm×10cm×2cm且質量為1kg之重物之大小為6cm×10cm之面接觸於前述試片中的保護膜形成用膜，將前述重物載置於前述保護膜形成用膜上，沿相對於前述試片之與前述多孔台之接觸面為平行的方向，使前述重物以10mm/min之速度移動，測定前述重物的即將開始移動前的荷重時，前述荷重的測定值為20N以下。 A composite sheet for forming a protective film, including a support sheet and a film for forming a protective film formed on one side of the support sheet; in the composite sheet for forming a protective film, the surface resistivity of the outermost layer on the side of the support sheet is 1.0× 10 11 Ω/□ or less; from the composite sheet for forming a protective film after heating at 70°C for 1 minute, cut a test piece with a size of 10cm × 20cm, and make the outermost layer of the support sheet side of the test piece contact the porous platform surface, whereby the aforementioned test piece is placed on the aforementioned porous stage, so that the 6cm × 10cm surface of the weight of 6cm × 10cm × 2cm and a mass of 1kg contacts the protective film in the aforementioned test piece. Using a film, place the aforementioned heavy object on the aforementioned protective film forming film, move the aforementioned heavy object at a speed of 10 mm/min in a direction parallel to the contact surface of the aforementioned test piece and the aforementioned porous stage, and measure When the weight is applied immediately before movement of the weight begins, the measured value of the load is 20 N or less. 如請求項1所記載之保護膜形成用複合片，其中前述保護膜形成用膜為熱硬化性；前述表面電阻率係前述保護膜形成用複合片中的前述保護膜形成用膜於130℃熱硬化2小時後之前述支撐片側的最表層的表面電阻率。 The protective film-forming composite sheet according to claim 1, wherein the protective film-forming film is thermosetting; and the surface resistivity is the result of the protective film-forming film in the protective film-forming composite sheet being heated at 130°C. Surface resistivity of the outermost layer on the support sheet side after 2 hours of hardening. 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 has a base material and an antistatic layer formed on one or both sides of the base material; or the support sheet has an antistatic layer. The base material acts 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 or both sides of the base material is 100 nm or less. 如請求項1或2所記載之保護膜形成用複合片，其中前述支撐片的全光線透過率為80%以上。 The composite sheet for forming a protective film according to claim 1 or 2, wherein the total light transmittance of the support sheet is 80% or more. 如請求項3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 claim 3, wherein the pressing surface of the pressing mechanism having a flat pressing surface with an area of 2 cm×2 cm is covered with a flannel cloth, and the flannel cloth is covered with the flannel cloth as described above. The pressing surface is pressed against the surface of the antistatic layer, and while the pressing mechanism applies a load of 125g/cm 2 to the antistatic layer in the above state, the pressing mechanism is allowed to reciprocate at a linear distance of 10cm for 10 seconds. After rubbing the antistatic layer once, no scratches were confirmed when an area of 2 cm × 2 cm on the friction surface of the antistatic layer was visually observed. 一種半導體晶片之製造方法，具有下述步驟：將如請求項1至6中任一項所記載之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，製作由具備有支撐片、設置於前述支撐片的一面上之切斷後的前述保護膜或保護膜形成用膜、及設置於前述切斷後的保護膜或保護膜形成用膜之與前述支撐片側為相反側的面上之半導體晶片而成之積層體之步驟；以及將前述積層體中之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；進而，於前述積層體製作步驟與前述拾取步驟之間，具有將固定於台上之前述積層體自前述台扯離之步驟； 於前述扯離步驟中，固定於台上之前述積層體於前述積層體之前述支撐片側的最表層的表面接觸於前述台，前述台之前述積層體的固定面為陶瓷製或不銹鋼製。 A method for manufacturing a semiconductor wafer, which has the following steps: affixing the protective film-forming film in the protective film-forming composite sheet according to any one of claims 1 to 6 to the semiconductor wafer; The step of curing the protective film-forming film attached to the semiconductor wafer to form a protective film; dividing the semiconductor wafer, cutting the protective film or the protective film-forming film, and producing a support sheet provided on the aforementioned It is composed of the cut protective film or protective film forming film on one side of the support sheet, and a semiconductor wafer provided on the side of the cut protective film or protective film forming film opposite to the support sheet side. The step of forming a laminated body; and the step of picking up the semiconductor wafer having the aforementioned cut protective film or protective film-forming film in the aforementioned laminated body from the aforementioned supporting sheet; furthermore, in the aforementioned step of producing the laminated body, Between the aforementioned picking-up steps, there is a step of pulling off the aforementioned laminated body fixed on the stage from the aforementioned stage; In the aforementioned tearing-off step, the surface of the outermost layer of the laminated body on the side of the supporting sheet of the laminated body before being fixed on the table is in contact with the table. The fixing surface of the laminated body on the front of the table is made of ceramic or stainless steel.
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