TW202348757A - Protective film-forming film, composite sheet for forming protective film, method of manufacturing semiconductor device, and use of protective film-forming film providing a protective film-forming composite sheet including a support sheet and the protective film-forming film provided on one surface of the support sheet - Google Patents

Protective film-forming film, composite sheet for forming protective film, method of manufacturing semiconductor device, and use of protective film-forming film providing a protective film-forming composite sheet including a support sheet and the protective film-forming film provided on one surface of the support sheet Download PDF

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TW202348757A
TW202348757A TW112109095A TW112109095A TW202348757A TW 202348757 A TW202348757 A TW 202348757A TW 112109095 A TW112109095 A TW 112109095A TW 112109095 A TW112109095 A TW 112109095A TW 202348757 A TW202348757 A TW 202348757A
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protective film
film
forming
semiconductor wafer
aforementioned
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山本大輔
堂下美紗季
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日商琳得科股份有限公司
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    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
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    • H01L23/00—Details of semiconductor or other solid state devices
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    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
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Abstract

The present invention provides a protective film-forming film, which is a thermosetting protective film-forming film. A test piece of the protective film-forming film has a heating start temperature more than 160 DEG C as measured by differential scanning calorimetry by heating the test piece from 23 DEG C to 300 DEG C at a heating rate of 10 DEG C/min. The present invention provides a protective film-forming composite sheet including a support sheet and the protective film-forming film provided on one surface of the support sheet.

Description

保護膜形成膜、保護膜形成用複合片、半導體裝置之製造方法、以及保護膜形成膜之使用Protective film forming film, protective film forming composite sheet, manufacturing method of semiconductor device, and use of protective film forming film

本發明係關於一種保護膜形成膜、保護膜形成用複合片、半導體裝置之製造方法、以及保護膜形成膜之使用。 本案係基於2022年3月30日在日本提出申請之日本特願2022-055428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 protective film-forming film, a protective film-forming composite sheet, a manufacturing method of a semiconductor device, and the use of the protective film-forming film. This case claims priority based on Japanese Patent Application No. 2022-055428 filed in Japan on March 30, 2022, and the contents of the application are cited in this article.

於半導體晶圓，有些在其中一面(電路面)形成有電路，進而在該面(電路面)上具有凸塊等突狀電極。這種半導體晶圓係藉由分割而作成半導體晶片，使該突狀電極被連接於電路基板上的連接墊，而搭載於前述電路基板。 為了抑制在這種半導體晶圓或半導體晶片之中產生龜裂等破損，有時將與電路面為相反側之面(內面)以保護膜來進行保護。 Some semiconductor wafers have circuits formed on one side (circuit surface), and have protruding electrodes such as bumps on this surface (circuit surface). This semiconductor wafer is divided into semiconductor wafers, and the protruding electrodes are connected to connection pads on the circuit board, and then mounted on the circuit board. In order to suppress the occurrence of damage such as cracks in such a semiconductor wafer or semiconductor wafer, the surface opposite to the circuit surface (inner surface) may be protected with a protective film.

為了形成這種保護膜，係於半導體晶圓的內面貼附用以形成保護膜之保護膜形成膜。保護膜形成膜係被積層於用以支撐此保護膜形成膜之支撐片上，亦有時以保護膜形成用複合片的狀態來使用，亦有時不積層於支撐片上來使用。然後，通常於內面具備保護膜形成膜之半導體晶圓(具保護膜形成膜之半導體晶圓)在經過之後的各種步驟而加工成為於內面具備保護膜之半導體晶片(具保護膜之半導體晶片)。這種具保護膜之半導體晶片在拾取後被搭載於基板的電路面，構成半導體裝置。保護膜形成膜係例如藉由硬化而形成保護膜。In order to form such a protective film, a protective film-forming film for forming a protective film is attached to the inner surface of the semiconductor wafer. The protective film-forming film is laminated on a support sheet for supporting the protective film-forming film. It may be used in the form of a protective film-forming composite sheet, or may be used without being laminated on the support sheet. Then, a semiconductor wafer having a protective film-forming film on its inner surface (a semiconductor wafer with a protective film-forming film) is usually processed into a semiconductor wafer having a protective film on its inner surface (a semiconductor wafer with a protective film) through various subsequent steps. wafer). This semiconductor wafer with a protective film is picked up and mounted on the circuit surface of the substrate to form a semiconductor device. The protective film-forming film system forms a protective film by curing, for example.

保護膜形成膜最終能夠在保護膜的狀態下充分地保護半導體晶片的內面，要求抑制於半導體晶片中產生微小的缺損(亦即碎屑)。並且，順應這種目的之保護膜形成膜已被揭示(參照專利文獻1)。 [先前技術文獻] [專利文獻] The protective film-forming film is required to sufficiently protect the inner surface of the semiconductor wafer in the form of a protective film and to suppress the occurrence of minute defects (that is, chips) in the semiconductor wafer. Furthermore, a protective film-forming film that meets this purpose has been disclosed (see Patent Document 1). [Prior technical literature] [Patent Document]

[專利文獻1]日本專利第4897979號公報。[Patent Document 1] Japanese Patent No. 4897979.

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

此外，保護膜形成膜之中，藉由加熱進行硬化之熱硬化性的保護膜形成膜，通常建議在製造之後當下至使用時為止進行冷藏保存。理由在於，當不將保護膜形成膜進行冷藏而保存之情形時，保護膜形成膜的穩定性低，有可能導致表現熱硬化性所必要的保護膜形成膜的含有成分之一部分於保存中進行反應，而在實際使用時使得保護膜形成膜無法充分地發揮功能。然而，於冷藏保存的情形時，相較於常溫保存的情形時在保存所需要的成本更高，保護膜形成膜的操作亦繁雜。因此，近年來有需要對於即使以常溫保存亦可無問題地使用之保護膜形成膜。 相對於此，在專利文獻1所揭示之保護膜形成膜在常溫保存之情形時的穩定性低。 Furthermore, among the protective film-forming films, thermosetting protective film-forming films that are cured by heating are generally recommended to be refrigerated after production until use. The reason is that when the protective film-forming film is stored without refrigeration, the stability of the protective film-forming film is low, and part of the components contained in the protective film-forming film necessary to express thermosetting properties may be lost during storage. reaction, which prevents the protective film-forming film from fully functioning during actual use. However, in the case of refrigerated storage, the cost of storage is higher than in the case of normal temperature storage, and the operation of forming a protective film is also complicated. Therefore, in recent years, there has been a need to form a protective film that can be used without problems even when stored at room temperature. In contrast, the protective film-forming film disclosed in Patent Document 1 has low stability when stored at room temperature.

本發明的目的在於提供一種以常溫保存之情形時的穩定性高的保護膜形成膜、具備前述保護膜形成膜之保護膜形成用複合片、以及使用前述保護膜形成膜或保護膜形成用複合片之半導體裝置之製造方法。 [用以解決課題之手段] An object of the present invention is to provide a protective film-forming film with high stability when stored at room temperature, a protective film-forming composite sheet provided with the aforementioned protective film-forming film, and a protective film-forming composite sheet using the aforementioned protective film-forming film or protective film-forming composite sheet. Method for manufacturing a chip semiconductor device. [Means used to solve problems]

為解決上述課題，本發明係採用以下的構成。 [1].一種保護膜形成膜，係熱硬化性的保護膜形成膜，藉由差示掃描熱量分析法，將前述保護膜形成膜的試片以升溫速度10℃/min、自23℃升溫至300℃為止時的發熱起始溫度為160℃以上。 [2].如[1]所記載之保護膜形成膜，其中前述保護膜形成膜含有填充材(D)，前述保護膜形成膜之中，相對於前述保護膜形成膜的總質量，前述填充材(D)的含量的比率為63質量%以下。 [3].如[1]或[2]所記載之保護膜形成膜，其中前述保護膜形成膜含有填充材(D)，前述保護膜形成膜之中，相對於前述保護膜形成膜的總質量，前述填充材(D)的含量的比率為50質量%以上。 [4].如[1]至[3]中任一項所記載之保護膜形成膜，其中前述發熱起始溫度為170℃以上。 [5].一種保護膜形成用複合片，係具備支撐片、以及設置於前述支撐片的一面上之保護膜形成膜，前述保護膜形成膜係如[1]至[4]中任一項所記載之保護膜形成膜。 In order to solve the above-mentioned problems, the present invention adopts the following configuration. [1]. A protective film-forming film, which is a thermosetting protective film-forming film. Using differential scanning calorimetry, a test piece of the protective film-forming film is heated from 23°C at a heating rate of 10°C/min. The heat generation starting temperature is 160°C or higher until it reaches 300°C. [2]. The protective film-forming film according to [1], wherein the protective film-forming film contains a filler (D), and among the protective film-forming films, the filler is The content ratio of material (D) is 63% by mass or less. [3]. The protective film-forming film according to [1] or [2], wherein the protective film-forming film contains a filler (D), and among the protective film-forming films, relative to the total of the protective film-forming film Mass, the content ratio of the filler (D) is 50 mass % or more. [4]. The protective film-forming film according to any one of [1] to [3], wherein the heat generation starting temperature is 170°C or higher. [5]. A composite sheet for forming a protective film, which is provided with a support sheet and a protective film-forming film provided on one side of the support sheet. The protective film-forming film is any one of [1] to [4]. The described protective film forms a film.

[6].一種半導體裝置之製造方法，係用於製造半導體裝置；前述製造方法係具有如下步驟：貼附步驟，將如[1]至[4]中任一項所記載之保護膜形成膜之一面、或是[5]所記載之保護膜形成用複合片中之保護膜形成膜的露出面貼附於半導體晶圓的內面；熱硬化步驟，在前述貼附步驟之後，使前述保護膜形成膜熱硬化而形成保護膜；印字步驟，在前述熱硬化步驟之後，於使用前述保護膜形成用複合片之情形時，在前述保護膜形成用複合片中的前述保護膜的前述支撐片側之面進行雷射印字，於使用未構成前述保護膜形成用複合片之前述保護膜形成膜之情形時，在前述保護膜的另一面進行雷射印字；加工步驟，在前述印字步驟之後，於使用前述保護膜形成用複合片之情形時，在前述保護膜形成用複合片中之前述支撐片上，將前述半導體晶圓分割成半導體晶片，沿著前述半導體晶圓的分割部位來切斷前述保護膜，於使用未構成前述保護膜形成用複合片之前述保護膜形成膜之情形時，在前述保護膜的另一面貼附切割片之後，在前述切割片上，將前述半導體晶圓分割成半導體晶片，沿著前述半導體晶圓的分割部位來切斷前述保護膜，藉此製作具備前述半導體晶片以及設置於前述半導體晶片的內面之切斷後的前述保護膜之具保護膜之半導體晶片；拾取步驟，在前述加工步驟之後，將前述具保護膜之半導體晶片自前述切割片或支撐片扯離而進行拾取。 [7].如[6]所記載之半導體裝置之製造方法，其中將前述保護膜形成用複合片、或是未構成前述保護膜形成用複合片之前述保護膜形成膜以常溫保存30日之後，用於前述貼附步驟。 [6]. A manufacturing method of a semiconductor device, which is used to manufacture a semiconductor device; the manufacturing method has the following steps: an attachment step, forming a protective film as described in any one of [1] to [4]; One side or the exposed surface of the protective film forming film in the protective film forming composite sheet described in [5] is attached to the inner surface of the semiconductor wafer; the thermal hardening step is to make the aforementioned protective film after the aforementioned attaching step. The film-forming film is thermally cured to form a protective film; and the printing step is, after the thermal curing step, when the composite sheet for forming a protective film is used, on the supporting sheet side of the protective film in the composite sheet for forming a protective film. When using the protective film-forming film that does not constitute the protective film-forming composite sheet, laser printing is performed on the other side of the protective film; the processing step is to perform the laser printing on the other side of the protective film after the printing step. When using the composite sheet for forming a protective film, the semiconductor wafer is divided into semiconductor wafers on the supporting sheet in the composite sheet for forming a protective film, and the protective film is cut along the divided portions of the semiconductor wafer. Film, when using the protective film forming film that does not constitute the protective film forming composite sheet, after attaching a dicing piece to the other side of the protective film, the semiconductor wafer is divided into semiconductor wafers on the dicing piece. , cutting the protective film along the divided portions of the semiconductor wafer, thereby producing a semiconductor wafer with a protective film including the semiconductor wafer and the cut protective film disposed on the inner surface of the semiconductor wafer; picking up step , after the aforementioned processing steps, the aforementioned semiconductor wafer with the protective film is pulled away from the aforementioned cutting piece or the supporting piece and picked up. [7]. The manufacturing method of a semiconductor device according to [6], wherein the protective film-forming composite sheet or the protective film-forming film before forming the protective film-forming composite sheet is stored at room temperature for 30 days. , used in the aforementioned attaching step.

[8].一種保護膜形成膜之使用，係用以貼附於半導體晶圓中與電路面為相反側之內面，且於分割前述半導體晶圓所獲得之半導體晶片的內面形成保護膜；前述保護膜形成膜係如[1]至[4]中任一項所記載之保護膜形成膜。 [9].如[8]所記載之保護膜形成膜之使用，其中將前述保護膜形成膜以常溫保存30日之後，貼附於前述半導體晶圓的前述內面。 [發明功效] [8]. The use of a protective film-forming film, which is used to adhere to the inner surface of a semiconductor wafer on the opposite side to the circuit surface, and to form a protective film on the inner surface of the semiconductor wafer obtained by dividing the aforementioned semiconductor wafer. ; The aforementioned protective film-forming film is a protective film-forming film described in any one of [1] to [4]. [9]. Use of the protective film-forming film as described in [8], wherein the protective film-forming film is stored at room temperature for 30 days and then attached to the inner surface of the semiconductor wafer. [Invention effect]

根據本發明，可提供一種在常溫保存之情形時的穩定性高的保護膜形成膜、具備前述保護膜形成膜之保護膜形成用複合片、以及使用前述保護膜形成膜或保護膜形成用複合片之半導體裝置之製造方法。According to the present invention, it is possible to provide a protective film-forming film with high stability when stored at room temperature, a protective film-forming composite sheet provided with the aforementioned protective film-forming film, and a protective film-forming film or protective film-forming composite sheet using the aforementioned protective film-forming film. Method for manufacturing a chip semiconductor device.

◇保護膜形成膜 本發明之一實施形態之保護膜形成膜，係熱硬化性的保護膜形成膜，藉由差示掃描熱量分析(DSC；Differential Scanning Calorimetry)法，將前述保護膜形成膜的試片以升溫速度10℃/min，自23℃升溫至300℃為止時的發熱起始溫度(本說明書中，有時簡稱為「發熱起始溫度」)為160℃以上。 本實施形態之保護膜形成膜，能夠例如藉由如後述般與支撐片進行積層而構成保護膜形成用複合片。 ◇Protective film forming film The protective film-forming film according to one embodiment of the present invention is a thermosetting protective film-forming film. By differential scanning calorimetry (DSC; Differential Scanning Calorimetry), a test piece of the protective film-forming film is heated at a heating rate The heat generation start temperature (sometimes referred to as "heat generation start temperature" in this specification) when the temperature is raised from 23°C to 300°C at 10°C/min is 160°C or above. The protective film-forming film of this embodiment can be laminated with a support sheet as described later to form a protective film-forming composite sheet.

本實施形態之保護膜形成膜具有如下特性：在使用接下來所製作之試片藉由DSC法測定發熱起始溫度時，該發熱起始溫度成為160℃以上。具有這種特性之本實施形態之保護膜形成膜在常溫保存之情形時的穩定性高。 本說明書中，所謂「常溫」，意指不特別冷或特別熱的溫度，亦即平常的溫度，例如可列舉15℃至25℃之溫度等。 The protective film-forming film of this embodiment has the following characteristics: when the heat generation onset temperature is measured by the DSC method using the test piece produced next, the heat generation onset temperature becomes 160° C. or higher. The protective film-forming film of this embodiment having such characteristics has high stability when stored at room temperature. 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.

藉由使用本實施形態之保護膜形成膜、或是具備該保護膜形成膜之保護膜形成用複合片，能夠製造具備半導體晶片以及設置於前述半導體晶片的內面之保護膜形成膜之具保護膜形成膜之半導體晶片。進而，能夠由前述具保護膜形成膜之半導體晶片製造具備半導體晶片以及設置於前述半導體晶片的內面之保護膜之具保護膜之半導體晶片。進而，能夠使用具保護膜之半導體晶片來製造半導體裝置。By using the protective film-forming film of this embodiment or the protective film-forming composite sheet provided with the protective film-forming film, it is possible to manufacture a protective device including a semiconductor wafer and a protective film-forming film provided on the inner surface of the semiconductor wafer. The film forms the film on the semiconductor wafer. Furthermore, a semiconductor wafer with a protective film including a semiconductor wafer and a protective film provided on the inner surface of the semiconductor wafer can be produced from the semiconductor wafer having the protective film forming film. Furthermore, a semiconductor device can be manufactured using a semiconductor wafer provided with a protective film.

於這些半導體晶圓其中一面上形成有電路，在本說明書之中，將如此般形成有電路之側之半導體晶圓之面稱為「電路面」。並且將半導體晶圓中與電路面為相反側之面稱為「內面」。 半導體晶圓係藉由切割等手段進行分割而成為半導體晶片。本說明書之中，與半導體晶圓的情形相同，將形成有電路之側之半導體晶片之面稱為「電路面」，半導體晶片中與電路面為相反側之面稱為「內面」。 較佳係於半導體晶圓的電路面與半導體晶片的電路面皆設置有凸塊、支柱等突狀電極。突狀電極較佳係以焊料所構成。 A circuit is formed on one side of these semiconductor wafers. In this specification, the side of the semiconductor wafer on which the circuit is formed is called a "circuit side". The surface of the semiconductor wafer that is opposite to the circuit surface is called the "inner surface". The semiconductor wafer is divided into semiconductor wafers by means such as dicing. In this specification, as in the case of a semiconductor wafer, the surface of the semiconductor wafer on which the circuit is formed is called the "circuit surface", and the surface of the semiconductor wafer opposite to the circuit surface is called the "inner surface". Preferably, protruding electrodes such as bumps and pillars are provided on both the circuit surface of the semiconductor wafer and the circuit surface of the semiconductor wafer. The protruding electrode is preferably made of solder.

進而，可藉由使用前述具保護膜之半導體晶片，來製造半導體裝置。 本說明書之中，作為「半導體裝置」，可列舉如具保護膜之半導體晶片於半導體晶片之電路面上的突狀電極來覆晶連接電路基板上的連接墊所構成之半導體裝置。 Furthermore, a semiconductor device can be manufactured by using the aforementioned semiconductor wafer with a protective film. In this specification, the term "semiconductor device" includes, for example, a semiconductor device in which a semiconductor wafer with a protective film is placed on a protruding electrode on the circuit surface of the semiconductor wafer and is flip-chip connected to a connection pad on a circuit substrate.

本實施形態之保護膜形成膜係具有熱硬化性，藉由該熱硬化作為保護膜而發揮功能。The protective film-forming film system of this embodiment has thermosetting property, and functions as a protective film by this thermosetting.

藉由將常溫的保護膜形成膜加熱至超過常溫之溫度為止，繼而冷卻至常溫為止，作成加熱、冷卻後的保護膜形成膜，當將加熱、冷卻後的保護膜形成膜的硬度以及加熱前的保護膜形成膜的硬度以相同溫度進行比較時，當在加熱、冷卻後的保護膜形成膜較硬的情形時，該保護膜形成膜為熱硬化性。By heating the protective film forming film at normal temperature to a temperature exceeding normal temperature and then cooling it to normal temperature, a protective film forming film after heating and cooling is produced. When the hardness of the protective film forming film after heating and cooling is compared with the hardness of the protective film forming film before heating. When the hardness of the protective film-forming film is compared at the same temperature, if the protective film-forming film after heating and cooling is harder, the protective film-forming film is thermosetting.

本實施形態之保護膜形成膜可由1層(單層)所構成，亦可由2層以上之多層所構成。於保護膜形成膜由多層所構成之情形時，這些多層相互可相同亦可不同，這些多層的組合並無特別限定。The protective film-forming film of this embodiment may be composed of one layer (single layer), or may be composed of multiple layers of two or more layers. When the protective film-forming film is composed of multiple layers, these multiple layers may be the same as or different from each other, and the combination of these multiple layers is not particularly limited.

本說明書之中，不限於保護膜形成膜之情形，所謂「多層相互可相同亦可不同」，意指「可所有層相同，亦可所有層皆不同，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 this specification, the term "multiple layers may be the same or different from each other" is not limited to the case where the protective film is formed into a film, which means "all the layers may be the same, all the layers may be different, or only some of the layers may be the same", and further, 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."

[發熱起始溫度] 在DSC之前述試片的發熱起始溫度為160℃以上，較佳為170℃以上，例如亦可為173℃以上、176℃以上、以及180℃以上之中任一者。前述發熱起始溫度越高，保護膜形成膜在常溫之保存穩定性越高。 前述發熱起始溫度的上限值並無特別限定。例如由容易獲得保護膜形成膜的方面來看，前述發熱起始溫度亦可為195℃以下。 一實施形態中，前述發熱起始溫度例如亦可為160℃至195℃、170℃至195℃、173℃至195℃、176℃至195℃、以及180℃至195℃中任一者。然而，這些溫度為前述發熱起始溫度之一例。 [Fever starting temperature] The heat generation starting temperature of the test piece before DSC is 160°C or higher, preferably 170°C or higher, and may be any one of 173°C or higher, 176°C or higher, and 180°C or higher. The higher the aforementioned heating onset temperature, the higher the storage stability of the protective film-forming film at room temperature. The upper limit of the aforementioned heat generation starting temperature is not particularly limited. For example, from the viewpoint of easily obtaining a protective film-forming film, the heat generation starting temperature may be 195°C or lower. In one embodiment, the heat generation starting temperature may be, for example, any one of 160°C to 195°C, 170°C to 195°C, 173°C to 195°C, 176°C to 195°C, and 180°C to 195°C. However, these temperatures are examples of the aforementioned heat generation starting temperatures.

供於DSC之前述試片的形態只要是可以高精度進行DSC，則並無特別限定。例如能夠藉由積層多片保護膜形成膜，切成適切的形狀而製作前述試片。作為試片，例如只要是4mg至10mg左右的質量即為充分。The form of the test piece to be used for DSC is not particularly limited as long as it can perform DSC with high accuracy. For example, the test piece can be produced by laminating a plurality of protective films to form a film and cutting it into an appropriate shape. As a test piece, it is sufficient if it has a mass of about 4 mg to 10 mg, for example.

在DSC之前述試片的發熱起始溫度係被定義為如下的溫度：例如顯示DSC曲線(將DSC資料經繪圖所獲得之曲線)的微分曲線在最初顯示負值之點之切線與前述微分曲線在顯示極大值(最初被觀測到之極值)之溫度之切線的交點的溫度。The heating onset temperature of the test piece before DSC is defined as the following temperature: For example, the tangent line between the point where the differential curve showing the DSC curve (the curve obtained by plotting the DSC data) initially shows a negative value and the aforementioned differential curve The temperature at the intersection of the tangent line to the temperature showing the maximum value (the extreme value initially observed).

在DSC之前述試片的發熱起始溫度能夠藉由調節前述保護膜形成膜的含有成分的種類以及含量而加以調節。 例如，於保護膜形成膜含有後述之硬化促進劑(C)之情形時，能夠藉由調節硬化促進劑(C)的反應性，更容易地調節前述發熱起始溫度。更具體而言，例如，能夠藉由選擇反應起始溫度較低者作為硬化促進劑(C)，增加這種硬化促進劑(C)的含量，而提高前述發熱起始溫度。 例如，於保護膜形成膜含有後述之熱硬化劑(B2)之情形時，為了提高前述發熱起始溫度，較佳係選擇在常溫為固體狀者作為熱硬化劑(B2)。 The heat generation starting temperature of the test piece before DSC can be adjusted by adjusting the type and content of the components contained in the protective film-forming film. For example, when the protective film-forming film contains a hardening accelerator (C) described below, the heat generation starting temperature can be more easily adjusted by adjusting the reactivity of the hardening accelerator (C). More specifically, for example, by selecting one with a lower reaction start temperature as the hardening accelerator (C) and increasing the content of the hardening accelerator (C), the heat generation start temperature can be increased. For example, when the protective film-forming film contains a thermosetting agent (B2) described below, in order to increase the heat generation starting temperature, it is preferable to select a thermosetting agent (B2) that is solid at room temperature.

保護膜形成膜的厚度並無特別限定。 保護膜形成膜的厚度較佳為50μm以下，例如亦可為40μm以下、以及30μm以下之中任一者。藉由保護膜形成膜的厚度為前述上限值以下，避免保護膜形成膜的厚度變得過剩。 另一方面，保護膜形成膜的厚度在能夠形成保護性能更高的保護膜的方面來看，較佳為5μm以上。 一實施形態中，保護膜形成膜的厚度例如亦可為5μm至50μm、5μm至40μm、以及5μm至30μm中任一者。然而，這些厚度為保護膜形成膜的厚度之一例。 The thickness of the protective film-forming film is not particularly limited. The thickness of the protective film-forming film is preferably 50 μm or less, and may be any of 40 μm or less and 30 μm or less, for example. By setting the thickness of the protective film-forming film to be equal to or less than the aforementioned upper limit, the thickness of the protective film-forming film can be prevented from becoming excessive. On the other hand, the thickness of the protective film-forming film is preferably 5 μm or more in order to form a protective film with higher protective performance. In one embodiment, the thickness of the protective film forming film may be, for example, any one of 5 μm to 50 μm, 5 μm to 40 μm, and 5 μm to 30 μm. However, these thicknesses are examples of the thicknesses of the protective film forming films.

本說明書之中，所謂「保護膜形成膜的厚度」，意指保護膜形成膜整體的厚度，例如，所謂由多層所構成之保護膜形成膜的厚度，意指構成保護膜形成膜之所有層的合計的厚度。In this specification, the so-called "thickness of the protective film-forming film" means the thickness of the entire protective film-forming film. For example, the so-called thickness of the protective film-forming film composed of multiple layers means all the layers constituting the protective film-forming film. the total thickness.

本說明書之中，不限於保護膜形成膜之情形，所謂「厚度」，只要無特別說明，係對象物中隨機地選出之5部位所測定之厚度的平均所表示之值，能夠依據JIS K7130，使用定壓厚度測定器來取得。In this specification, the so-called "thickness" is not limited to the case where a protective film is formed into a film. Unless otherwise specified, it is a value expressed as the average of the thicknesses measured at five randomly selected locations in the object. It can be based on JIS K7130. Use a constant pressure thickness gauge to obtain it.

將前述保護膜形成膜貼附於半導體晶圓的目標部位，進行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功能之程度的硬化度，則並無特別限定，根據保護膜形成膜的種類而適當選擇即可。The curing conditions when the protective film-forming film is attached to a target portion of the semiconductor wafer and thermally cured to form a protective film are not particularly limited as long as the protective film has a degree of curing that allows it to fully function. Depending on the protection The type of film forming film may be appropriately selected.

例如，保護膜形成膜的熱硬化時的加熱溫度亦可為100℃至200℃、110℃至180℃、以及120℃至160℃中任一者。 前述熱硬化時的加熱時間，考慮加熱溫度而適當設定即可，例如亦可為3分鐘至5小時、10分鐘至4小時、以及30分鐘至3小時中任一者。 For example, the heating temperature during thermosetting of the protective film-forming film may be any one of 100°C to 200°C, 110°C to 180°C, and 120°C to 160°C. The heating time during thermal hardening may be appropriately set in consideration of the heating temperature. For example, it may be any one of 3 minutes to 5 hours, 10 minutes to 4 hours, and 30 minutes to 3 hours.

本實施形態之保護膜形成膜，係能夠用於貼附半導體晶圓中與電路面為相反側之內面，於分割前述半導體晶圓所獲得之半導體晶片的內面形成保護膜。 本實施形態之保護膜形成膜對於半導體晶圓中前述內面之貼附性良好，半導體晶片的保護性能高。 本實施形態之保護膜形成膜即使以常溫保存中，仍抑制在表現熱硬化性所必要的含有成分之目標外的反應。亦即，本實施形態之保護膜形成膜在常溫保存之情形時的穩定性高。因此，例如即使將保護膜形成膜以常溫保存30日之後，在貼附於半導體晶圓之前述內面之情形時，貼附性仍良好，半導體晶片的保護性能仍高。 The protective film-forming film of this embodiment can be used to adhere the inner surface of a semiconductor wafer opposite to the circuit surface, and form a protective film on the inner surface of the semiconductor wafer obtained by dividing the semiconductor wafer. The protective film-forming film of this embodiment has good adhesion to the inner surface of the semiconductor wafer, and has high protective performance of the semiconductor wafer. Even when the protective film-forming film of this embodiment is stored at normal temperature, it suppresses unintended reactions containing components necessary to express thermosetting properties. That is, the protective film-forming film of this embodiment has high stability when stored at room temperature. Therefore, for example, even after the protective film-forming film is stored at normal temperature for 30 days, the adhesion is still good when it is attached to the inner surface of the semiconductor wafer, and the protective performance of the semiconductor wafer is still high.

[保護膜形成用組成物] 前述保護膜形成膜能夠使用含有該構成材料之保護膜形成用組成物(更具體而言為熱硬化性保護膜形成用組成物)來形成。例如，保護膜形成膜能夠藉由在該形成對象面塗敷保護膜形成用組成物，並視需要進行乾燥來形成。保護膜形成用組成物中在常溫下不會氣化之成分彼此的含量之比率通常與保護膜形成膜中之前述成分彼此的含量之比率相同。 [Composition for protective film formation] The protective film-forming film can be formed using a protective film-forming composition (more specifically, a thermosetting protective film-forming composition) containing the constituent material. For example, the protective film-forming film can be formed by applying a protective film-forming composition to the formation target surface and drying it if necessary. The ratio of the contents of components that do not vaporize at normal temperature in the protective film-forming composition to each other is generally the same as the ratio of the contents of the aforementioned components to each other in the protective film-forming film.

前述保護膜形成膜除熱硬化性以外，亦可具有能量線硬化性。The protective film-forming film may have energy ray curability in addition to thermosetting properties.

本說明書中，所謂「能量線」，意指具有能量量子之電磁波或帶電粒子束，作為能量線的例示，可列舉如紫外線、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)燈等作為紫外線源而進行照射。電子束可照射藉由電子束加速器等產生之電子束。 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 rays" mean electromagnetic waves or charged particle beams having 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 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.

保護膜形成膜中，相對於保護膜形成膜的總質量，保護膜形成膜中1種或2種以上的後述之含有成分的合計含量的比率不超過100質量%。 同樣地，保護膜形成用組成物中，相對於保護膜形成用組成物的總質量，保護膜形成用組成物的1種或2種以上的後述之含有成分的合計含量的比率不超過100質量%。 In the protective film-forming film, the ratio of the total content of one or more of the components described below in the protective film-forming film to the total mass of the protective film-forming film does not exceed 100 mass %. Similarly, in the protective film-forming composition, the ratio of the total content of one or more of the components described below in the protective film-forming composition to the total mass of the protective film-forming composition does not exceed 100 mass. %.

利用公知的方法塗敷保護膜形成用組成物即可，例如可列舉使用以下各種塗佈機之方法：氣刀塗佈機、刮刀塗佈機、棒式塗佈機、凹版塗佈機、輥式塗佈機、輥刀塗佈機、簾幕式塗佈機、模具塗佈機、刀式塗佈機、網版塗佈機、繞線棒(Mayer bar)式塗佈機、輕觸式塗佈機等。The composition for forming a protective film may be applied by a known method. For example, the following methods may be used: air knife coater, blade coater, rod coater, gravure coater, roller coater, etc. Type coater, roller knife coater, curtain type coater, mold coater, knife type coater, screen coater, Mayer bar type coater, light touch type Coating machine, etc.

保護膜形成用組成物的乾燥條件並無特別限定。但是，於保護膜形成用組成物含有後述之溶媒之情形時，較佳係進行加熱乾燥。並且，含有溶媒之保護膜形成用組成物例如較佳為於70℃至130℃且10秒至5分鐘的條件下進行加熱乾燥。但是，由於保護膜形成用組成物為熱硬化性，故較佳為以該組成物本身以及由該組成物所形成之熱硬化性之保護膜形成膜不會熱硬化之方式來進行加熱乾燥。The drying conditions of the protective film forming composition are not particularly limited. 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 under conditions of 70°C to 130°C for 10 seconds to 5 minutes, for example. However, since the protective film-forming composition is thermosetting, it is preferably heated and dried in such a manner that the composition itself and the thermosetting protective film-forming film formed from the composition are not thermally cured.

作為較佳的保護膜形成膜，例如可列舉含有硬化促進劑(C)之保護膜形成膜，作為更佳的保護膜形成膜，例如可列舉含有聚合物成分(A)、熱硬化性成分(B)、硬化促進劑(C)以及填充材(D)之保護膜形成膜。聚合物成分(A)可視為聚合性化合物進行聚合反應所形成之成分。熱硬化性成分(B)係將熱作為反應的觸發，經硬化(聚合)反應所獲得之成分。此外，本說明書中之聚合反應亦包含縮聚反應。 以下針對保護膜形成用組成物的組成進行詳細地說明。 Preferable protective film-forming films include, for example, a protective film-forming film containing a curing accelerator (C). Examples of more preferable protective film-forming films include a polymer component (A), a thermosetting component ( The protective film of B), hardening accelerator (C) and filler (D) forms a film. The polymer component (A) can be regarded as a component formed by a polymerization reaction of a polymerizable compound. The thermosetting component (B) is a component obtained through a curing (polymerization) reaction using heat as a trigger for the reaction. In addition, the polymerization reaction in this specification also includes polycondensation reaction. The composition of the protective film forming composition will be described in detail below.

[保護膜形成用組成物(III)] 作為較佳的保護膜形成用組成物，例如可列舉：含有硬化促進劑(C)之保護膜形成用組成物(III)(本說明書之中，有時簡記為「組成物(III)」)等。保護膜形成用組成物(III)更佳係含有聚合物成分(A)、熱硬化性成分(B)、硬化促進劑(C)以及填充材(D)。 [Protective film forming composition (III)] As a preferable protective film forming composition, for example, a protective film forming composition (III) containing a hardening accelerator (C) (herein, may be abbreviated as "composition (III)") wait. The protective film forming composition (III) more preferably contains a polymer component (A), a thermosetting component (B), a curing accelerator (C), and a filler (D).

[聚合物成分(A)] 聚合物成分(A)係用以賦予保護膜形成膜造膜性或可撓性等之聚合物化合物。此外，本說明書中之聚合物化合物亦包含縮聚反應的產物。 [Polymer component (A)] The polymer component (A) is a polymer compound for imparting film-forming properties, flexibility, etc. to the protective film-forming film. In addition, the polymer compounds in this specification also include products of polycondensation reactions.

組成物(III)以及保護膜形成膜所含有之聚合物成分(A)可僅為1種，亦可為2種以上，為2種以上之情形時，這些聚合物成分(A)的組合以及比率可任意選擇。The polymer component (A) contained in the composition (III) and the protective film-forming film may be only one type or two or more types. In the case of two or more types, the combination of these polymer components (A) and The ratio can be chosen arbitrarily.

作為聚合物成分(A)，例如可列舉：丙烯酸樹脂、胺基甲酸酯樹脂、苯氧基樹脂、聚矽氧樹脂、飽和聚酯樹脂等，較佳為丙烯酸樹脂。Examples of the polymer component (A) include acrylic resin, urethane resin, phenoxy resin, silicone resin, saturated polyester resin, and the like, and acrylic resin is preferred.

作為聚合物成分(A)之前述丙烯酸樹脂，可列舉如公知的丙烯酸聚合物。 丙烯酸樹脂的重量平均分子量(Mw)較佳為10000至2000000，更佳為100000至1500000，又更佳為200000至1200000，尤佳為300000至1000000。藉由丙烯酸樹脂的重量平均分子量為前述下限值以上，提高保護膜形成膜的造膜性。藉由丙烯酸樹脂的重量平均分子量為前述上限值以下，保護膜形成膜變得容易追隨受附著體的凹凸面。 Examples of the acrylic resin as 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, still more preferably 200,000 to 1,200,000, even more preferably 300,000 to 1,000,000. When the weight average molecular weight of the acrylic resin is equal to or higher than the aforementioned lower limit, the film-forming properties of the protective film-forming film are improved. When the weight average molecular weight of the acrylic resin is equal to or less than the upper limit, the protective film-forming film can easily follow the uneven surface of the adherend.

本說明書之中，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法(GPC；Gel Permeation Chromatography)所測定之聚苯乙烯換算值。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.

丙烯酸樹脂的玻璃轉移溫度(Tg)較佳為－60℃至70℃，更佳為－50℃至50℃，又更佳為－50℃至20℃。藉由丙烯酸樹脂的Tg為前述下限值以上，例如，保護膜形成膜的硬化物與支撐片之密接性得到抑制，支撐片的剝離性適度地提高。藉由丙烯酸樹脂的Tg為前述上限值以下，熱硬化性保護膜形成膜以及其硬化物與受附著體之接著力提高。The glass transition temperature (Tg) of the acrylic resin is preferably -60°C to 70°C, more preferably -50°C to 50°C, still more preferably -50°C to 20°C. When the Tg of the acrylic resin is equal to or higher than the aforementioned lower limit, for example, the adhesion 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. 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.

丙烯酸樹脂係具有m種(m為2以上的整數)的構成單元，相對於衍生這些構成單元之m種的單體，分別依序分配1至m為止中任一者之不重複之編號，取名為「單體m」之情形時，丙烯酸樹脂的玻璃轉移溫度(Tg)能夠使用以下所示之Fox的式來算出。Acrylic resin has m types of structural units (m is an integer of 2 or more). The m types of monomers from which these structural units are derived are assigned non-overlapping numbers from 1 to m, respectively. In the case of "monomer m", the glass transition temperature (Tg) of the acrylic resin can be calculated using Fox's formula shown below.

[數1] (式中，Tg為丙烯酸樹脂的玻璃轉移溫度；m為2以上的整數；Tg k為單體m的均聚物的玻璃轉移溫度；W k為丙烯酸樹脂中衍生自單體m之構成單元m的質量分率，其中，W k係滿足下述式。) [Number 1] (In the formula, Tg is the glass transition temperature of acrylic resin; m is an integer above 2; Tg k is the glass transition temperature of the homopolymer of monomer m; W k is the structural unit m derived from monomer m in acrylic resin The mass fraction of , where W k satisfies the following formula.)

[數2] (式中，m以及W k係與前述相同。) [Number 2] (In the formula, m and W k are the same as mentioned above.)

作為前述Tg k，能夠使用高分子資料/手冊、黏著手冊或Polymer Handbook等所記載之值。例如，丙烯酸甲酯的均聚物的Tg k為10℃，甲基丙烯酸甲酯的均聚物的Tg k為105℃，丙烯酸-2-羥乙酯的均聚物的Tg k為－15℃，甲基丙烯酸縮水甘油酯的均聚物的Tg k為41℃，丙烯酸-2-乙基己酯的均聚物的Tg k為－70℃，丙烯酸的均聚物的Tg k為103℃，丙烯腈的均聚物的Tg k為97℃，丙烯酸正丁酯的均聚物的Tg k為－54℃，丙烯酸乙酯的均聚物的Tg k為－24℃。 As the above-mentioned Tg k , the value described in polymer materials/handbooks, adhesive handbooks, Polymer Handbooks, etc. can be used. For example, the Tg k of the homopolymer of methyl acrylate is 10°C, the Tg k of the homopolymer of methyl methacrylate is 105°C, and the Tg k of the homopolymer of 2-hydroxyethyl acrylate is -15°C. , the Tg k of the homopolymer of glycidyl methacrylate is 41°C, the Tg k of the homopolymer of 2-ethylhexyl acrylate is -70°C, and the Tg k of the homopolymer of acrylic acid is 103°C. The Tg k of the homopolymer of acrylonitrile is 97°C, the Tg k of the homopolymer of n-butyl acrylate is -54°C, and the Tg k of the homopolymer of ethyl acrylate is -24°C.

作為丙烯酸樹脂，例如可列舉：1種或2種以上的(甲基)丙烯酸酯的聚合物；選自前述(甲基)丙烯酸酯、(甲基)丙烯酸、伊康酸、乙酸乙烯酯、丙烯腈、苯乙烯以及N-羥甲基丙烯醯胺等之2種以上的單體的共聚物等。Examples of the acrylic resin include polymers of one or more (meth)acrylic acid esters, selected from the group consisting of the aforementioned (meth)acrylic acid esters, (meth)acrylic acid, itaconic acid, vinyl acetate, and acrylic acid. Copolymers of two or more monomers such as nitrile, styrene, and N-hydroxymethylacrylamide, etc.

作為構成丙烯酸樹脂之前述(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)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(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)丙烯酸硬脂酸酯)等構成烷基酯之烷基係碳數為1至18的鏈狀結構之(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)丙烯酸苄基酯等(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)丙烯酸醯亞胺；(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)丙烯酸羥甲酯、(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-2-羥丙酯、(甲基)丙烯酸-3-羥丙酯、(甲基)丙烯酸-2-羥丁酯、(甲基)丙烯酸-3-羥丁酯、(甲基)丙烯酸-4-羥丁酯等含羥基之(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」，意指具有胺基的1個或2個氫原子由氫原子以外的基取代而成之結構之基。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 ester , n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate )Hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-octyl (meth)acrylate Nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate) , Tridecyl (meth)acrylate, Myristyl (meth)acrylate (Myristyl (meth)acrylate), Pentadecyl (meth)acrylate, Tendecyl (meth)acrylate Alkyl groups are composed of hexalkyl ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate ((meth)acrylic acid stearate), etc. The alkyl group of the ester is a (meth)acrylic acid alkyl ester with a chain structure of 1 to 18 carbon atoms; (meth)acrylic acid rings such as (meth)isobornyl acrylate and (meth)acrylic acid dicyclopentyl ester Alkyl esters; aralkyl (meth)acrylates such as benzyl (meth)acrylate; cycloalkenyl acrylates such as dicyclopentenyl (meth)acrylate; bicyclic (meth)acrylate (Meth)acrylic acid cycloalkenyloxyalkyl esters such as pentenyloxyethyl ester; (meth)acrylic acid imide; (meth)acrylic acid glycidyl ester and other glycidyl group-containing (meth)acrylic acid esters; Hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylic acid -2-Hydroxybutyl ester, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyl-containing (meth)acrylates; (meth)acrylic acid N-methyl Aminoethyl ester and other (meth)acrylate containing substituted amine groups. Here, the "substituted amino group" means a group having a structure in which one or two hydrogen atoms of the amine group are substituted with groups other than hydrogen atoms.

本說明書之中，所謂「(甲基)丙烯酸」的概念包括「丙烯酸」以及「甲基丙烯酸」兩者。關於與(甲基)丙烯酸類似的用語亦相同，例如所謂「(甲基)丙烯醯基」的概念包括「丙烯醯基」以及「甲基丙烯醯基」兩者，所謂「(甲基)丙烯酸酯」的概念包括「丙烯酸酯」以及「甲基丙烯酸酯」兩者。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". The so-called "(meth)acrylic acid" The concept of "ester" includes both "acrylate" and "methacrylate".

構成丙烯酸樹脂之單體可僅為1種，亦可為2種以上，為2種以上之情形時，這些單體的組合以及比率可任意選擇。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.

丙烯酸樹脂亦可具有能夠與乙烯基、(甲基)丙烯醯基、胺基、羥基、羧基、異氰酸酯基等其他化合物鍵結之官能基。丙烯酸樹脂之前述官能基可經由後述之交聯劑(F)而與其他化合物鍵結，亦可不經由交聯劑(F)而與其他化合物直接鍵結。Acrylic resin 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 groups 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).

本發明之中，作為聚合物成分(A)，亦可單獨使用丙烯酸樹脂以外的熱塑性樹脂(以下有時簡記為「熱塑性樹脂」)而不使用丙烯酸樹脂，亦可併用丙烯酸樹脂。藉由使用前述熱塑性樹脂，有時保護膜自支撐片之剝離性提高，保護膜形成膜變得容易追隨受附著體的凹凸面。In the present invention, as the polymer component (A), a thermoplastic resin other than an acrylic resin (hereinafter sometimes abbreviated as “thermoplastic resin”) may be used alone instead of an acrylic resin, or an acrylic resin may be used in combination. By using the aforementioned thermoplastic resin, the peelability of the protective film self-supporting sheet may be improved, and the protective film-forming film may easily follow the uneven surface of the adherend.

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)以及保護膜形成膜所含有之前述熱塑性樹脂可僅為1種，亦可為2種以上，為2種以上之情形時，這些前述熱塑性樹脂的組合以及比率可任意選擇。The composition (III) and the protective film-forming film may contain only one type of thermoplastic resin, or may contain two or more types. In the case of two or more types, the combination and ratio of these thermoplastic resins may be selected arbitrarily.

組成物(III)中，無關聚合物成分(A)的種類，聚合物成分(A)的含量相對於溶媒以外的所有成分的總含量之比率，較佳為10質量%至85質量%，更佳為10質量%至65質量%，又更佳為10質量%至45質量%，例如亦可為10質量%至35質量%。 此內容係與如下內容相同含義：保護膜形成膜中，無關聚合物成分(A)的種類，相對於保護膜形成膜的總質量，聚合物成分(A)的含量的比率較佳為10質量%至85質量%，更佳為10質量%至65質量%，又更佳為10質量%至45質量%，例如亦可為10質量%至35質量%。 這是由於在從含有溶媒之樹脂組成物去除溶媒而形成樹脂膜之過程中，溶媒以外的成分的量通常不會變化，而樹脂組成物與樹脂膜在溶媒以外之成分彼此的含量的比率相同。因此，本說明書之中，以下不限於保護膜形成膜之情形，對於溶媒以外的成分的含量，僅記載在從樹脂組成物去除溶媒之樹脂膜之含量。 In composition (III), regardless of the type of polymer component (A), the ratio of the content of polymer component (A) to the total content of all components except the solvent is preferably 10 mass% to 85 mass%, more preferably Preferably, it is 10 mass % to 65 mass %, More preferably, it is 10 mass % to 45 mass %, For example, it may also be 10 mass % to 35 mass %. This content has the same meaning as the following: In the protective film-forming film, regardless of the type of the polymer component (A), the ratio of the content of the polymer component (A) to the total mass of the protective film-forming film is preferably 10 mass % to 85 mass%, more preferably 10 mass% to 65 mass%, more preferably 10 mass% to 45 mass%, for example, 10 mass% to 35 mass%. This is because in the process of forming a resin film by removing the solvent from the resin composition containing the solvent, the amounts of components other than the solvent usually do not change, and the ratios of the contents of components other than the solvent in the resin composition and the resin film are the same. . Therefore, in this specification, the following description is not limited to the case where a protective film is formed of a film. The contents of components other than the solvent are only described in the resin film after removing the solvent from the resin composition.

聚合物成分(A)有時亦相當於熱硬化性成分(B)。本發明之中，組成物(III)含有相當於這種聚合物成分(A)以及熱硬化性成分(B)兩者之成分之情形時，組成物(III)視為含有聚合物成分(A)以及熱硬化性成分(B)。The polymer component (A) may also correspond to the thermosetting component (B). In the present invention, when the composition (III) contains components corresponding to both the polymer component (A) and the thermosetting component (B), the composition (III) is deemed to contain the polymer component (A). ) and thermosetting component (B).

[熱硬化性成分(B)] 熱硬化性成分(B)係用以使保護膜形成膜硬化之成分。 組成物(III)以及保護膜形成膜所含有之熱硬化性成分(B)可僅為1種，亦可為2種以上，為2種以上之情形時，這些熱硬化性成分(B)的組合以及比率可任意選擇。 [Thermosetting ingredient (B)] The thermosetting component (B) is a component for hardening the protective film-forming film. The thermosetting component (B) contained in the composition (III) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the thermosetting component (B) may be Combinations and ratios 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、熱硬化性聚醯亞胺樹脂、不飽和聚酯樹脂等，較佳為環氧系熱硬化性樹脂。 本說明書之中，所謂熱硬化性聚醯亞胺樹脂，意指藉由熱硬化而形成聚醯亞胺樹脂之聚醯亞胺前驅物、以及熱硬化性聚醯亞胺之總稱。 Examples of the thermosetting component (B) include epoxy thermosetting resins, thermosetting polyimide resins, unsaturated polyester resins, and the like, and epoxy thermosetting resins are preferred. In this specification, the thermosetting polyimide resin refers to the general name of the polyimide precursor that forms the polyimide resin by thermal curing, and the thermosetting polyimide.

(環氧系熱硬化性樹脂) 環氧系熱硬化性樹脂係由環氧樹脂(B1)以及熱硬化劑(B2)所構成。 組成物(III)以及保護膜形成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，為2種以上之情形時，這些環氧系熱硬化性樹脂的組合以及比率可任意選擇。 (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) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the number of these epoxy-based thermosetting resins may be Combinations and ratios can be selected arbitrarily.

・環氧樹脂(B1) 作為環氧樹脂(B1)，可列舉如公知之環氧樹脂，例如可列舉：多官能系環氧樹脂、聯苯化合物、雙酚A二縮水甘油醚以及其氫化物、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官能以上的環氧化合物。 ・Epoxy resin (B1) Examples of the epoxy resin (B1) include known epoxy resins, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, and o-cresol novolak rings. Oxygen 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 bifunctional or higher ring oxygen compounds.

作為環氧樹脂(B1)，亦可使用具有不飽和烴基之環氧樹脂。As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can also be used.

環氧樹脂(B1)的數量平均分子量並無特別限定，由保護膜形成膜的硬化性、以及保護膜的強度以及耐熱性的方面來看，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 from the viewpoint of the hardening properties of the protective film-forming film, the strength and heat resistance of the protective film, it is preferably 300 to 30,000, and more preferably 300 to 10,000. , especially 300 to 3000. 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)係作為針對環氧樹脂(B1)之硬化劑而發揮功能。 作為熱硬化劑(B2)例如可列舉：1分子中具有2個以上可與環氧基進行反應之官能基之化合物。作為前述官能基，例如可列舉：酚性羥基、醇性羥基、胺基、羧基、酸基經酐化而成之基等，較佳為酚性羥基、胺基、或酸基經酐化而成之基，更佳為酚性羥基或胺基。 ・Thermal hardener (B2) The thermosetting agent (B2) functions as a hardening agent 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)之中，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)之中，作為具有胺基之胺系硬化劑，例如可列舉二氰二胺等。 Among the thermal curing agents (B2), examples of phenolic curing agents having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl groups. Type 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。The thermal hardener (B2) may have an unsaturated hydrocarbon group.

使用酚系硬化劑作為熱硬化劑(B2)之情形時，由保護膜自支撐片之剝離性提高的方面來看，熱硬化劑(B2)較佳係軟化點或玻璃轉移溫度高之熱硬化劑。When a phenolic hardener is used as the thermosetting agent (B2), from the viewpoint of improving the peelability of the protective film self-supporting sheet, the thermosetting agent (B2) is preferably one with a high softening point or glass transition temperature. agent.

熱硬化劑(B2)之中，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)之中，例如，聯苯酚、二氰二胺等非樹脂成分的分子量並無特別限定，例如較佳為60至500。 Among the thermosetting agents (B2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolac-type phenol resin, dicyclopentadiene-type phenol resin, and aralkyl-type phenol resin is preferably 300 to 30,000. , preferably 400 to 10,000, particularly preferably 500 to 3,000. Among the thermosetting agents (B2), the molecular weight of non-resin components such as biphenol and dicyandiamine is not particularly limited, but is preferably 60 to 500, for example.

熱硬化劑(B2)可單獨使用1種，亦可併用2種以上，於併用2種以上之情形時，這些熱硬化劑(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.

由在DSC之前述試片的發熱起始溫度變得更高的方面來看，熱硬化劑(B2)較佳係在常溫為固體狀，作為這種熱硬化劑，例如可列舉二氰二胺等。 亦即，前述保護膜形成膜較佳係含有至少在常溫為固體狀之熱硬化劑作為熱硬化劑(B2)。 Since the heat generation start temperature of the test piece before DSC becomes higher, the thermosetting agent (B2) is preferably solid at room temperature. Examples of such a thermosetting agent include dicyandiamide. wait. That is, the protective film-forming film preferably contains a thermosetting agent that is solid at least at room temperature as the thermosetting agent (B2).

組成物(III)以及保護膜形成膜中，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100質量份，更佳為0.5質量份至50質量份，例如亦可為0.5質量份至25質量份、0.5質量份至10質量份、以及0.5質量份至5質量份中任一者。藉由熱硬化劑(B2)之前述含量為前述下限值以上，保護膜形成膜的硬化變得更容易進行。藉由熱硬化劑(B2)之前述含量為前述上限值以下，保護膜形成膜的吸濕率減低，使用保護膜形成膜所獲得之封裝體的可靠性更加提高。In the composition (III) and the protective film-forming film, the content of the thermosetting agent (B2) is preferably 0.1 to 100 parts by mass, more preferably 0.5, based on 100 parts by mass of the epoxy resin (B1). Parts by mass to 50 parts by mass, for example, any one of 0.5 parts by mass to 25 parts by mass, 0.5 parts by mass to 10 parts by mass, and 0.5 parts by mass to 5 parts by mass. When the content of the thermosetting agent (B2) is equal to or higher than the lower limit, the protective film-forming film can be cured more easily. When the content of the thermosetting agent (B2) is equal to or less than the upper limit, the moisture absorption rate of the protective film-forming film is reduced, and the reliability of the package obtained using the protective film-forming film is further improved.

組成物(III)以及保護膜形成膜中，相對於熱硬化劑(B2)的總含量，在常溫為固體狀之熱硬化劑(B2)的含量的比率較佳為50質量%以上，更佳為70質量%以上，又更佳為90質量%以上，例如亦可為95質量%以上、97質量%以上、以及99質量%以上之中任一者，亦可為100質量%(亦即，組成物(III)以及保護膜形成膜僅含有在常溫為固體狀之熱硬化劑作為熱硬化劑(B2))。前述比率越高，在DSC之前述試片的發熱起始溫度有變高的傾向。In the composition (III) and the protective film-forming film, the ratio of the content of the thermosetting agent (B2) that is solid at normal temperature to the total content of the thermosetting agent (B2) is preferably 50 mass % or more, more preferably It is 70 mass% or more, more preferably 90 mass% or more. For example, it may be any one of 95 mass% or more, 97 mass% or more, and 99 mass% or more, and it may be 100 mass% (that is, The composition (III) and the protective film-forming film contain only a thermosetting agent that is solid at normal temperature as the thermosetting agent (B2)). The higher the ratio, the higher the heat generation starting temperature of the test piece before DSC.

組成物(III)以及保護膜形成膜中，熱硬化性成分(B)的含量，相對於聚合物成分(A)以及熱硬化性成分(B)的總含量100質量份，較佳為10質量份至70質量份，更佳為20質量份至65質量份，又更佳為30質量份至60質量份，例如亦可為40質量份至55質量份。藉由熱硬化性成分(B)之前述含量為這種範圍，例如，保護膜形成膜的硬化物與支撐片之密接性得到抑制，支撐片的剝離性提高。In the composition (III) and the protective film-forming film, the content of the thermosetting component (B) is preferably 10 parts by mass relative to 100 parts by mass of the total content of the polymer component (A) and the thermosetting component (B). parts by mass to 70 parts by mass, more preferably 20 parts by mass to 65 parts by mass, still more preferably 30 parts by mass to 60 parts by mass, for example, 40 parts by mass to 55 parts by mass. When the aforementioned content of the thermosetting component (B) is in this range, for example, the adhesion 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)] 硬化促進劑(C)係用以調整組成物(III)的硬化速度之成分。 作為較佳的硬化促進劑(C)，例如可列舉：三乙烯二胺、苄基二甲胺、三乙醇胺、二甲胺基乙醇、三(二甲胺基甲基)苯酚等三级胺；2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4,5-二羥甲基咪唑、2-苯基-4-甲基-5-羥甲基咪唑、2-十七烷基咪唑等咪唑類(1個以上的氫原子由氫原子以外的基所取代之咪唑)；三丁基膦、二苯基膦、三苯基磷等有機膦類(1個以上的氫原子由有機基所取代之膦)；四苯基鏻四苯基硼酸鹽、三苯基膦四苯基硼酸鹽等四苯基硼酸鹽等。 [Harding accelerator (C)] The hardening accelerator (C) is a component used to adjust the hardening speed of the composition (III). 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 and 2-heptadecylimidazole (imidazole in which more than one hydrogen atom is replaced by a group other than a hydrogen atom); organic compounds such as tributylphosphine, diphenylphosphine, triphenylphosphine, etc. Phosphines (phosphines in which one or more hydrogen atoms are replaced by organic groups); tetraphenylborate such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, etc.

組成物(III)以及保護膜形成膜所含有之硬化促進劑(C)可僅為1種，亦可為2種以上，為2種以上之情形時，這些硬化促進劑(C)的組合以及比率可任意選擇。The hardening accelerator (C) contained in the composition (III) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination of these hardening accelerators (C) and The ratio can be chosen arbitrarily.

由在DSC之前述試片的發熱起始溫度變得更高的方面來看，硬化促進劑(C)較佳為反應起始溫度較低之硬化促進劑，作為這種硬化促進劑，例如可列舉咪唑類等。 前述保護膜形成膜較佳係至少含有咪唑類作為硬化促進劑(C)。 Since the heat generation start temperature of the test piece before DSC becomes higher, the hardening accelerator (C) is preferably a hardening accelerator with a lower reaction start temperature. As such a hardening accelerator, for example, Examples include imidazoles and the like. The protective film-forming film preferably contains at least imidazoles as a hardening accelerator (C).

當使用硬化促進劑(C)之情形時，組成物(III)以及保護膜形成膜中，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，例如亦可為0.5質量份至5質量份、以及0.5質量份至3.5質量份中任一者。藉由硬化促進劑(C)之前述含量為前述下限值以上，更顯著地獲得使用硬化促進劑(C)所帶來之功效。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)於高溫及高濕度條件下抑制在保護膜形成膜中移動至與受附著體之接著界面側而偏析之功效變高。結果，使用保護膜形成膜所獲得之具保護膜之半導體晶片的可靠性更加提高。When a hardening accelerator (C) is used, the content of the hardening accelerator (C) in the composition (III) and the protective film-forming film is preferably 100 parts by mass relative to the content of the thermosetting component (B). It is 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, and for example, it may be any one of 0.5 to 5 parts by mass, and 0.5 to 3.5 parts by mass. By setting the aforementioned content of the hardening accelerator (C) to be above the aforementioned lower limit, the effect of using the hardening accelerator (C) can be more significantly obtained. By setting the content of the hardening accelerator (C) below the aforementioned upper limit, for example, the highly polar hardening accelerator (C) is prevented from moving in the protective film-forming film to adhere to the adherend under conditions of high temperature and high humidity. The efficiency of segregation becomes higher when the interface is lateral. As a result, the reliability of the semiconductor wafer with the protective film obtained using the protective film-forming film is further improved.

組成物(III)以及保護膜形成膜中，相對於硬化促進劑(C)的總含量，咪唑類之硬化促進劑(C)的含量的比率較佳為50質量%以上，更佳為70質量%以上，又更佳為90質量%以上，例如亦可為95質量%以上、97質量%以上、以及99質量%以上之中任一者，亦可為100質量%(亦即，組成物(III)以及保護膜形成膜僅含有咪唑類作為硬化促進劑(C))。前述比率越高，在DSC之前述試片的發熱起始溫度有變高的傾向。In the composition (III) and the protective film-forming film, the ratio of the content of the imidazole-based hardening accelerator (C) to the total content of the hardening accelerator (C) is preferably 50 mass % or more, more preferably 70 mass % % or more, and more preferably 90 mass% or more, for example, it may be any one of 95 mass% or more, 97 mass% or more, and 99 mass% or more, and it may be 100 mass% (that is, the composition ( III) and the protective film-forming film contains only imidazoles as hardening accelerator (C)). The higher the ratio, the higher the heat generation starting temperature of the test piece before DSC.

[填充材(D)] 藉由保護膜形成膜含有填充材(D)，熱硬化性保護膜形成膜與保護膜之熱膨脹係數的調整變得容易，藉由將該熱膨脹係數針對保護膜的形成對象物進行最佳化，使用保護膜形成膜所獲得之具保護膜之半導體晶片的可靠性更加提高。另外，藉由熱硬化性保護膜形成膜含有填充材(D)，亦能夠減低保護膜的吸濕率，或是提高散熱性。 [Filling material (D)] When the protective film-forming film contains the filler (D), the thermal expansion coefficient of the thermosetting protective film-forming film and the protective film can be easily adjusted. By optimizing the thermal expansion coefficient for the object to be formed of the protective film, The reliability of the semiconductor wafer with the protective film obtained by using the protective film forming film is 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(D)亦可為有機填充材以及無機填充材中任一者，較佳為無機填充材。 作為較佳的無機填充材，例如可列舉：二氧化矽、氧化鋁、滑石、碳酸鈣、鈦白、鐵丹、碳化矽、氮化硼等粉末；將這些無機填充材進行球形化之珠粒；這些無機填充材的表面改質品；這些無機填充材的單晶纖維；玻璃纖維等。 這些之中，無機填充材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. Preferred inorganic fillers include, for example, powders such as silica, alumina, talc, calcium carbonate, titanium dioxide, titanium dioxide, silicon carbide, boron nitride, etc.; these inorganic fillers can be made into spherical beads. ; Surface modification products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. Among these, the inorganic filler is preferably silica or alumina, and more preferably silica.

保護膜形成用組成物中，從填充材(D)相對於填充材(D)以外的成分之分散性提高的方面來看，前述二氧化矽較佳係以有機基進行表面修飾之二氧化矽，更佳係以乙烯基、環氧基、苯基或甲基丙烯酸基進行表面修飾之二氧化矽，尤佳係以乙烯基或環氧基進行表面修飾之二氧化矽。In the composition for forming a protective film, from the viewpoint of improving the dispersibility of the filler (D) with respect to components other than the filler (D), the silica is preferably silica surface-modified with an organic group. , more preferably silicon dioxide surface-modified with vinyl, epoxy, phenyl or methacrylic acid groups, particularly preferably silicon dioxide surface-modified with vinyl or epoxy groups.

保護膜形成用組成物中，從填充材(D)相對於填充材(D)以外的成分之分散性提高的方面來看，填充材(D)的平均粒徑較佳為0.02μm至2μm，更佳為0.05μm至1μm，尤佳為0.07μm至0.7μm。In the composition for forming a protective film, the average particle diameter of the filler (D) is preferably 0.02 μm to 2 μm, in order to improve the dispersibility of the filler (D) with respect to components other than the filler (D). More preferably, it is 0.05 μm to 1 μm, and even more preferably, it is 0.07 μm to 0.7 μm.

本說明書中所謂「平均粒徑」，只要無特別說明，意指使用電子顯微鏡，觀察作為對象物之粒子，隨機選擇100個粒子，這些粒子以俯視算出粒徑時之算術平均值([在100個粒子的俯視之粒徑的合計值]/100)。然後，能夠採用將在粒子的俯視之外周上任意的2點連結所獲得之線段的最大值作為此時之粒徑。 例如，如保護膜形成膜中之填充材(D)般，對於樹脂膜中之粒子，能夠藉由燒成樹脂膜而使樹脂成分消失之後，對於剩餘之粒子，藉由上述的方法而求得平均粒徑。 The so-called "average particle diameter" in this specification, unless otherwise specified, means that the particles of the object are observed using an electron microscope, 100 particles are randomly selected, and the arithmetic mean of the particle diameters of these particles is calculated from a top view ([in 100 The total value of the particle diameters of the particles]/100). Then, the maximum value of a line segment obtained by connecting two arbitrary points on the outer circumference of the particle in a plan view can be used as the particle diameter at this time. For example, like the filler (D) in the protective film-forming film, the particles in the resin film can be obtained by the method described above for the remaining particles after the resin component disappears by burning the resin film. Average particle size.

組成物(III)以及保護膜形成膜所含有之填充材(D)可僅為1種，亦可為2種以上，為2種以上之情形時，這些填充材(D)的組合以及比率可任意選擇。The filler (D) contained in the composition (III) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these fillers (D) may be Take your pick.

當保護膜形成膜含有填充材(D)之情形時，保護膜形成膜中，相對於保護膜形成膜的總質量，填充材(D)的含量的比率亦可為40質量%以上，較佳為50質量%以上，例如亦可為55質量%以上、以及60質量%以上之中任一者。藉由前述比率為前述下限值以上，保護膜形成膜能夠形成保護性能更高的保護膜，例如，抑制在具保護膜之半導體晶片之碎屑的功效變高。When the protective film-forming film contains the filler (D), the content ratio of the filler (D) in the protective film-forming film relative to the total mass of the protective film-forming film may be 40% by mass or more, which is preferred. It is 50 mass % or more, for example, it may be any one of 55 mass % or more, and 60 mass % or more. When the ratio is equal to or higher than the lower limit, the protective film-forming film can form a protective film with higher protective performance. For example, the effect of suppressing chips on a semiconductor wafer provided with the protective film becomes higher.

當保護膜形成膜含有填充材(D)之情形時，保護膜形成膜中，相對於保護膜形成膜的總質量，填充材(D)的含量的比率亦可為65質量%以下，較佳為63質量%以下，例如亦可為57質量%以下、以及50質量%以下之中任一者。藉由前述比率為前述上限值以下，當將保護膜形成膜貼附於保護對象的受附著體時，抑制保護膜與受附著體之積層物的翹曲的功效變高，例如，抑制在具保護膜之半導體晶圓之翹曲的功效變高。When the protective film-forming film contains the filler (D), the content ratio of the filler (D) in the protective film-forming film relative to the total mass of the protective film-forming film may be 65% by mass or less, which is preferred. It is 63 mass % or less, for example, it may be any one of 57 mass % or less, and 50 mass % or less. When the above-mentioned ratio is below the above-mentioned upper limit, when the protective film-forming film is attached to an adherend to be protected, the effect of suppressing the warpage of the laminate of the protective film and the adherend becomes higher, for example, Semiconductor wafers with protective films are more susceptible to warping.

保護膜形成膜中，相對於保護膜形成膜的總質量，填充材(D)的含量的比率可設定在將上述之任一下限值與任一上限值任意組合之範圍內來適當調節。 一實施形態中之前述比率亦可為40質量%至65質量%、40質量%至63質量%、40質量%至57質量%、以及40質量%至50質量%中任一者，亦可為50質量%至65質量%、50質量%至63質量%、以及50質量%至57質量%中任一者，亦可為55質量%至65質量%、以及55質量%至63質量%中任一者，亦可為60質量%至65質量%。然而，這些為前述比率之一例。 In the protective film-forming film, the ratio of the content of the filler (D) relative to the total mass of the protective film-forming film can be appropriately adjusted within the range of any combination of the above-mentioned lower limit value and any upper limit value. In one embodiment, the aforementioned ratio may be any one of 40 mass% to 65 mass%, 40 mass% to 63 mass%, 40 mass% to 57 mass%, and 40 mass% to 50 mass%, or it may be Any one of 50 mass % to 65 mass %, 50 mass % to 63 mass %, and 50 mass % to 57 mass % can also be any one of 55 mass % to 65 mass %, and 55 mass % to 63 mass %. Alternatively, it may be 60% by mass to 65% by mass. However, these are examples of the aforementioned ratios.

[偶合劑(E)] 組成物(III)以及保護膜形成膜亦可含有偶合劑(E)。藉由使用具有可與無機化合物或有機化合物進行反應的官能基者作為偶合劑(E)，能夠提高自保護膜形成膜所形成之保護膜對於受附著體之接著性。另外，藉由使用偶合劑(E)，前述保護膜能夠以不損及耐熱性的方式而提高耐水性。 [Coupling agent (E)] The composition (III) and the protective film-forming film may also contain the coupling agent (E). By using a coupling agent (E) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesiveness of the protective film formed by the self-protective film-forming film to the adherend can be improved. In addition, by using the coupling agent (E), the water resistance of the protective film can be improved without impairing the heat resistance.

偶合劑(E)較佳係具有可與聚合物成分(A)、熱硬化性成分(B)等所具有之官能基進行反應的官能基之化合物，更佳為矽烷偶合劑。The coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional group possessed by the polymer component (A), the thermosetting component (B), etc., and is more preferably a silane coupling agent.

作為較佳的前述矽烷偶合劑，例如可列舉：3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基甲基二乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基甲基二乙氧基矽烷、3-(苯基胺基)丙基三甲氧基矽烷、3-苯胺基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、雙(3-三乙氧基矽基丙基)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。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)以及保護膜形成膜所含有之偶合劑(E)可僅為1種，亦可為2種以上，為2種以上之情形時，這些偶合劑(E)的組合以及比率可任意選擇。The coupling agent (E) contained in the composition (III) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these coupling agents (E) may be Take your pick.

當使用偶合劑(E)之情形時，組成物(III)以及保護膜形成膜中，偶合劑(E)的含量，相對於聚合物成分(A)以及熱硬化性成分(B)的總含量100質量份，較佳為0.03質量份至10質量份，更佳為0.05質量份至5質量份，尤佳為0.1質量份至2質量份。藉由偶合劑(E)之前述含量為這種範圍，能夠若干控制保護膜形成膜與受附著體之化學性的互適性，更容易地調整黏著性與剝離性。另一方面，藉由偶合劑(E)之前述含量為前述下限值以上，而提高填充材(D)於樹脂之分散性、或提高保護膜形成膜與受附著體之接著性等，更顯著地獲得藉由使用偶合劑(E)所帶來之功效。藉由偶合劑(E)之前述含量為前述上限值以下，更加抑制逸氣的產生。When a coupling agent (E) is used, the content of the coupling agent (E) in the composition (III) and the protective film-forming film is relative to the total content of the polymer component (A) and the thermosetting component (B). 100 parts by mass, preferably 0.03 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, particularly preferably 0.1 to 2 parts by mass. By setting the aforementioned content of the coupling agent (E) within this range, the chemical compatibility of the protective film-forming film and the adherend can be somewhat controlled, and the adhesion and peelability can be adjusted more easily. On the other hand, by making the coupling agent (E) have the above-mentioned content above the above-mentioned lower limit, the dispersibility of the filler (D) in the resin can be improved, or the adhesion between the protective film-forming film and the adherend can be improved, etc., and more The effects brought about by the use of coupling agent (E) are significantly obtained. By setting the aforementioned content of the coupling agent (E) below the aforementioned upper limit, the generation of outgassing can be further suppressed.

[交聯劑(F)] 當使用上述的丙烯酸樹脂等具有可與其他化合物鍵結的乙烯基、(甲基)丙烯醯基、胺基、羥基、羧基、異氰酸酯基等官能基者作為聚合物成分(A)之情形時，組成物(III)以及保護膜形成膜亦可含有交聯劑(F)。交聯劑(F)係用以使聚合物成分(A)中之前述官能基與其他化合物鍵結進行交聯之成分，藉由這樣進行交聯，能夠調節保護膜形成膜的黏著力以及凝聚力。 [Crosslinking agent (F)] When the above-mentioned acrylic resin or the like having functional groups such as a vinyl group, a (meth)acryl group, an amine group, a hydroxyl group, a carboxyl group, and an isocyanate group that can be bonded to other compounds is used as the polymer component (A), The composition (III) and the protective film-forming film may also contain a cross-linking agent (F). The cross-linking agent (F) is a component used to cross-link the aforementioned functional groups in the polymer component (A) by bonding them to other compounds. By cross-linking in this way, the adhesive force and cohesion of the protective film-forming film can be adjusted. .

作為交聯劑(F)，例如可列舉：有機多元異氰酸酯化合物、有機多元亞胺化合物、金屬螯合物系交聯劑(具有金屬螯合物結構之交聯劑)、氮丙啶系交聯劑(具有氮丙啶基之交聯劑)等。Examples of the 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.

組成物(III)以及保護膜形成膜所含有之交聯劑(F)可僅為1種，亦可為2種以上，為2種以上之情形時，這些交聯劑(F)的組合以及比率可任意選擇。The cross-linking agent (F) contained in the composition (III) and the protective film-forming film may be only one type, or two or more types. In the case of two or more types, the combination of these cross-linking agents (F) and The ratio can be chosen arbitrarily.

由提高保護膜形成用組成物的經時穩定性的方面來看，較佳係組成物(III)不含交聯劑(F)、或是組成物(III)中交聯劑(F)的含量相對於聚合物成分(A)的含量100質量份例如未達0.01質量份等交聯劑(F)的含量少之情況。 相對於此，當使用一定量以上的交聯劑(F)之情形時，組成物(III)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)之前述含量為前述下限值以上，而更顯著地獲得使用交聯劑(F)所帶來之功效。藉由交聯劑(F)之前述含量為前述上限值以下，抑制交聯劑(F)的過度使用。 From the viewpoint of improving the stability over time of the composition for forming a protective film, it is preferable that the composition (III) does not contain the cross-linking agent (F), or that the composition (III) contains the cross-linking agent (F). The content of the cross-linking agent (F) is small, for example, less than 0.01 parts by mass relative to 100 parts by mass of the content of the polymer component (A). On the other hand, when more than a certain amount of the cross-linking agent (F) is used, the content of the cross-linking agent (F) in the composition (III) is, relative to 100 parts by mass of the content of the polymer component (A), Preferably it is 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, still more preferably 0.5 to 5 parts by mass. By setting the aforementioned content of the cross-linking agent (F) to be above the aforementioned lower limit, the effects brought about by the use of the cross-linking agent (F) can be more significantly obtained. When the content of the cross-linking agent (F) is equal to or less than the upper limit, excessive use of the cross-linking agent (F) is suppressed.

[能量線硬化性樹脂(G)] 組成物(III)以及保護膜形成膜亦可含有能量線硬化性樹脂(G)。保護膜形成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) and the protective film-forming film may contain energy ray curable resin (G). Since the protective film-forming film contains energy ray curable resin (G), its properties can be changed by irradiating energy rays.

能量線硬化性樹脂(G)係能量線硬化性化合物或是可視為由能量線硬化性化合物所合成之寡聚物或是聚合物(polymer)。 作為前述能量線硬化性化合物，例如可列舉在分子內具有至少1個聚合性雙鍵之化合物，較佳係具有(甲基)丙烯醯基之丙烯酸酯系化合物。 The energy ray curable resin (G) is an energy ray curable compound or can be regarded as an oligomer or polymer synthesized from 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)丙烯酸酯等聚烷二醇(甲基)丙烯酸酯；寡酯(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲酸酯寡聚物；環氧改質(甲基)丙烯酸酯；前述聚烷二醇(甲基)丙烯酸酯以外的聚醚(甲基)丙烯酸酯；伊康酸寡聚物等。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) Acrylates; polyether (meth)acrylates other than the aforementioned polyalkylene glycol (meth)acrylates; itaconic acid oligomers, 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.

用於前述寡聚物或是聚合物的合成之前述能量線硬化性化合物可僅為1種，亦可為2種以上，為2種以上之情形時，這些前述能量線硬化性化合物的組合以及比率可任意選擇。The energy ray curable compound used for the synthesis of the oligomer or polymer may be only one type, or two or more types. In the case of two or more types, the combination of these energy ray curable compounds and The ratio can be chosen arbitrarily.

組成物(III)以及保護膜形成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，為2種以上之情形時，這些能量線硬化性樹脂(G)的組合以及比率可任意選擇。The energy ray curable resin (G) contained in the composition (III) and the protective film-forming film may be only one type, or two or more types. In the case of two or more types, these energy ray curable resins (G) ) combinations and ratios can be selected arbitrarily.

當使用能量線硬化性樹脂(G)之情形時，組成物(III)中，相對於組成物(III)的總質量，能量線硬化性樹脂(G)的含量的比率較佳為1質量%至30質量%，更佳為5質量%至25質量%，尤佳為10質量%至20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) relative to the total mass of the composition (III) is preferably 1% by mass. to 30% by mass, more preferably 5% to 25% by mass, particularly preferably 10% to 20% by mass.

[光聚合起始劑(H)] 當組成物(III)以及保護膜形成膜含有能量線硬化性樹脂(G)之情形時，為了更有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) and the protective film-forming film contain the energy ray curable resin (G), a photopolymerization initiator may be included in order to perform the polymerization reaction of the energy ray curable resin (G) more efficiently. (H).

作為組成物(III)中之光聚合起始劑(H)，例如可列舉：安息香、安息香甲醚、安息香***、安息香異丙醚、安息香異丁醚、安息香苯甲酸、安息香苯甲酸甲酯、安息香二甲基縮酮等安息香化合物；苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、2-羥基-1-(4-(4-(2-羥基-2-甲基丙醯基)苄基)苯基)-2-甲基丙烷-1-酮、2-(二甲胺基)-1-(4-嗎啉苯基)-2-苄基-1-丁酮等苯乙酮化合物；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；1-氯蒽醌、2-氯蒽醌等醌化合物。 另外，作為光聚合起始劑(H)，例如可列舉：胺等光敏劑等。 Examples of the photopolymerization initiator (H) in the composition (III) include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoic acid, benzoin methyl benzoate, Benzoin compounds such as benzoin dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane Alkane-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanyl)benzyl)phenyl)-2-methylpropan-1-one, 2- Acetophenone compounds such as (dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone; bis(2,4,6-trimethylbenzoyl)benzene 1 -α-ketool compounds such as hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diethyl Dione compounds such as benzoyl; benzoyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1 -[4-(1-methylvinyl)phenyl]acetone; 1-chloroanthraquinone, 2-chloroanthraquinone and other quinone compounds. Examples of the photopolymerization initiator (H) include photosensitizers such as amines.

組成物(III)以及保護膜形成膜所含有之光聚合起始劑(H)可僅為1種，亦可為2種以上，為2種以上之情形時，這些光聚合起始劑(H)的組合以及比率可任意選擇。The photopolymerization initiator (H) contained in the composition (III) and the protective film-forming film may be only one type, or two or more types. In the case of two or more types, these photopolymerization initiators (H) ) combinations and ratios can be selected arbitrarily.

使用光聚合起始劑(H)之情形時，組成物(III)之中，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) is preferably 100 parts by mass relative to the content of the energy ray curable resin (G). 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, particularly preferably 2 to 5 parts by mass.

[著色劑(I)] 組成物(III)以及保護膜形成膜較佳係含有著色劑(I)。藉由含有著色劑(I)，能夠更容易地調節保護膜形成膜以及保護膜的光穿透性。 [Color(I)] The composition (III) and the protective film-forming film preferably contain the colorant (I). By containing the colorant (I), the light transmittance of the protective film-forming film and the protective film can be adjusted more easily.

作為著色劑(I)，例如可列舉：無機系顏料、有機系顏料、有機系染料等公知之顏料。Examples of the colorant (I) include well-known pigments such as inorganic pigments, organic pigments, and organic dyes.

作為前述有機系顏料以及有機系染料，例如可列舉：胺鎓系色素、花青系色素、部花青系色素、克酮鎓系色素、角鯊烯鎓系色素、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、芘酮系色素、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、喹酞酮系色素、吡咯系色素、硫靛藍系色素、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、吲哚苯酚系色素、三烯丙基甲烷系色素、蒽醌系色素、萘酚系色素、甲亞胺系色素、苯并咪唑酮系色素、皮蒽酮系色素以及士林系色素等。Examples of the organic pigments and organic dyes include amine-based pigments, cyanine-based pigments, merocyanine-based pigments, ketonium-based pigments, squalenium-based pigments, azulium-based pigments, and polysulfide pigments. Methyl pigments, naphthoquinone pigments, pyranium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphtholactam pigments, azo pigments, condensed azo pigments, indigo pigments, pyrene Ketone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinphthalone pigments, pyrrole pigments, thioindigo pigments, metal complex pigments (Metal complex dyes), dithiol metal complex pigments, indolephenol pigments, triallylmethane pigments, anthraquinone pigments, naphthol pigments, methimine pigments, benzimidazole Ketone pigments, picanthrone pigments and Shilin 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) based pigments, ATO (Antimony Tin Oxide, antimony tin oxide) based pigments, etc.

組成物(III)以及保護膜形成膜所含有之著色劑(I)可僅為1種，亦可為2種以上，為2種以上之情形時，這些著色劑(I)的組合以及比率可任意選擇。The colorant (I) contained in the composition (III) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these coloring agents (I) may be Take your pick.

當使用著色劑(I)之情形時，保護膜形成膜的著色劑(I)的含量只要根據目的而適當調節即可。例如，藉由調節保護膜形成膜的著色劑(I)的含量，調節保護膜形成膜的光穿透性，能夠調節對於保護膜形成膜或保護膜進行雷射印字之情形時的印字可讀性。另外，藉由調節保護膜形成膜的著色劑(I)的含量，能夠提高保護膜的設計性、或是亦能夠使得晶圓的內面的磨削痕不易見到。若考慮這些方面，保護膜形成膜中著色劑(I)的含量相對於保護膜形成膜的總質量之比率較佳為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%。藉由前述比率為前述下限值以上，可更顯著地獲得使用著色劑(I)所帶來之功效。例如，當從受附著體剝離保護膜形成膜時，保護膜形成膜於受附著體之中有無殘留，能夠藉由目視而容易地確認。藉由前述比率為前述上限值以下，著色劑(I)的過度使用得到抑制。When the colorant (I) is used, the content of the colorant (I) in the protective film-forming film may be appropriately adjusted depending on the purpose. For example, by adjusting the content of the colorant (I) in the protective film-forming film and adjusting the light transmittance of the protective film-forming film, it is possible to adjust the readability of the protective film-forming film or the protective film when laser printing is performed. sex. In addition, by adjusting the content of the colorant (I) in the protective film-forming film, the designability of the protective film can be improved, or the grinding marks on the inner surface of the wafer can be made less visible. Taking these aspects into consideration, the ratio of the content of the colorant (I) in the protective film-forming film to the total mass of the protective film-forming film is preferably 0.1 mass % to 10 mass %, more preferably 0.1 mass % to 7.5 mass %. Particularly preferably, it is 0.1% by 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. For example, when the protective film-forming film is peeled off from the adherend, whether or not the protective film-forming film remains in the adherend can be easily confirmed by visual inspection. When the ratio is equal to or less than the upper limit, excessive use of the colorant (I) is suppressed.

[通用添加劑(J)] 組成物(III)以及保護膜形成膜在不損及本發明的功效之範圍內，亦可含有通用添加劑(J)。 通用添加劑(J)可為公知者，可根據目的而任意選擇，並無特別限定，作為較佳的通用添加劑，例如可列舉：塑化劑、抗靜電劑、抗氧化劑、吸氣劑、紫外線吸收劑等。 [General Additive(J)] The composition (III) and the protective film-forming film may also contain a general additive (J) within the scope that does not impair the efficacy of the present invention. The general-purpose additive (J) can be a well-known one and can be selected arbitrarily according to the purpose, and is not particularly limited. Examples of preferred general-purpose additives include plasticizers, antistatic agents, antioxidants, getters, and ultraviolet absorbers. Agents, etc.

組成物(III)以及保護膜形成膜所含有之通用添加劑(J)可僅為1種，亦可為2種以上，為2種以上之情形時，這些通用添加劑(J)的組合以及比率可任意選擇。 組成物(III)以及保護膜形成膜的通用添加劑(J)的含量並無特別限定，可根據目的而適當選擇即可。 The general additive (J) contained in the composition (III) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these general additives (J) may be Take your pick. The contents of the composition (III) and the general additive (J) for forming a protective film are not particularly limited and can be appropriately selected depending on the purpose.

[溶媒] 組成物(III)較佳係進而含有溶媒。含有溶媒之組成物(III)之操作性變得良好。 本說明書之中，所謂「溶媒」，只要無特別說明，意指不僅使對象成分溶解，亦包含使對象成分分散之分散媒之概念。 [solvent] The composition (III) preferably further contains a solvent. The composition (III) containing a solvent has good operability. In this specification, the term "solvent" means a dispersion medium that not only dissolves the target component but also disperses the target component unless otherwise specified.

前述溶媒並無特別限定，作為較佳的溶媒，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-甲基吡咯烷酮等醯胺(具有醯胺鍵之化合物)等。 組成物(III)所含有之溶媒可僅為1種，亦可為2種以上，為2種以上之情形時，這些溶媒的組合以及比率可任意選擇。 The aforementioned 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), etc. The composition (III) 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.

組成物(III)所含有之溶媒，例如由可使組成物(III)中的含有成分更均勻混合的方面來看，作為更佳之溶媒可列舉甲基乙基酮、甲苯、乙酸乙酯等。The solvent contained in the composition (III) can, for example, mix the components contained in the composition (III) more uniformly. Examples of more preferable solvents include methyl ethyl ketone, toluene, ethyl acetate, and the like.

組成物(III)的溶媒的含量並無特別限定，例如可根據溶媒以外之成分之種類而適當選擇即可。The content of the solvent in the composition (III) is not particularly limited, and may be appropriately selected depending on the types of components other than the solvent.

[保護膜形成用組成物(III)之製造方法] 組成物(III)可藉由調配用以構成該組成物之各成分而獲得。 各成分的調配時之添加順序並無特別限定，亦可將2種以上的成分同時添加。 於調配時混合各成分之方法並無特別限定，自以下之公知的方法中適當選擇即可：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，適當調節即可，溫度較佳為15℃至30℃。 [Production method of protective film forming composition (III)] Composition (III) can be obtained by blending each component constituting the 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. 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; application of ultrasonic waves Mixing methods, etc. The temperature and time when adding and mixing each component are not particularly limited as long as each component is not deteriorated, and can be adjusted appropriately. The temperature is preferably 15°C to 30°C.

◎保護膜形成膜之例 圖1係示意性地表示本實施形態的保護膜形成膜之一例之剖面圖。此外，以下之說明所用之圖有時為了容易理解本發明之特徵，為方便起見而將成為要部之部分放大表示，各構成要素之尺寸比率等未必與實際相同。 ◎Examples of protective film forming films FIG. 1 is a cross-sectional view schematically showing an example of the protective film-forming film according to this embodiment. In addition, the drawings used in the following description may show essential parts enlarged for convenience in order to facilitate understanding of the features of the present invention, and the dimensional ratios of each component may not be the same as the actual ones.

此處所示之保護膜形成膜13於其中一面(本說明書之中，有時稱為「第一面」)13a上具備第一剝離膜151，於與前述第一面13a為相反側之另一面(本說明書之中，有時稱為「第二面」)13b上具備第二剝離膜152。 這種保護膜形成膜13係合適於例如作成輥狀來進行儲存。 The protective film forming film 13 shown here is provided with a first release film 151 on one side (sometimes referred to as the "first side" in this specification) 13a, and on the other side opposite to the first side 13a. The second release film 152 is provided on one side (sometimes referred to as the "second side" in this specification) 13b. This protective film-forming film 13 is suitable for storage in a roll shape, for example.

由保護膜形成膜13所製作之前述試片之上述在DSC之發熱起始溫度為160℃以上。The DSC heating onset temperature of the above-described test piece made of the protective film-forming film 13 is 160° C. or higher.

保護膜形成膜13可使用上述之保護膜形成用組成物來形成。The protective film forming film 13 can be formed using the above protective film forming composition.

第一剝離膜151以及第二剝離膜152可皆為公知者。 第一剝離膜151以及第二剝離膜152亦可彼此相同，亦可相互不同，例如自保護膜形成膜13剝離時所必需的剝離力相互不同等。 Both the first release film 151 and the second release film 152 may be known ones. The first release film 151 and the second release film 152 may be the same as each other, or may be different from each other. For example, the peeling forces necessary for peeling off the protective film forming film 13 may be different from each other.

圖1所示之保護膜形成膜13中移除第一剝離膜151以及第二剝離膜152中任一者而產生之露出面係成為對半導體晶圓(省略圖示)中內面之貼附面。並且，在使用後述之支撐片或切割片之情形時，第一剝離膜151以及第二剝離膜152之剩餘另一剝離膜被移除所產生之保護膜形成膜13之露出面成為前述支撐片或是切割片的貼附面。The exposed surface of the protective film forming film 13 shown in FIG. 1 by removing either the first release film 151 or the second release film 152 becomes the attachment surface to the inner surface of the semiconductor wafer (not shown). noodle. In addition, when a support sheet or a cutting sheet described later is used, the exposed surface of the protective film forming film 13 produced by removing the remaining release film of the first release film 151 and the second release film 152 becomes the support sheet. Or the attached surface of the cutting piece.

圖1之中，表示剝離膜設置在保護膜形成膜13的兩面(第一面13a、第二面13b)之例，但剝離膜亦可僅設置於保護膜形成膜13的任一面(亦即僅第一面13a、或是僅第二面13b)。FIG. 1 shows an example in which the release film is provided on both sides (the first surface 13 a and the second surface 13 b ) of the protective film-forming film 13 . However, the release film may be provided only on any one surface of the protective film-forming film 13 (that is, Only the first side 13a, or only the second side 13b).

作為本實施形態之較佳的保護膜形成膜之一例，可列舉如下之保護膜形成膜：一種熱硬化性的保護膜形成膜，藉由差示掃描熱量分析法，將前述保護膜形成膜的試片以升溫速度10℃/min、自23℃升溫至300℃為止時的發熱起始溫度為160℃以上，前述保護膜形成膜含有聚合物成分(A)、熱硬化性成分(B)、硬化促進劑(C)以及填充材(D)，前述聚合物成分(A)為丙烯酸樹脂，前述熱硬化性成分(B)係由環氧樹脂(B1)以及熱硬化劑(B2)所構成(亦即環氧系熱硬化性樹脂)，前述保護膜形成膜係至少含有咪唑類作為前述硬化促進劑(C)，前述填充材(D)為二氧化矽或氧化鋁的表面改質品。 這種保護膜形成膜中，前述填充材(D)亦可為以乙烯基、環氧基、苯基或甲基丙烯酸基進行表面修飾之二氧化矽。 這種保護膜形成膜亦可進而含有偶合劑(E)以及著色劑(I)中任一者或兩者，前述偶合劑(E)亦可為矽烷偶合劑。 As an example of a preferable protective film-forming film of this embodiment, the following protective film-forming film can be cited: a thermosetting protective film-forming film, which is obtained by using differential scanning calorimetry. When the test piece is heated from 23°C to 300°C at a heating rate of 10°C/min, the heating onset temperature is 160°C or above. The protective film-forming film contains a polymer component (A), a thermosetting component (B), Hardening accelerator (C) and filler (D), the aforementioned polymer component (A) is an acrylic resin, and the aforementioned thermosetting component (B) is composed of an epoxy resin (B1) and a thermosetting agent (B2) ( That is, an epoxy thermosetting resin), the protective film-forming film system contains at least imidazoles as the hardening accelerator (C), and the filler (D) is a surface modified product of silica or alumina. In this protective film-forming film, the filler (D) may also be silicon dioxide surface-modified with vinyl, epoxy, phenyl or methacrylic groups. This protective film-forming film may further contain any one or both of a coupling agent (E) and a coloring agent (I), and the coupling agent (E) may be a silane coupling agent.

作為本實施形態之較佳的保護膜形成膜之另一例，可列舉如下之保護膜形成膜：一種熱硬化性的保護膜形成膜，藉由差示掃描熱量分析法，將前述保護膜形成膜的試片以升溫速度10℃/min、自23℃升溫至300℃為止時的發熱起始溫度為160℃以上，前述保護膜形成膜含有聚合物成分(A)、熱硬化性成分(B)、硬化促進劑(C)以及填充材(D)，前述聚合物成分(A)為丙烯酸樹脂，前述熱硬化性成分(B)係由環氧樹脂(B1)以及熱硬化劑(B2)所構成(亦即環氧系熱硬化性樹脂)，前述保護膜形成膜係至少含有咪唑類作為前述硬化促進劑(C)，前述填充材(D)為二氧化矽或氧化鋁的表面改質品，前述保護膜形成膜中，相對於前述保護膜形成膜的總質量，前述聚合物成分(A)的含量的比率為10質量%至85質量%，前述保護膜形成膜中，相對於前述聚合物成分(A)以及熱硬化性成分(B)的總含量100質量份，前述熱硬化性成分(B)的含量為10質量份至70質量份，前述保護膜形成膜中，相對於前述熱硬化性成分(B)的含量100質量份，前述硬化促進劑(C)的含量為0.01質量份至10質量份，前述保護膜形成膜中，相對於前述保護膜形成膜的總質量，前述填充材(D)的含量的比率為40質量%至65質量%，前述保護膜形成膜中，相對於前述環氧樹脂(B1)的含量100質量份，前述熱硬化劑(B2)的含量為0.1質量%至100質量份，前述保護膜形成膜中，相對於前述熱硬化劑(B2)的總含量，在常溫為固體狀之前述熱硬化劑(B2)的含量的比率為50質量%以上，前述保護膜形成膜中，相對於前述硬化促進劑(C)的總含量，咪唑類之前述硬化促進劑(C)的含量的比率為50質量%以上，前述保護膜形成膜中，相對於前述保護膜形成膜的總質量，前述聚合物成分(A)、熱硬化性成分(B)、硬化促進劑(C)以及填充材(D)的合計含量的比率不超過100質量%。 這種其他例之保護膜形成膜中，前述填充材(D)亦可為以乙烯基、環氧基、苯基或甲基丙烯酸基進行表面修飾之二氧化矽。 這種其他例之保護膜形成膜中，前述聚合物成分(A)、熱硬化性成分(B)、環氧樹脂(B1)、熱硬化劑(B2)、硬化促進劑(C)以及填充材(D)之前述含量亦可進而為前文所說明之數值範圍中任一者。 As another example of a preferred protective film-forming film in this embodiment, the following protective film-forming film can be cited: a thermosetting protective film-forming film, the aforementioned protective film-forming film is obtained by differential scanning calorimetry. When the test piece is heated from 23°C to 300°C at a heating rate of 10°C/min, the heating onset temperature is 160°C or above. The protective film-forming film contains a polymer component (A) and a thermosetting component (B). , hardening accelerator (C) and filler (D), the aforementioned polymer component (A) is an acrylic resin, and the aforementioned thermosetting component (B) is composed of an epoxy resin (B1) and a thermosetting agent (B2). (that is, an epoxy thermosetting resin), the protective film-forming film system contains at least imidazole as the hardening accelerator (C), and the filler (D) is a surface modified product of silicon dioxide or alumina, In the protective film-forming film, the content ratio of the polymer component (A) is 10 mass % to 85 mass % with respect to the total mass of the protective film-forming film, and in the protective film-forming film, the content of the polymer component (A) is The total content of component (A) and thermosetting component (B) is 100 parts by mass, and the content of the aforementioned thermosetting component (B) is 10 to 70 parts by mass. In the aforementioned protective film-forming film, relative to the aforementioned thermosetting The content of the protective component (B) is 100 parts by mass, the content of the hardening accelerator (C) is 0.01 to 10 parts by mass, and in the protective film-forming film, the filler is The content ratio of (D) is 40 mass % to 65 mass %. In the protective film-forming film, the content of the thermosetting agent (B2) is 0.1 mass parts with respect to 100 mass parts of the epoxy resin (B1). % to 100 parts by mass, the ratio of the content of the thermal hardening agent (B2) in the solid state at normal temperature to the total content of the thermal hardening agent (B2) in the protective film-forming film is 50 mass % or more, the aforementioned In the protective film-forming film, the ratio of the content of the imidazole-based hardening accelerator (C) to the total content of the hardening accelerator (C) is 50 mass % or more, and in the protective film-forming film, the ratio of the content of the imidazoles to the total content of the hardening accelerator (C) is 50 mass % or more. The ratio of the total content of the polymer component (A), thermosetting component (B), hardening accelerator (C), and filler (D) to the total mass of the film-forming film does not exceed 100 mass %. In this other example of the protective film-forming film, the filler (D) may be silicon dioxide surface-modified with a vinyl group, an epoxy group, a phenyl group or a methacrylic acid group. In this other example of the protective film-forming film, the aforementioned polymer component (A), thermosetting component (B), epoxy resin (B1), thermosetting agent (B2), hardening accelerator (C), and filler (D) The aforementioned content may further be any one of the numerical ranges described above.

這種其他例之保護膜形成膜亦可進而含有偶合劑(E)以及著色劑(I)中任一者或兩者，於此情形時，前述偶合劑(E)為矽烷偶合劑，前述保護膜形成膜含有前述偶合劑(E)之情形時，前述保護膜形成膜中，相對於前述聚合物成分(A)以及熱硬化性成分(B)的總含量100質量份，前述偶合劑(E)的含量為0.03質量份至10質量份，前述保護膜形成膜含有前述著色劑(I)之情形時，前述保護膜形成膜中，相對於前述保護膜形成膜的總質量，前述著色劑(I)的含量的比率為0.1質量%至10質量%，前述保護膜形成膜中，相對於前述保護膜形成膜的總質量，前述聚合物成分(A)、熱硬化性成分(B)、硬化促進劑(C)、填充材(D)、偶合劑(E)以及著色劑(I)的合計含量的比率不超過100質量%。 這種其他例之保護膜形成膜中，前述聚合物成分(A)、熱硬化性成分(B)、環氧樹脂(B1)、熱硬化劑(B2)、硬化促進劑(C)、填充材(D)、偶合劑(E)以及著色劑(I)之前述含量亦可進而為前文所說明之數值範圍中任一者。 The protective film-forming film of this other example may further contain any one or both of the coupling agent (E) and the coloring agent (I). In this case, the aforementioned coupling agent (E) is a silane coupling agent, and the aforementioned protective film When the film-forming film contains the coupling agent (E), the coupling agent (E) is contained in the protective film-forming film relative to 100 parts by mass of the total content of the polymer component (A) and the thermosetting component (B). ) content is 0.03 parts by mass to 10 parts by mass, and when the protective film-forming film contains the colorant (I), in the protective film-forming film, relative to the total mass of the protective film-forming film, the colorant (I) The content ratio of I) is 0.1% by mass to 10% by mass. In the protective film-forming film, the polymer component (A), the thermosetting component (B), the cured The total content ratio of the accelerator (C), filler (D), coupling agent (E), and colorant (I) does not exceed 100% by mass. In this other example of the protective film-forming film, the aforementioned polymer component (A), thermosetting component (B), epoxy resin (B1), thermosetting agent (B2), hardening accelerator (C), filler The aforementioned contents of (D), coupling agent (E) and colorant (I) may further be any one of the numerical ranges described above.

本實施形態的保護膜形成膜藉由與後述之支撐片併用，可構成能夠一併進行保護膜的形成與切割之保護膜形成用複合片。以下對於這種保護膜形成用複合片進行說明。By using the protective film-forming film of this embodiment together with a support sheet described later, a protective film-forming composite sheet capable of simultaneously forming and cutting the protective film can be constructed. The composite sheet for forming a protective film will be described below.

◇保護膜形成用複合片 本發明的一實施形態之保護膜形成用複合片係具備支撐片、以及設置於前述支撐片之一面上之保護膜形成膜，前述保護膜形成膜係上述的本發明之一實施形態之保護膜形成膜。 本實施形態之保護膜形成用複合片能夠藉由其中之保護膜形成膜貼附於半導體晶圓的內面。 ◇Composite sheet for protective film formation A composite sheet for forming a protective film according to an embodiment of the present invention includes a support sheet and a protective film-forming film provided on one surface of the support sheet. The protective film-forming film is the protective film according to the above-mentioned embodiment of the present invention. Form a film. The protective film-forming composite sheet of this embodiment can be attached to the inner surface of the semiconductor wafer via the protective film-forming film therein.

本說明書之中，即使在保護膜形成膜硬化之後，只要維持支撐片與保護膜形成膜的硬化物之積層結構，仍稱該積層結構體為「保護膜形成用複合片」。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 is maintained, the laminated structure is called a "composite sheet for protective film formation."

以下對於構成前述保護膜形成用複合片之各層進行詳細的說明。Each layer constituting the composite sheet for forming a protective film will be described in detail below.

◎支撐片 前述支撐片可由1層(單層)所構成，亦可由2層以上的多層所構成。支撐片由多層所構成之情形時，這些多層的構成材料以及厚度可以互相相同或不同，這些多層的組合只要不損及本發明之功效，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 multiple layers of two or more layers. When the support sheet is composed of multiple layers, the constituent materials and thicknesses of these multiple layers may be the same or different from each other. The combination of these multiple layers is not particularly limited as long as the effect of the present invention is not impaired.

支撐片可為透明以及非透明中任一者，亦可根據目的進行著色。 在保護膜形成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。 The support sheet may be either transparent or non-transparent, and may be colored according to the purpose. When the protective film-forming film has energy ray curability, it is preferable that the support sheet allows energy rays to penetrate.

作為支撐片，例如可列舉：具備基材、以及設置於前述基材其中一面上之黏著劑層之支撐片；僅由基材所構成之支撐片等。支撐片具備黏著劑層之情形時，黏著劑層於保護膜形成用複合片之中係配置在基材與保護膜形成膜之間。Examples of the support sheet include a support sheet including a base material and an adhesive layer provided on one side of the base material; a support sheet consisting only of the base material; and the like. When the support sheet has an adhesive layer, the adhesive layer is disposed between the base material and the protective film-forming film in the protective film-forming composite sheet.

使用具備基材以及黏著劑層之支撐片之情形時，可容易地調節保護膜形成用複合片中之支撐片與保護膜形成膜之間的密接性以及剝離性。 使用僅由基材所構成之支撐片之情形時，可以低成本來製造保護膜形成用複合片。 When a support sheet including a base material and an adhesive layer is used, the adhesiveness and peelability between the support sheet and the protective film-forming film in the composite sheet for protective film formation can be easily adjusted. When a support sheet composed only of a base material is used, a composite sheet for forming a protective film can be produced at low cost.

以下，對這種支撐片的每個種類一邊參照圖式一邊說明本實施形態的保護膜形成用複合片之例。Hereinafter, examples of the composite sheet for forming a protective film according to the present embodiment will be described for each type of such support sheet with reference to the drawings.

◎保護膜形成用複合片之一例 圖2係示意性地表示本實施形態的保護膜形成用複合片的一例之剖面圖。 此外，圖2以下之圖之中，對於既已說明的圖所示相同構成要素，標附與該已說明的圖之情形相同符號，並省略該構成要素之詳細說明。 ◎An example of composite sheet for protective film formation FIG. 2 is a cross-sectional view schematically showing an example of the composite sheet for forming a protective film according to this embodiment. In addition, in the drawings following 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101的構成係具備：支撐片10、設置於支撐片10其中一面(本說明書之中，有時稱為「第一面」)10a上之保護膜形成膜13。 支撐片10的構成係具備：基材11、設置於基材11其中一面(第一面)11a上之黏著劑層12。保護膜形成用複合片101中，黏著劑層12係配置於基材11與保護膜形成膜13之間。 亦即，保護膜形成用複合片101係由基材11、黏著劑層12以及保護膜形成膜13依序於這些層的厚度方向積層而構成。 支撐片10的第一面10a係與黏著劑層12中與基材11側為相反側之面(本說明書之中，有時稱為「第一面」)12a相同。 The protective film-forming composite sheet 101 shown here is constituted by a support sheet 10 and a protective film-forming sheet provided on one side (sometimes referred to as the “first side” in this specification) 10 a of the support sheet 10 Membrane 13. The support sheet 10 is composed of a base material 11 and an adhesive layer 12 provided on one side (first side) 11 a of the base material 11 . In the protective film-forming composite sheet 101 , the adhesive layer 12 is disposed between the base material 11 and the protective film-forming film 13 . That is, the protective film-forming composite sheet 101 is composed of 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. The first surface 10a of the support sheet 10 is the same as 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).

保護膜形成用複合片101係進而於保護膜形成膜13上具備治具用接著劑層16以及剝離膜15。 保護膜形成用複合片101之中，於黏著劑層12的第一面12a的整面或是幾乎整面積層有保護膜形成膜13，而於保護膜形成膜13中與黏著劑層12側為相反側之面(本說明書之中，有時稱為「第一面」)13a的一部分、亦即於周緣部附近的區域積層有治具用接著劑層16。進而，於保護膜形成膜13的第一面13a之中，於未積層治具用接著劑層16之區域、以及治具用接著劑層16中與保護膜形成膜13側為相反側之面(本說明書之中，有時稱為「第一面」)16a，積層有剝離膜15。於保護膜形成膜13中與第一面13a為相反側之面(本說明書之中，有時稱為「第二面」)13b設置支撐片10。 The protective film forming composite sheet 101 further includes a jig adhesive layer 16 and a release film 15 on the protective film forming film 13 . In the protective film-forming composite sheet 101, the protective film-forming film 13 is laminated on the entire surface or almost the entire surface of the first surface 12a of the adhesive layer 12, and the protective film-forming film 13 is connected to the adhesive layer 12 side. 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. Furthermore, among the first surface 13 a of the protective film-forming film 13 , there are areas where the jig adhesive layer 16 is not laminated, and the surface of the jig adhesive layer 16 that is opposite to the protective film-forming film 13 side. (In this specification, it may be called "first surface") 16a, and the release film 15 is laminated|stacked. The support sheet 10 is provided on the surface 13b of the protective film forming film 13 opposite to the first surface 13a (sometimes referred to as the “second surface” in this specification).

不限於保護膜形成用複合片101的情形，本實施形態的保護膜形成用複合片之中，剝離膜(例如圖2所示之剝離膜15)為任意的構成，本實施形態的保護膜形成用複合片亦可具備剝離膜，亦可不具備剝離膜。It is not limited to the case of the protective film-forming composite sheet 101. In the protective film-forming composite sheet of this embodiment, the release film (for example, the release film 15 shown in FIG. 2) has an arbitrary structure. The protective film of this embodiment is formed The composite sheet may or may not have a release film.

治具用接著劑層16係用以將保護膜形成用複合片101固定於環形框等治具。 治具用接著劑層16例如亦可具有含有接著劑成分或黏著劑成分之單層結構，亦可具有多層結構，此多層結構具備作為芯材之片、以及設置於前述片的兩面之含有接著劑成分或黏著劑成分之層。 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 an adhesive component, or may have a multi-layer structure including a sheet as a core material, and adhesive-containing adhesive layers provided on both sides of the sheet. layer of agent ingredients or adhesive ingredients.

保護膜形成用複合片101在剝離膜15被移除之狀態下，於保護膜形成膜13的第一面13a貼附半導體晶圓的內面，進而治具用接著劑層16的第一面16a被貼附在環形框等治具而使用。With the release film 15 removed, the protective film forming composite sheet 101 is attached to the inner surface of the semiconductor wafer on the first surface 13 a of the protective film forming film 13 and then the first surface of the jig adhesive layer 16 16a is used by attaching it to a jig such as a ring frame.

圖3係以示意方式表示本實施形態的保護膜形成用複合片的另一例之剖面圖。 此處所示之保護膜形成用複合片102除了在保護膜形成膜的大小不同、不具備治具用接著劑層16的方面以外，係與圖2所示之保護膜形成用複合片101相同。 FIG. 3 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to this embodiment. The protective film-forming composite sheet 102 shown here is the same as the protective film-forming composite sheet 101 shown in FIG. 2 except that the size of the protective film-forming film is different and the jig adhesive layer 16 is not provided. .

更具體而言，保護膜形成用複合片102之中，保護膜形成膜23係積層於黏著劑層12的第一面12a的一部分的區域(亦即黏著劑層12的寬度方向(圖3之左右方向)之中央側之區域)。並且，於保護膜形成膜23中與黏著劑層12側為相反側之面(本說明書之中，有時稱為「第一面」)23a與黏著劑層12的第一面12a之中未積層保護膜形成膜23之區域積層有剝離膜15。於保護膜形成膜23中與第一面23a為相反側之面(本說明書之中，有時稱為「第二面」)23b設置有支撐片10。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. 3 The area on the central side of the left and right directions). In addition, there is no surface between 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 12a of the adhesive layer 12. The release film 15 is laminated in the area where the protective film forming film 23 is laminated. The support sheet 10 is provided on the surface 23b of the protective film forming film 23 opposite to the first surface 23a (sometimes referred to as the “second surface” in this specification).

本實施形態的保護膜形成用複合片不限定於圖2至圖3所示，亦可於不損及本發明功效之範圍內，於圖2至圖3所示者中變更或是刪除一部分構成，亦可進而追加其他構成於到目前為止所說明者。The composite sheet for forming a protective film according to this embodiment is not limited to that shown in FIGS. 2 to 3 , and part of the structure may be changed or deleted from those shown in FIGS. 2 to 3 within the scope that does not impair the effect of the present invention. , it is also possible to add other structures described so far.

再來，對於構成支撐片之各層進而詳細的說明。Next, each layer constituting the support sheet will be described in detail.

○基材 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)、直鏈狀低密度聚乙烯(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(使用乙烯作為單體所獲得之共聚物)；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所獲得之樹脂)；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、所有構成單元具有芳香族環式基之全芳香族聚酯等聚酯；2種以上的聚酯共聚物；聚(甲基)丙烯酸酯；聚胺基甲酸酯；聚胺基甲酸酯丙烯酸酯；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。 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。 作為前述樹脂，例如亦可列舉：至此為止所例示之前述樹脂之1種或2種以上交聯而成之交聯樹脂；使用至此為止所例示之前述樹脂之1種或2種以上之離子聚合物等改質樹脂。 前述樹脂在耐熱性優異之方面來看，較佳為聚丙烯或聚對苯二甲酸丁二酯。 ○Substrate 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 resin include polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE). ; 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 Resins obtained from vinyl chloride as a monomer); polystyrene; polycyclic olefins; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyisophthalic acid Polyesters such as ethylene glycol, polyethylene 2,6-naphthalate, fully aromatic polyesters in which all structural units have aromatic cyclic groups; 2 or more types of polyester copolymers; poly(meth)acrylic acid Ester; polyurethane; polyurethane acrylate; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; poly Silica; 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: a cross-linked resin obtained by cross-linking one or more of the above-described resins; and an ion polymerization using one or two or more of the above-described resins. Materials and other modified resins. Since the resin is excellent in heat resistance, polypropylene or polybutylene terephthalate is preferred.

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

基材亦可由1層(單層)所構成，亦可由2層以上之多層所構成。於基材由多層所構成之情形時，這些多層相互可相同亦可不同，這些多層的組合並無特別限定。The base material may be composed of one layer (single layer), or may be composed of two or more layers. When the base material 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50μm至300μm，更佳為60μm至100μm。藉由基材的厚度為這種範圍，可更提高保護膜形成用複合片的可撓性、對晶圓之貼附適性。 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，意指構成基材之所有層的合計的厚度。 The thickness of the base material is preferably 50 μm to 300 μm, more preferably 60 μm to 100 μm. When the thickness of the base material is in this range, the flexibility of the composite sheet for forming a protective film and the adhesion suitability to the wafer can be 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.

基材除了前述樹脂等主要構成材料以外，亦可含有填充材、著色劑、抗氧化劑、有機滑劑、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 well-known additives such as fillers, colorants, antioxidants, organic lubricants, catalysts, and softeners (plasticizers).

基材可為透明以及非透明中任一者，亦可根據目的而著色，亦可蒸鍍其他層。 於保護膜形成膜具有能量線硬化性之情形時，基材較佳為使能量線穿透。 The base material may be either transparent or non-transparent, may be colored according to the purpose, and may be vapor-deposited with other layers. When the protective film-forming film has energy ray curability, it is preferable that the base material allows energy rays to penetrate.

基材為了調節相對於設置於基材上之層(例如黏著劑層、保護膜形成膜、或是前述其他層)之密接性，亦可於表面施加如下處理：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；親油處理；親水處理等。另外，基材之表面亦可進行底塗處理。In order to adjust the adhesion of the base material to the layer provided on the base material (such as an adhesive layer, a protective film-forming film, or other layers mentioned above), the following treatments can also be applied to the surface: sandblasting, solvent treatment, etc. Chemical treatment; corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone-ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments; lipophilic treatment; hydrophilic treatment, etc. In addition, the surface of the substrate can also be primed.

基材亦可藉由含有特定範圍的成分(例如樹脂等)，而於至少一面具有黏著性。The base material can also be adhesive on at least one side by containing a specific range of components (such as resin, etc.).

基材可利用公知的方法進行製造。例如，含有樹脂之基材可藉由將含有前述樹脂之樹脂組成物成形而進行製造。The base material can be produced by a known method. For example, 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是膜狀，含有黏著劑。 作為前述黏著劑，例如可列舉：丙烯酸樹脂、胺基甲酸酯樹脂、橡膠系樹脂、聚矽氧樹脂、環氧系樹脂、聚乙烯醚、聚碳酸酯、酯系樹脂等黏著性樹脂。 ○Adhesive layer The aforementioned adhesive layer is in the form of a sheet or film and contains adhesive. Examples of the adhesive include adhesive resins such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, and ester resin.

黏著劑層亦可由1層(單層)所構成，亦可由2層以上之多層所構成，於黏著劑層由多層所構成之情形時，這些多層相互可相同亦可不同，這些多層的組合並無特別限定。The adhesive layer may be composed of one layer (single layer), or may be composed of two or more multiple layers. When the adhesive layer is composed of multiple layers, these multiple layers may be the same or different from each other. The combination of these multiple layers No special restrictions.

黏著劑層的厚度並無特別限定，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所有層的合計的厚度。 The thickness of the adhesive layer is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, and 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.

黏著劑層可為透明以及非透明中任一者，亦可根據目的而進行著色。 保護膜形成膜具有能量線硬化性之情形時，黏著劑層較佳係使能量線穿透。 The adhesive layer may be either transparent or non-transparent, and may be colored according to the purpose. When the protective film-forming film has energy ray curability, it is preferable that the adhesive layer allows energy rays to penetrate.

黏著劑層可為能量線硬化性以及非能量線硬化性中任一者。能量線硬化性黏著劑層能夠調節在硬化前以及硬化後之物性。例如在後述拾取具保護膜之半導體晶片之前，藉由使能量線硬化性黏著劑層硬化，可更容易拾取該具保護膜之半導體晶片。The adhesive layer may be either energy ray curable or non-energy ray curable. The energy ray hardening adhesive layer can adjust the physical properties before and after hardening. For example, before picking up the semiconductor wafer with the protective film as described later, by hardening the energy ray curable adhesive layer, the semiconductor wafer with the protective film can be picked up more easily.

本說明書之中，即使在能量線硬化性黏著劑層經能量線硬化之後，只要維持基材與能量線硬化性黏著劑層的硬化物之積層結構，仍稱該積層結構體為「支撐片」。In this specification, even after the energy ray curable adhesive layer is cured by energy rays, as long as the laminated structure of the cured product of the base material and the energy ray curable adhesive layer is maintained, the laminated structure is still called a "support sheet" .

黏著劑層可使用含有黏著劑之黏著劑組成物來形成。例如藉由於黏著劑層的形成對象面塗敷黏著劑組成物，並視需要進行乾燥，可於目的部位形成黏著劑層。黏著劑組成物中的常溫下不會氣化之成分彼此的含量之比率通常與黏著劑層中之前述成分彼此的含量之比率相同。The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, by applying the adhesive composition to the surface to be formed of the adhesive layer and drying it if necessary, the adhesive layer can be formed at the target site. The ratio of the contents of the components that do not vaporize at normal temperature in the adhesive composition to each other is usually the same as the ratio of the contents of the aforementioned components to each other in the adhesive layer.

黏著劑組成物的塗敷以及乾燥，例如可藉由與上述之保護膜形成用組成物的塗敷以及乾燥之情形相同方法來進行。The application and drying of the adhesive composition can be performed, for example, by the same method as the above-described application and drying of the protective film forming composition.

黏著劑層為能量線硬化性之情形時，作為能量線硬化性的黏著劑組成物，例如可列舉：含有非能量線硬化性的黏著性樹脂(I-1a)(以下有時簡記為「黏著性樹脂(I-1a)」)以及能量線硬化性化合物之黏著劑組成物(I-1)；含有於非能量線硬化性之黏著性樹脂(I-1a)之側鏈導入不飽和基之能量線硬化性之黏著性樹脂(I-2a)(以下有時縮寫為「黏著性樹脂(I-2a)」)之黏著劑組成物(I-2)；含有前述黏著性樹脂(I-2a)、能量線硬化性化合物之黏著劑組成物(I-3)等。When the adhesive layer is energy ray curable, examples of the energy ray curable adhesive composition include a non-energy ray curable adhesive resin (I-1a) (hereinafter sometimes abbreviated as "adhesive"). adhesive resin (I-1a)") and an adhesive composition (I-1) of an energy ray curable compound; containing an unsaturated group introduced into the side chain of a non-energy ray curable adhesive resin (I-1a) Adhesive composition (I-2) of energy ray curable adhesive resin (I-2a) (hereinafter sometimes abbreviated as "adhesive resin (I-2a)"); containing the aforementioned adhesive resin (I-2a) ), energy ray curable compound adhesive composition (I-3), etc.

黏著劑層為非能量線硬化性之情形時，作為非能量線硬化性的黏著劑組成物，例如可列舉：含有前述非能量線硬化性的黏著性樹脂(I-1a)之黏著劑組成物(I-4)等。When the adhesive layer is non-energy ray curable, examples of the non-energy ray curable adhesive composition include an adhesive composition containing the aforementioned non-energy ray curable adhesive resin (I-1a). (I-4) etc.

[非能量線硬化性之黏著性樹脂(I-1a)] 前述黏著性樹脂(I-1a)較佳為丙烯酸樹脂。 作為前述丙烯酸樹脂，例如可列舉至少具有源自(甲基)丙烯酸烷基酯的構成單元之丙烯酸聚合物。 [Non-energy ray curable adhesive resin (I-1a)] The aforementioned 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.

前述丙烯酸聚合物除了源自(甲基)丙烯酸烷基酯的構成單元以外，較佳係進而具有源自含官能基之單體的構成單元。 作為前述含官能基之單體，例如可列舉：藉由前述官能基與後述之交聯劑進行反應而成為交聯的起點之單體。 作為前述含官能基之單體，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。 The acrylic polymer preferably further has a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from a (meth)acrylic acid alkyl ester. Examples of the functional group-containing monomer include a monomer that becomes a starting point for crosslinking by reacting the functional group with a crosslinking agent described later. Examples of the functional group-containing monomer include hydroxyl group-containing monomers, carboxyl group-containing monomers, amine group-containing monomers, epoxy group-containing monomers, and the like.

前述丙烯酸聚合物，除了源自(甲基)丙烯酸烷基酯的構成單元、以及源自含官能基之單體的構成單元以外，亦可進而具有源自其他單體的構成單元。 前述其他單體只要是可與(甲基)丙烯酸烷基酯等進行共聚者即可並無特別限定。 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.

前述黏著劑組成物(I-1)、黏著劑組成物(I-2)、黏著劑組成物(I-3)以及黏著劑組成物(I-4)(以下包括這些黏著劑組成物，縮寫為「黏著劑組成物(I-1)至黏著劑組成物(I-4)」)之中，前述丙烯酸聚合物等前述丙烯酸樹脂所具有之構成單元可僅為1種，亦可為2種以上，為2種以上之情形時，這些構成單元的組合以及比率可任意選擇。The aforementioned adhesive composition (I-1), adhesive composition (I-2), adhesive composition (I-3) and adhesive composition (I-4) (hereinafter including these adhesive compositions, abbreviations Among the "adhesive compositions (I-1) to adhesive compositions (I-4)"), the acrylic resin such as the acrylic polymer may have only one type of structural unit or two types of structural units. When the above is two or more cases, the combination and ratio of these structural units can be selected arbitrarily.

黏著劑組成物(I-1)或黏著劑組成物(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，為2種以上之情形時，這些黏著性樹脂(I-1a)的組合以及比率可任意選擇。The adhesive resin (I-1a) contained in the adhesive composition (I-1) or 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 adhesive resins (I-1a) can be selected arbitrarily.

由黏著劑組成物(I-1)或是黏著劑組成物(I-4)所形成之黏著劑層之中，黏著性樹脂(I-1a)的含量相對於前述黏著劑層的總質量之比率較佳為5質量%至99質量%。In the adhesive layer formed by the adhesive composition (I-1) or the adhesive composition (I-4), the content of the adhesive resin (I-1a) is relative to the total mass of the aforementioned adhesive layer. The ratio is preferably 5% by mass to 99% by mass.

[能量線硬化性之黏著性樹脂(I-2a)] 前述黏著性樹脂(I-2a)，例如可使得黏著性樹脂(I-1a)中的官能基與具有能量線聚合性不飽和基之含有不飽和基之化合物進行反應而獲得。 [Energy ray curable adhesive resin (I-2a)] The adhesive resin (I-2a) can be 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.

前述含有不飽和基之化合物為除了具有前述能量線聚合性不飽和基以外、進而具有可藉著與黏著性樹脂(I-1a)中的官能基進行反應而可與黏著性樹脂(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。 作為可與黏著性樹脂(I-1a)中的官能基鍵結之基，例如可列舉：可與羥基或是胺基鍵結之異氰酸酯基以及縮水甘油基、以及可與羧基或是環氧基鍵結之羥基以及胺基等。 The aforementioned compound containing an unsaturated group, in addition to having the aforementioned energy ray polymerizable unsaturated group, further has the ability to react with the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a). ) compound of the bonding base. Examples of the energy ray polymerizable unsaturated group include (meth)acrylyl, vinyl (ethylidene), allyl (2-propenyl), and the like, and (meth)acrylyl is preferred. base. 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. Bonded hydroxyl and amine groups, etc.

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

黏著劑組成物(I-2)或黏著劑組成物(I-3)所含有之黏著性樹脂(I-2a)可僅為1種，亦可為2種以上，為2種以上之情形時，這些黏著性樹脂(I-2a)的組合以及比率可任意選擇。The adhesive resin (I-2a) contained in the adhesive composition (I-2) or 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 adhesive resins (I-2a) can be selected arbitrarily.

自黏著劑組成物(I-2)或是黏著劑組成物(I-3)所形成之黏著劑層之中，黏著性樹脂(I-2a)的含量相對於前述黏著劑層的總質量之比率較佳為5質量%至99質量%。In the adhesive layer formed from the adhesive composition (I-2) or the adhesive composition (I-3), the content of the adhesive resin (I-2a) is relative to the total mass of the aforementioned adhesive layer. The ratio is preferably 5% by mass to 99% by mass.

[能量線硬化性化合物] 作為前述黏著劑組成物(I-1)或是黏著劑組成物(I-3)所含有之前述能量線硬化性化合物，可列舉如具有能量線聚合性不飽和基並可藉由照射能量線而硬化之單體或是寡聚物。 [Energy ray curing compound] Examples of the energy-beam-curable compound contained in the adhesive composition (I-1) or the adhesive composition (I-3) include energy-beam-polymerizable unsaturated groups that can be cured by irradiation with energy-beams. And hardened monomers or oligomers.

能量線硬化性化合物之中，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之中，作為寡聚物，例如可列舉在上述所例示之單體的聚合物之寡聚物等。 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 amine Formate; polyester (meth)acrylate; polyether (meth)acrylate; epoxy (meth)acrylate, etc. Among the energy ray curable compounds, examples of oligomers include oligomers of polymers of the monomers exemplified above.

黏著劑組成物(I-1)或黏著劑組成物(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，為2種以上之情形時，這些能量線硬化性化合物的組合以及比率可任意選擇。The adhesive composition (I-1) or the adhesive composition (I-3) may contain only one type of energy ray curable compound, or two or more types. In the case of two or more types, these The combination and ratio of energy ray curable compounds can be selected arbitrarily.

自黏著劑組成物(I-1)或是黏著劑組成物(I-3)所形成之黏著劑層之中，前述能量線硬化性化合物的含量相對於前述黏著劑層的總質量之比率，較佳為1質量%至95質量%。In the adhesive layer formed from the adhesive composition (I-1) or the adhesive composition (I-3), the ratio of the content of the energy ray curable compound to the total mass of the adhesive layer, Preferably it is 1 mass % to 95 mass %.

[交聯劑] 作為黏著性樹脂(I-1a)，當使用除了具有源自(甲基)丙烯酸烷基酯的構成單元以外進而具有源自含官能基之單體的構成單元之前述丙烯酸聚合物之情形時，黏著劑組成物(I-1)或是黏著劑組成物(I-4)較佳係進而含有交聯劑。 另外，作為黏著性樹脂(I-2a)，例如使用與黏著性樹脂(I-1a)中相同之具有源自含官能基之單體的構成單元之前述丙烯酸聚合物之情形時，黏著劑組成物(I-2)或是黏著劑組成物(I-3)亦可進而含有交聯劑。 [Cross-linking agent] As the adhesive resin (I-1a), when the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate is used, The adhesive composition (I-1) or the adhesive composition (I-4) preferably further contains a cross-linking agent. In addition, as the adhesive resin (I-2a), for example, when the aforementioned acrylic polymer having the same structural unit derived from the functional group-containing monomer as the adhesive resin (I-1a) is used, the adhesive composition The compound (I-2) or the adhesive composition (I-3) may further contain a cross-linking agent.

前述交聯劑例如與前述官能基進行反應，使黏著性樹脂(I-1a)彼此或是黏著性樹脂(I-2a)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、這些二異氰酸酯的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。 For example, the cross-linking agent reacts with the functional group to cross-link the adhesive resins (I-1a) or the adhesive resins (I-2a). 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 groups) such as ethylene glycol glycidyl ether; aziridine cross-linking agents such as hexa[1-(2-methyl)-aziridinyl] triphosphotriazine Cross-linking agent (cross-linking agent with aziridine group); metal chelate such as aluminum chelate is cross-linking agent (cross-linking agent with metal chelate structure); isocyanurate is cross-linking agent ( Cross-linking agent with isocyanuric acid skeleton), etc.

黏著劑組成物(I-1)至黏著劑組成物(I-4)所含有之交聯劑可僅為1種，亦可為2種以上，為2種以上之情形時，這些交聯劑的組合以及比率可任意選擇。The cross-linking agent contained in the adhesive composition (I-1) to 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 cross-linking agents The combination and ratio can be selected arbitrarily.

前述黏著劑組成物(I-1)或是黏著劑組成物(I-4)之中，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。 前述黏著劑組成物(I-2)或是黏著劑組成物(I-3)之中，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。 In the aforementioned adhesive composition (I-1) or adhesive composition (I-4), the content of the cross-linking agent is preferably 0.01 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-1a). parts to 50 parts by mass. In the aforementioned adhesive composition (I-2) or adhesive composition (I-3), the content of the cross-linking agent is preferably 0.01 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2a). parts to 50 parts by mass.

[光聚合起始劑] 黏著劑組成物(I-1)、黏著劑組成物(I-2)以及黏著劑組成物(I-3)(以下包括這些黏著劑組成物，縮寫為「黏著劑組成物(I-1)至黏著劑組成物(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-1)至黏著劑組成物(I-3)，即使照射紫外線等相對低能量之能量線，仍可充分地進行硬化反應。 [Photopolymerization initiator] Adhesive composition (I-1), adhesive composition (I-2) and adhesive composition (I-3) (hereinafter including these adhesive compositions, abbreviated as "adhesive composition (I-1)" The adhesive composition (I-3)") may further contain a photopolymerization initiator. The adhesive compositions (I-1) to (I-3) containing a photopolymerization initiator can fully proceed with the curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

作為前述光聚合起始劑，例如可列舉與上述光聚合起始劑(H)相同者。Examples of the photopolymerization initiator include the same ones as the photopolymerization initiator (H) described above.

黏著劑組成物(I-1)至黏著劑組成物(I-3)所含有之光聚合起始劑可僅為1種，亦可為2種以上，為2種以上之情形時，這些光聚合起始劑的組合以及比率可任意選擇。The photopolymerization initiator contained in the adhesive compositions (I-1) to (I-3) may be only one type, or may be two or more types. In the case of two or more types, these photopolymerization initiators may be The combination and ratio of polymerization initiators can be selected arbitrarily.

黏著劑組成物(I-1)之中，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。 黏著劑組成物(I-2)之中，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。 黏著劑組成物(I-3)之中，光聚合起始劑的含量相對於黏著性樹脂(I-2a)以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。 In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the energy ray curable compound. In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a). In the adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass.

[其他的添加劑] 黏著劑組成物(I-1)至黏著劑組成物(I-4)在不損及本發明之功效之範圍內，亦可含有不相當於上述中任一成分之其他的添加劑。 作為前述其他的添加劑，例如可列舉：抗靜電劑、抗氧化劑、軟化劑(塑化劑)、填充材(填料)、防鏽劑、著色劑(顏料、染料)、敏化劑、賦黏劑、反應延遲劑、交聯促進劑(觸媒)等公知的添加劑。 此外，所謂反應延遲劑，例如係用以抑制因混入於黏著劑組成物(I-1)至黏著劑組成物(I-4)中之觸媒的作用，而造成儲存中的黏著劑組成物(I-1)至黏著劑組成物(I-4)之中進行非目的之交聯反應的成分。作為反應延遲劑，例如可列舉藉由針對觸媒之螯合物來形成螯合物錯合物之反應延遲劑，更具體而言，例如可列舉於1分子中具有2個以上的羰基(-C(＝O)-)之反應延遲劑。 [Other additives] The adhesive compositions (I-1) to (I-4) may also contain other additives that are not equivalent to any of the above components within the scope that does not impair the efficacy of the present invention. Examples of the aforementioned other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers. , reaction retardants, cross-linking accelerators (catalysts) and other well-known additives. In addition, the so-called reaction delaying agent is, for example, used to inhibit the action of the catalyst mixed in the adhesive composition (I-1) to the adhesive composition (I-4), which may cause the adhesive composition to be stored during storage. (I-1) A component that undergoes an unintended cross-linking reaction in the adhesive composition (I-4). Examples of the reaction retardant include those that form a chelate complex with a chelate for a catalyst. More specifically, examples include those having two or more carbonyl groups (- in one molecule). C(=O)-) reaction retardant.

黏著劑組成物(I-1)至黏著劑組成物(I-4)所含有之其他的添加劑可僅為1種，亦可為2種以上，為2種以上之情形時，這些其他的添加劑的組合以及比率可任意選擇。The other additives contained in the adhesive compositions (I-1) to (I-4) may be only one type, or may be two or more types. In the case of two or more types, these other additives The combination and ratio can be selected arbitrarily.

黏著劑組成物(I-1)至黏著劑組成物(I-4)的其他的添加劑的含量並無特別限定，根據添加劑種類而適當選擇即可。The content of other additives in the adhesive composition (I-1) to the adhesive composition (I-4) is not particularly limited, and may be appropriately selected depending on the type of additive.

[溶媒] 黏著劑組成物(I-1)至黏著劑組成物(I-4)亦可含有溶媒。藉由黏著劑組成物(I-1)至黏著劑組成物(I-4)含有溶媒，可提高對塗敷對象面之塗敷適性。 [solvent] The adhesive compositions (I-1) to (I-4) may also contain a solvent. Since the adhesive compositions (I-1) to (I-4) contain a solvent, the coating suitability for the surface to be coated can be improved.

前述溶媒較佳為有機溶媒，作為前述有機溶媒，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.

黏著劑組成物(I-1)至黏著劑組成物(I-4)所含有之溶媒可僅為1種，亦可為2種以上，為2種以上之情形時，這些溶媒的組合以及比率可任意選擇。The solvent contained in the adhesive composition (I-1) to 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 solvents You can choose whatever you want.

黏著劑組成物(I-1)至黏著劑組成物(I-4)的溶媒的含量並無特別限定，只要適當調節即可。The content of the solvent in the adhesive composition (I-1) to the adhesive composition (I-4) is not particularly limited, as long as it is appropriately adjusted.

○黏著劑組成物之製造方法 黏著劑組成物，例如除了調配成分的種類不同的方面以外，可以與前文所說明之保護膜形成用組成物之情形相同方法來製造。 ○Manufacturing method of adhesive composition The adhesive composition can be produced in the same manner as in the case of the protective film forming composition described above, except that the types of ingredients are different.

◇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成為對應上述之各層之位置關係的方式進行積層，並視需要調節一部分或是所有層的形狀來製造。各層的形成方法係如前文所說明。 ◇Production method of composite sheet for protective film formation The composite sheet for forming a protective film can be produced by laminating the layers so as to correspond to the positional relationship of the above-mentioned layers and adjusting the shapes of some or all of the layers as necessary. The formation methods of each layer are as described above.

例如在製造支撐片時，於基材上積層黏著劑層之情形時，只要於基材上塗敷上述之黏著劑組成物，並視需要進行乾燥即可。 另外，即使是藉由於剝離膜上塗敷黏著劑組成物，並視需要乾燥，於剝離膜上預先形成黏著劑層，將該黏著劑層的露出面貼合於基材的一表面之方法，亦可於基材上積層黏著劑層。此時，黏著劑組成物較佳係塗敷於剝離膜的剝離處理面。另外，此情形之剝離膜可在保護膜形成用複合片之製造過程或使用過程中任一時機移除即可。 至此為止，列舉了於基材上積層黏著劑層之情形之例，然上述之方法亦可適用在例如於基材上積層黏著劑層以外的其他層之情形時。 For example, when manufacturing a support sheet and laminating an adhesive layer on a base material, it is sufficient to apply the above-mentioned adhesive composition on the base material and dry it if necessary. In addition, even the method of forming an adhesive layer on the release film in advance by applying an adhesive composition on the release film and drying it if necessary, and bonding the exposed surface of the adhesive layer to a surface of the base material is also applicable. An adhesive layer can be laminated on the substrate. At this time, the adhesive composition is preferably applied to the release-treated surface of the release film. In addition, the release film in this case may be removed at any time during the manufacturing process or use of the protective film-forming composite sheet. So far, the example in which an adhesive layer is laminated on a base material has been exemplified. However, the above method may also be applied when, for example, a layer other than an adhesive layer is laminated on a base material.

另一方面，例如於已積層於基材上的黏著劑層之上，進而積層保護膜形成膜之情形時，可於黏著劑層上塗敷保護膜形成用組成物，直接形成保護膜形成膜。保護膜形成膜以外的層亦可使用用以形成該層之組成物，並以相同的方法於黏著劑層之上積層該層。如此，於已積層於基材上之任一層(以下縮寫為「第一層」)上形成新的層(以下縮寫為「第二層」)，來形成連續之2層的積層結構(換言之為第一層以及第二層的積層結構)之情形時，可適用如下之方法：於前述第一層上塗敷用以形成前述第二層之組成物，並視需要進行乾燥。 其中，第二層較佳係藉由使用用以形成第二層之組成物而預先形成於剝離膜上，將此已形成的第二層中與接觸於前述剝離膜之側為相反側之露出面貼合於第一層的露出面，而形成連續之2層的積層結構。此時，前述組成物較佳係塗敷於剝離膜的剝離處理面。剝離膜係在形成積層結構後視需要移除即可。 此處，雖然列舉了於黏著劑層上積層保護膜形成膜之情形為例，但例如於黏著劑層上積層保護膜形成膜以外的層(膜)之情形等，可任意選擇作為對象之積層結構。 On the other hand, for example, when a protective film is laminated on an adhesive layer laminated on a substrate to form a film, the protective film-forming composition can be applied on the adhesive layer to directly form a protective film-forming film. The composition for forming this layer can also be used as a layer other than the protective film-forming film, and this layer can be laminated on the adhesive layer in the same manner. In this way, a new layer (hereinafter abbreviated as the "second layer") is formed on any layer that has been laminated on the substrate (hereinafter abbreviated as the "first layer") to form a continuous 2-layer laminated structure (in other words In the case of a laminated structure of a first layer and a second layer), the following method can be applied: apply a composition for forming the second layer on the first layer, and dry it if necessary. Among them, the second layer is preferably formed in advance on the release film by using a composition for forming the second layer, and the side of the formed second layer opposite to the side in contact with the release film is exposed. The surface is attached to the exposed surface of the first layer to form a continuous two-layer laminated structure. At this time, the composition is preferably applied to the release-treated surface of the release film. The peel-off film can be removed if necessary after forming a laminated structure. Here, the case where a protective film is laminated on the adhesive layer to form a film is given as an example. However, for example, when a layer (film) other than a protective film is laminated on the adhesive layer, the target laminate can be selected arbitrarily. structure.

如此，由於構成保護膜形成用複合片之基材以外的層皆能以預先形成於剝離膜上再貼合於目的層的表面之方法進行積層，故只要視需要適當選擇採用這種步驟之層，來製造保護膜形成用複合片即可。In this way, since 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, it is only necessary to appropriately select the layer using this step as necessary. , to produce a composite sheet for protective film formation.

此外，保護膜形成用複合片通常係於與該支撐片為相反側之最表層(例如保護膜形成膜)的表面貼合有剝離膜之狀態來儲存。因此，於該剝離膜(較佳為剝離膜之剝離處理面)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，並視需要進行乾燥，藉此於剝離膜上預先形成構成最表層之層，於該層中與剝離膜接觸之側為相反側之露出面上積層剩餘的各層，不移除剝離膜而保持貼合之狀態，藉此獲得具剝離膜之保護膜形成用複合片。In addition, the composite sheet for protective film formation is usually stored in a state where a release film is bonded to the surface of the outermost layer (for example, the protective film forming film) on the opposite side to the support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as a protective film-forming composition, is applied to the release film (preferably the release-treated surface of the release film), and dried if necessary, thereby forming a protective film on the release film. A layer constituting the outermost layer is formed in advance, and the remaining layers are laminated on the exposed surface opposite to the side in contact with the peeling film. The peeling film remains attached without removing the peeling film, thereby obtaining the protection of the peeling film. Composite sheet for film formation.

◇半導體裝置之製造方法(保護膜形成膜以及保護膜形成用複合片的使用方法) 前述保護膜形成膜以及保護膜形成用複合片，能夠用於製作前述具保護膜之半導體晶片，進而使用該半導體晶片來製造半導體裝置。 ◇Manufacturing method of semiconductor device (how to use protective film forming film and protective film forming composite sheet) The protective film-forming film and protective film-forming composite sheet can be used to produce the semiconductor wafer with the protective film, and the semiconductor wafer can be used to manufacture a semiconductor device.

本實施形態之半導體裝置之製造方法係具有如下步驟：貼附步驟，將前述保護膜形成膜之一面、或是前述保護膜形成用複合片中之前述保護膜形成膜的露出面貼附於半導體晶圓的內面；熱硬化步驟，在前述貼附步驟之後，使前述保護膜形成膜熱硬化而形成保護膜；印字步驟，在前述熱硬化步驟之後，於使用前述保護膜形成用複合片之情形時，在前述保護膜形成用複合片中的前述保護膜的前述支撐片側之面進行雷射印字，於使用未構成前述保護膜形成用複合片之前述保護膜形成膜之情形時，在前述保護膜的另一面進行雷射印字；加工步驟，在前述印字步驟之後，於使用前述保護膜形成用複合片之情形時，在前述保護膜形成用複合片中之前述支撐片上，將前述半導體晶圓分割成半導體晶片，沿著前述半導體晶圓的分割部位來切斷前述保護膜，於使用未構成前述保護膜形成用複合片之前述保護膜形成膜之情形時，在前述保護膜的另一面貼附切割片之後，在前述切割片上，將前述半導體晶圓分割成半導體晶片，沿著前述半導體晶圓的分割部位來切斷前述保護膜，藉此製作具備前述半導體晶片以及設置於前述半導體晶片的內面之切斷後的前述保護膜之具保護膜之半導體晶片；拾取步驟，在前述加工步驟之後，將前述具保護膜之半導體晶片自前述切割片或支撐片扯離而進行拾取。The manufacturing method of a semiconductor device according to this embodiment includes the following steps: an attaching step of attaching one side of the protective film-forming film or the exposed surface of the protective film-forming film in the protective film-forming composite sheet to the semiconductor The inner surface of the wafer; a thermal hardening step, after the aforementioned attaching step, to thermally harden the aforementioned protective film-forming film to form a protective film; and a printing step, after the aforementioned thermal curing step, before using the aforementioned composite sheet for protective film formation In this case, laser printing is performed on the surface of the supporting sheet side of the protective film in the protective film-forming composite sheet, and in the case of using the protective film-forming film that does not constitute the protective film-forming composite sheet, in the above-mentioned The other side of the protective film is subjected to laser printing; the processing step is, after the aforementioned printing step, when the aforementioned protective film forming composite sheet is used, the aforementioned semiconductor wafer is placed on the aforementioned support sheet in the aforementioned protective film forming composite sheet. The semiconductor wafer is circularly divided, and the protective film is cut along the divided portions of the semiconductor wafer. When the protective film-forming film that does not constitute the protective film-forming composite sheet is used, the protective film is formed on the other side of the protective film. After attaching the dicing sheet, the semiconductor wafer is divided into semiconductor wafers on the dicing sheet, and the protective film is cut along the divided parts of the semiconductor wafer, thereby producing the semiconductor wafer and the semiconductor wafer provided on the semiconductor wafer. The semiconductor wafer with the protective film on the cut inner surface of the protective film; the picking step, after the aforementioned processing step, the semiconductor wafer with the protective film is pulled away from the aforementioned cutting piece or support piece and picked up.

前述保護膜形成膜在常溫保存之情形時的穩定性高。因此，前述製造方法之中，於使用以常溫保存後的保護膜形成膜之情形時，最強力地表現本發明的功效。 例如，本實施形態之半導體裝置之製造方法之中，亦可將前述保護膜形成用複合片、或是未構成前述保護膜形成用複合片之前述保護膜形成膜以常溫保存30日之後，用於前述貼附步驟。 The aforementioned protective film-forming film has high stability when stored at room temperature. Therefore, among the above-mentioned manufacturing methods, the effect of the present invention is most strongly expressed when a film is formed using a protective film stored at room temperature. For example, in the method of manufacturing a semiconductor device according to this embodiment, the protective film-forming composite sheet or the protective film-forming film that does not constitute the protective film-forming composite sheet may be stored at room temperature for 30 days, and then used Follow the attachment steps mentioned above.

以下關於半導體裝置之製造方法，一邊引用圖式一邊加以說明。 圖4A至圖4E係用以示意性地說明本實施形態之半導體裝置之製造方法之中使用保護膜形成用複合片之情形時之製造方法之一例(本說明書之中有時稱為「製造方法(1)」)之剖面圖。此處，加以說明關於使用圖2所示之保護膜形成用複合片101之情形。 A method of manufacturing a semiconductor device will be described below with reference to the drawings. 4A to 4E are schematically illustrating an example of the manufacturing method when a protective film forming composite sheet is used in the manufacturing method of the semiconductor device according to this embodiment (sometimes referred to as "manufacturing method in this specification"). (1)") cross-sectional view. Here, a case of using the protective film forming composite sheet 101 shown in FIG. 2 will be described.

[製造方法(1)] [貼附步驟] 前述製造方法(1)之前述貼附步驟之中，如圖4A所示，藉由將移除了剝離膜15之前述保護膜形成用複合片101中之保護膜形成膜13貼附於半導體晶圓9的內面9b，製作具備半導體晶圓9以及設置於半導體晶圓9的內面9b之保護膜形成膜13之具保護膜形成膜之半導體晶圓901。保護膜形成膜13將露出面之第一面13a貼合於半導體晶圓9的內面9b。 圖4A中，符號9a係表示半導體晶圓9的電路面。 [Manufacturing method (1)] [Attach steps] In the above-mentioned attachment step of the aforementioned manufacturing method (1), as shown in FIG. 4A , the protective film-forming film 13 in the protective film-forming composite sheet 101 before the release film 15 is removed is attached to the semiconductor wafer. On the inner surface 9 b of the circle 9 , a semiconductor wafer 901 with a protective film forming film including the semiconductor wafer 9 and the protective film forming film 13 provided on the inner surface 9 b of the semiconductor wafer 9 is produced. The protective film forming film 13 bonds the first exposed surface 13 a to the inner surface 9 b of the semiconductor wafer 9 . In FIG. 4A , reference numeral 9 a indicates the circuit surface of the semiconductor wafer 9 .

此外，圖4A至圖4E之中，係省略半導體晶圓或半導體晶片的電路面之電路與突狀電極等圖示。這在以後的圖中亦相同。In addition, in FIGS. 4A to 4E , illustrations of the semiconductor wafer or the circuits and protruding electrodes on the circuit surface of the semiconductor wafer are omitted. This is also the case in subsequent figures.

保護膜形成膜13對半導體晶圓9之貼附能夠以使用輥之方法等公知的方法來進行。The protective film forming film 13 can be attached to the semiconductor wafer 9 by a known method such as using a roller.

保護膜形成膜13對半導體晶圓9之貼附條件並無特別限定。通常，貼附時的保護膜形成膜13的溫度(貼附溫度)較佳為20℃至100℃，更佳為65℃至85℃。貼附保護膜形成膜13之速度(貼附速度)較佳為0.1m/min至2m/min，於貼附時對保護膜形成膜13所施加之壓力(貼附壓力)較佳為0.1MPa至0.6MPa。Conditions for attaching the protective film forming film 13 to the semiconductor wafer 9 are not particularly limited. In general, the temperature of the protective film-forming film 13 during attachment (attachment temperature) is preferably 20°C to 100°C, more preferably 65°C to 85°C. The speed at which the protective film-forming film 13 is attached (attaching speed) is preferably 0.1m/min to 2m/min, and the pressure (attaching pressure) applied to the protective film-forming film 13 during attachment is preferably 0.1MPa. to 0.6MPa.

藉由保護膜形成膜13所製作之前述試片之上述在DSC之發熱起始溫度為160℃以上，貼附步驟之中，保護膜形成膜13對半導體晶圓9之貼附性良好。例如，即使使用以常溫保存後的保護膜形成膜13，保護膜形成膜13對半導體晶圓9之貼附性仍良好，因此，保護膜所帶來之半導體晶片的保護性能亦高。The aforementioned test piece produced by using the protective film-forming film 13 has a DSC heating starting temperature of 160° C. or above. In the attachment step, the protective film-forming film 13 has good adhesion to the semiconductor wafer 9 . For example, even if the protective film-forming film 13 stored at normal temperature is used, the adhesion of the protective film-forming film 13 to the semiconductor wafer 9 is still good. Therefore, the protective performance of the semiconductor wafer provided by the protective film is also high.

[熱硬化步驟] 製造方法(1)之前述貼附步驟之後，前述熱硬化步驟之中，使得具保護膜形成膜之半導體晶圓901中之保護膜形成膜13進行熱硬化，如圖4B所示，形成保護膜13’。藉此，具保護膜形成膜之半導體晶圓901係成為具備半導體晶圓9以及設置於半導體晶圓9的內面9b之保護膜13’之具保護膜之半導體晶圓901’。 圖4B中，符號13b’係表示保護膜13’的第二面，對應保護膜形成膜13的第二面13b。另外，符號13a’係表示保護膜13’的第一面，對應保護膜形成膜13的第一面13a。另外，在圖4B中，係將使保護膜形成膜13進行熱硬化後的保護膜形成用複合片加註新的符號101’來表示。 [Thermal hardening step] Manufacturing method (1) After the above-mentioned attaching step, during the above-mentioned thermal hardening step, the protective film-forming film 13 in the semiconductor wafer 901 with the protective film-forming film is thermally cured, as shown in FIG. 4B, to form a protective film. 13'. Thereby, the semiconductor wafer 901 with the protective film forming film becomes the semiconductor wafer with a protective film 901' including the semiconductor wafer 9 and the protective film 13' provided on the inner surface 9b of the semiconductor wafer 9. In FIG. 4B, symbol 13b' indicates the second surface of the protective film 13' and corresponds to the second surface 13b of the protective film forming film 13. In addition, the symbol 13a' indicates the first surface of the protective film 13' and corresponds to the first surface 13a of the protective film forming film 13. In addition, in FIG. 4B , the composite sheet for forming a protective film in which the protective film forming film 13 is thermally cured is denoted by a new symbol 101'.

熱硬化步驟中，保護膜形成膜13的熱硬化時的加熱溫度與加熱時間係如前文所說明。In the thermal curing step, the heating temperature and heating time during thermal curing of the protective film forming film 13 are as described above.

如前文所說明，使用保護膜形成膜中，相對於保護膜形成膜的總質量，填充材(D)的含量的比率為50質量%以上者作為保護膜形成膜13之情形時，具保護膜之半導體晶圓901’之中，保護膜13’具有高的保護性能，半導體晶圓9的保護功效高。As explained above, when a protective film-forming film is used as the protective film-forming film 13 in which the ratio of the filler (D) content relative to the total mass of the protective film-forming film is 50% by mass or more, the protective film-forming film 13 has a protective film. Among the semiconductor wafers 901', the protective film 13' has high protective performance, and the semiconductor wafer 9 has a high protective effect.

如前文所說明，使用保護膜形成膜中，相對於保護膜形成膜的總質量，填充材(D)的含量的比率為65質量%以下者作為保護膜形成膜13之情形時，抑制在具保護膜之半導體晶圓901’之翹曲的功效變高。As described above, when the protective film-forming film is used as the protective film-forming film 13 in which the content ratio of the filler (D) is 65% by mass or less relative to the total mass of the protective film-forming film, the protective film-forming film 13 is suppressed from being The effect of the protective film on warping of the semiconductor wafer 901' becomes higher.

[印字步驟] 製造方法(1)之前述熱硬化步驟之後，前述印字步驟之中，如圖4C所示，藉由於保護膜形成用複合片101’中之保護膜13’的支撐片10側之面(亦即第二面13b’)照射雷射光R，於前述面進行雷射印字。 雷射印字能夠以公知的方法來進行。例如，藉由將雷射光R的波長設為300nm至1100nm、掃描速度設為50mm/s至1000mm/s而照射雷射光R，能夠良好地進行雷射印字。作為代表性的雷射光R的波長，例如可列舉：355nm、532nm、1064nm等，這些波長為其中一例。 [Print steps] Manufacturing method (1) After the aforementioned thermal hardening step, during the aforementioned printing step, as shown in FIG. 4C , the surface of the protective film 13 ′ in the protective film forming composite sheet 101 ′ on the support sheet 10 side (that is, The second surface 13b') is irradiated with laser light R, and laser printing is performed on the aforementioned surface. Laser printing can be performed by a known method. For example, by irradiating the laser light R with a wavelength of 300 nm to 1100 nm and a scanning speed of 50 mm/s to 1000 mm/s, laser printing can be performed satisfactorily. Typical wavelengths of the laser light R include, for example, 355 nm, 532 nm, 1064 nm, and the like, and these wavelengths are examples.

[加工步驟] 製造方法(1)之前述印字步驟之後，前述加工步驟之中，於保護膜形成用複合片101’中之支撐片10上將半導體晶圓9分割成半導體晶片90，沿著半導體晶圓9的分割部位來切斷保護膜13’。藉此，如圖4D所示，製作具備半導體晶片90以及設置於半導體晶片90的內面90b之切斷後的保護膜130’之具保護膜之半導體晶片913’，且製作多個具保護膜之半導體晶片913’被固定在支撐片10上整齊排列所構成之具保護膜之半導體晶片群902。 圖4D中，符號130a’係表示切斷後的保護膜130’的第一面，對應保護膜13’的第一面13a’。另外，符號130b’係表示切斷後的保護膜130’的第二面，對應保護膜13’的第二面13b’。另外，符號90a係表示半導體晶片90的電路面，對應半導體晶圓9的電路面9a。 [Processing steps] Manufacturing method (1) After the aforementioned printing step and during the aforementioned processing step, the semiconductor wafer 9 is divided into semiconductor wafers 90 on the support sheet 10 in the protective film forming composite sheet 101'. Cut off the protective film 13' at the divided part. Thereby, as shown in FIG. 4D , a semiconductor wafer with a protective film 913 ′ including the semiconductor wafer 90 and the cut protective film 130 ′ provided on the inner surface 90 b of the semiconductor wafer 90 is produced, and a plurality of semiconductor wafers with a protective film are produced. The semiconductor wafer 913' is fixed on the support sheet 10 and is arranged in a neatly arranged semiconductor wafer group 902 with a protective film. In Figure 4D, symbol 130a' represents the first surface of the cut protective film 130', corresponding to the first surface 13a' of the protective film 13'. In addition, the symbol 130b' represents the second surface of the cut protective film 130', corresponding to the second surface 13b' of the protective film 13'. In addition, reference numeral 90a indicates the circuit surface of the semiconductor wafer 90 and corresponds to the circuit surface 9a of the semiconductor wafer 9.

製造方法(1)的加工步驟之中，例如亦可同時進行半導體晶圓9的分割與保護膜13’的切斷，亦可在進行半導體晶圓9的分割之後，進行保護膜13’的切斷。 製造方法(1)之中，在藉由不論順序且不中斷的同一操作來連續進行半導體晶圓的分割與保護膜的切斷之情形時，視為半導體晶圓的分割與保護膜形成膜的切斷同時進行。 In the processing steps of the manufacturing method (1), for example, the dividing of the semiconductor wafer 9 and the cutting of the protective film 13' may be performed simultaneously, or the protective film 13' may be cut after the dividing of the semiconductor wafer 9. break. In the manufacturing method (1), when the dividing of the semiconductor wafer and the cutting of the protective film are continuously performed by the same operation regardless of the order and without interruption, the dividing of the semiconductor wafer and the forming of the protective film are regarded as Cut off at the same time.

半導體晶圓9的分割與保護膜13’的切斷皆能夠根據進行這些的順序而以公知的方法來進行。Both the division of the semiconductor wafer 9 and the cutting of the protective film 13' can be performed by a known method according to the order in which these are performed.

例如，使用刀片之刀片切割、藉由照射雷射光之雷射切割、或是藉由噴附含有研磨劑之水之水力切割等各種切割，藉此可同時進行半導體晶圓9的分割與保護膜13’的切斷。 另外，就算是藉由隱形切割(註冊商標)形成改質層，且與未進行分割之半導體晶圓9與保護膜13’一起在平行於這些表面的方向進行拉伸(進行所謂擴展(expand))，也可以同時進行半導體晶圓9的分割與保護膜13’的切斷。這種擴展較佳係在－20℃至5℃等低溫進行。 For example, various cutting methods such as blade cutting using a blade, laser cutting by irradiating laser light, or hydraulic cutting by spraying water containing abrasives can be used to simultaneously separate and protect the semiconductor wafer 9 . 13' cut off. In addition, even if the modified layer is formed by stealth dicing (registered trademark), and the undivided semiconductor wafer 9 and the protective film 13' are stretched in a direction parallel to these surfaces (so-called expansion is performed) ), the division of the semiconductor wafer 9 and the cutting of the protective film 13' may be performed simultaneously. This expansion is best carried out at low temperatures such as -20°C to 5°C.

所謂隱形切割(註冊商標)，係如以下之方法。亦即，首先，藉由於半導體晶圓的內部設定預定分割部位，將該部位設為焦點，以聚焦於該焦點的方式照射雷射光，於半導體晶圓的內部形成改質層。半導體晶圓的改質層與半導體晶圓的其他部位不同，藉由照射雷射光而改質，強度變弱。因此，藉由於半導體晶圓施加力，半導體晶圓的內部的改質層中，產生朝半導體晶圓的兩面方向延伸之龜裂，成為半導體晶圓的分割的起點。然後，於半導體晶圓施加力，於前述改質層的部位分割半導體晶圓，製作半導體晶片。The so-called invisible cutting (registered trademark) is as follows. That is, first, a predetermined divided portion is set inside the semiconductor wafer, the portion is set as a focus, and laser light is irradiated to focus on the focus, thereby forming a modified layer inside the semiconductor wafer. Unlike other parts of the semiconductor wafer, the modified layer of the semiconductor wafer is modified by irradiation with laser light and becomes weaker in intensity. Therefore, when a force is exerted by the semiconductor wafer, cracks extending toward both surfaces of the semiconductor wafer are generated in the modified layer inside the semiconductor wafer, which become a starting point for dividing the semiconductor wafer. Then, force is applied to the semiconductor wafer, and the semiconductor wafer is divided at the portion of the modified layer to produce a semiconductor wafer.

如前文所說明，使用保護膜形成膜中相對於保護膜形成膜的總質量，填充材(D)的含量的比率為50質量%以上者作為保護膜形成膜13之情形時，具保護膜之半導體晶片913’之中，保護膜130’具有高的保護性能，半導體晶片90的保護功效高。例如，具保護膜之半導體晶片913’之中，碎屑得到抑制。As explained above, when the ratio of the content of the filler (D) in the protective film-forming film to the total mass of the protective film-forming film is 50% by mass or more as the protective film-forming film 13, it is necessary to have a protective film. Among the semiconductor wafers 913', the protective film 130' has high protective performance, and the semiconductor wafer 90 has a high protective effect. For example, in the semiconductor chip 913' with a protective film, debris is suppressed.

[拾取步驟] 製造方法(1)之前述加工步驟之後，前述拾取步驟之中，如圖4E所示，將具保護膜之半導體晶片913’自支撐片10扯離而加以拾取。 製造方法(1)的拾取步驟之中，在具保護膜之半導體晶片913’中之保護膜130’的第二面130b’與支撐片10中之黏著劑層12的第一面12a之間產生剝離。 [Pickup steps] After the aforementioned processing steps of the manufacturing method (1), during the aforementioned picking-up step, as shown in FIG. 4E, the semiconductor wafer 913' with the protective film is pulled away from the supporting sheet 10 and picked up. In the pick-up step of the manufacturing method (1), a gap is generated between the second surface 130b' of the protective film 130' in the semiconductor wafer 913' with a protective film and the first surface 12a of the adhesive layer 12 in the support sheet 10. Strip.

具保護膜之半導體晶片913’能夠以公知的方法進行拾取。 例如，製造方法(1)之中，能夠藉由將具保護膜之半導體晶片913’從支撐片10側經由(介設)支撐片10而使用銷頂起來進行拾取。圖4E係進而表示使用真空筒夾等扯離手段7，將具保護膜之半導體晶片913’於箭頭P方向進行扯離之情形。 The semiconductor wafer 913' with the protective film can be picked up by a known method. For example, in the manufacturing method (1), the semiconductor wafer 913' provided with the protective film can be picked up from the support sheet 10 side via (intermediately) the support sheet 10 using pins. FIG. 4E further shows the situation in which the semiconductor wafer 913' with the protective film is separated in the direction of arrow P using a separation means 7 such as a vacuum collet.

製造方法(1)之前述拾取步驟之後，例如藉由將所拾取之具保護膜之半導體晶片913’中之突狀電極以覆晶連接於基板的電路面，使具保護膜之半導體晶片913’接合於前述電路面(本說明書之中有時稱為「接合步驟」)。 前述突狀電極係設置於具保護膜之半導體晶片913’中之半導體晶片90的電路面90a。 接合步驟之中，例如能夠藉由使具保護膜之半導體晶片913’中之突狀電極接觸設置於基板的電路面之連接墊，而將前述突狀電極與前述電路面上之前述連接墊進行電性連接而覆晶連接。 具保護膜之半導體晶片913’對前述電路面之接合能夠以公知的方法進行。 After the aforementioned pickup step of the manufacturing method (1), for example, by flip-chip connecting the protruding electrodes in the picked up semiconductor wafer 913' with a protective film to the circuit surface of the substrate, the semiconductor wafer 913' with the protective film is Bonding to the aforementioned circuit surface (sometimes referred to as "bonding step" in this specification). The aforementioned protruding electrodes are provided on the circuit surface 90a of the semiconductor chip 90 in the semiconductor chip 913' having a protective film. In the bonding step, for example, the protruding electrodes in the semiconductor chip 913' with the protective film can be brought into contact with the connection pads provided on the circuit surface of the substrate, so that the protruding electrodes and the connection pads on the circuit surface can be connected. Electrical connection and flip chip connection. The semiconductor wafer 913' with the protective film can be bonded to the circuit surface by a known method.

前述接合步驟之後，藉由使用具備有具保護膜之半導體晶片913’之基板，以後依據公知的方法製作半導體封裝體，並使用該半導體封裝體，能夠製造目標之半導體裝置。After the above-mentioned bonding step, by using a substrate having a semiconductor wafer 913' with a protective film, a semiconductor package is produced according to a known method, and using the semiconductor package, a target semiconductor device can be manufactured.

至此為止，作為製造方法(1)，說明了關於使用保護膜形成用複合片之情形的半導體裝置之製造方法，但即使替代保護膜形成用複合片而改為使用未構成保護膜形成用複合片之保護膜形成膜，仍可製造半導體裝置。 圖5A至圖5F係用以示意性地說明本實施形態之半導體裝置之製造方法之中，使用未構成保護膜形成用複合片之保護膜形成膜之情形之製造方法之一例(本說明書之中有時稱為「製造方法(2)」)之剖面圖。此處，對於使用圖1所示之保護膜形成膜13之情形加以說明。 So far, the manufacturing method of a semiconductor device using the composite sheet for forming a protective film has been described as the manufacturing method (1). However, even if the composite sheet for forming a protective film is used instead of the composite sheet for forming a protective film, a composite sheet that does not constitute a protective film forming composite sheet is used. The protective film is formed into a film, and semiconductor devices can still be manufactured. 5A to 5F are schematically illustrating an example of a manufacturing method in which a protective film-forming film that does not constitute the protective film-forming composite sheet is used in the manufacturing method of the semiconductor device according to this embodiment (in this specification Sometimes called "manufacturing method (2)") cross-sectional view. Here, the case of using the protective film forming film 13 shown in FIG. 1 will be described.

[製造方法(2)] [貼附步驟] 前述製造方法(2)之前述貼附步驟之中，如圖5A所示，藉由將未構成前述保護膜形成用複合片之保護膜形成膜13(更具體而言，經移除第一剝離膜151之保護膜形成膜13)貼附於半導體晶圓9的內面9b，製作具保護膜形成膜之半導體晶圓901。 本步驟除了替代構成保護膜形成用複合片101(換言之係具備支撐片10之保護膜形成膜13)而改為使用具備第二剝離膜152之保護膜形成膜13的方面以外，係與製造方法(1)之前述貼附步驟相同。 [Manufacturing method (2)] [Attach steps] In the aforementioned attaching step of the aforementioned manufacturing method (2), as shown in FIG. 5A , the protective film forming film 13 (more specifically, after removing the first peeling film) that does not constitute the aforementioned protective film forming composite sheet is The protective film forming film 13) of the film 151 is attached to the inner surface 9b of the semiconductor wafer 9, and a semiconductor wafer 901 having a protective film forming film is produced. This step is the same as the manufacturing method except that the protective film forming film 13 provided with the second release film 152 is used instead of the protective film forming composite sheet 101 (in other words, the protective film forming film 13 provided with the support sheet 10 ). (1) The attaching steps are the same as mentioned above.

保護膜形成膜13亦可在貼附於半導體晶圓9的內面9b之前預先裁斷成與半導體晶圓9相同直徑或小於晶圓的直徑1mm至10mm之直徑的圓形狀。藉由如此，在貼附步驟之作業性以及移除後述的第二剝離膜152的作業性提高。The protective film forming film 13 may be pre-cut into a circular shape having the same diameter as the semiconductor wafer 9 or a diameter 1 mm to 10 mm smaller than the diameter of the wafer 9 before being attached to the inner surface 9 b of the semiconductor wafer 9 . This improves the workability in the attaching step and the workability in removing the second release film 152 described below.

製造方法(2)中，藉由自保護膜形成膜13所製作之前述試片之上述在DSC之發熱起始溫度為160℃以上，貼附步驟之中，保護膜形成膜13對半導體晶圓9之貼附性良好。例如，即使使用以常溫保存後的保護膜形成膜13，保護膜形成膜13對半導體晶圓9之貼附性仍良好，因此，保護膜所帶來之半導體晶片的保護性能亦高。In the manufacturing method (2), the above-mentioned test piece produced by the self-protective film-forming film 13 has a heat starting temperature in DSC of 160° C. or above. During the attachment step, the protective film-forming film 13 has no contact with the semiconductor wafer. 9. Good adhesion. For example, even if the protective film-forming film 13 stored at normal temperature is used, the adhesion of the protective film-forming film 13 to the semiconductor wafer 9 is still good. Therefore, the protective performance of the semiconductor wafer provided by the protective film is also high.

[熱硬化步驟] 製造方法(2)之前述貼附步驟之後，前述熱硬化步驟之中，使具保護膜形成膜之半導體晶圓901中之保護膜形成膜13進行熱硬化，如圖5B所示，形成保護膜13’。因此，具保護膜形成膜之半導體晶圓901成為具保護膜之半導體晶圓901’。 本步驟除了替代具備保護膜形成用複合片101之半導體晶圓9而改為使用具備保護膜形成膜13與第二剝離膜152的積層物之半導體晶圓9的方面以外，係與製造方法(1)之前述熱硬化步驟相同。 [Thermal hardening step] Manufacturing method (2) After the above-mentioned attaching step, during the above-mentioned thermal hardening step, the protective film-forming film 13 in the semiconductor wafer 901 with the protective film-forming film is thermally cured, as shown in FIG. 5B, to form a protective film. 13'. Therefore, the semiconductor wafer 901 with the protective film forming film becomes the semiconductor wafer with the protective film 901'. This step is the same as the manufacturing method ( 1) The same thermal hardening steps as mentioned above.

製造方法(2)中，如前文所說明，使用保護膜形成膜中，相對於保護膜形成膜的總質量，填充材(D)的含量的比率為50質量%以上者作為保護膜形成膜13之情形時，具保護膜之半導體晶圓901’之中，保護膜13’具有高的保護性能，半導體晶圓9的保護功效高。In the manufacturing method (2), as described above, a protective film-forming film in which the content ratio of the filler (D) is 50 mass % or more relative to the total mass of the protective film-forming film is used as the protective film-forming film 13 In this case, in the semiconductor wafer 901' with a protective film, the protective film 13' has high protective performance, and the semiconductor wafer 9 has a high protective effect.

製造方法(2)中，如前文所說明，使用保護膜形成膜中，相對於保護膜形成膜的總質量，填充材(D)的含量的比率為65質量%以下者作為保護膜形成膜13之情形時，抑制在具保護膜之半導體晶圓901’之翹曲的功效變高。In the manufacturing method (2), as described above, a protective film-forming film in which the content ratio of the filler (D) is 65 mass % or less relative to the total mass of the protective film-forming film is used as the protective film-forming film 13 In this case, the effect of suppressing warpage of the semiconductor wafer 901' provided with the protective film becomes higher.

[印字步驟] 製造方法(2)之前述熱硬化步驟之後，前述印字步驟之中，如圖5C所示，藉由自具保護膜之半導體晶圓901’移除第二剝離膜152，在因此所新產生之露出面(亦即保護膜13’的第二面13b’)照射雷射光R，於前述面進行雷射印字。雷射印字後的具保護膜之半導體晶圓901’係與製造方法(1)中雷射印字後的具保護膜之半導體晶圓901’相同。 本步驟之中，能夠以與製造方法(1)之前述印字步驟之情形相同方法於保護膜13’進行雷射印字。 [Print steps] After the aforementioned thermal hardening step of the manufacturing method (2), during the aforementioned printing step, as shown in FIG. 5C , the second release film 152 is removed from the semiconductor wafer 901' having the protective film. In the thus newly generated The exposed surface (that is, the second surface 13b' of the protective film 13') is irradiated with laser light R, and laser printing is performed on the surface. The semiconductor wafer 901' with a protective film after laser printing is the same as the semiconductor wafer 901' with a protective film after laser printing in the manufacturing method (1). In this step, laser printing can be performed on the protective film 13' in the same manner as in the aforementioned printing step of the manufacturing method (1).

[切割片貼附步驟] 製造方法(2)之前述印字步驟之後，如圖5D所示，於具保護膜之半導體晶圓901’中之保護膜13’的第二面13b’貼附切割片80。切割片80係具備基材81以及設置於其中一面之黏著劑層82。本步驟之中，將黏著劑層82中與基材81側為相反側之面(本說明書之中，有時稱為「第一面」)82a貼附於保護膜13’的第二面13b’。黏著劑層82的第一面82a係與切割片80的第一面80a相同。 如此，製造方法(2)係具有如下之切割片貼附步驟：在前述印字步驟與前述加工步驟之間，於前述具保護膜之半導體晶圓中之前述保護膜中與前述半導體晶圓側為相反側之面貼附切割片。 [Steps to attach cutting sheet] After the aforementioned printing step in the manufacturing method (2), as shown in FIG. 5D, the dicing sheet 80 is attached to the second surface 13b' of the protective film 13' in the semiconductor wafer 901' with the protective film. The cutting blade 80 includes a base material 81 and an adhesive layer 82 provided on one side. In this step, the side 82a of the adhesive layer 82 opposite to the side of the base material 81 (sometimes referred to as the "first side" in this specification) is attached to the second side 13b of the protective film 13'. '. The first side 82a of the adhesive layer 82 is the same as the first side 80a of the cutting blade 80. In this way, the manufacturing method (2) has the following dicing sheet attaching step: between the aforementioned printing step and the aforementioned processing step, in the aforementioned semiconductor wafer with a protective film, the center of the protective film and the side of the semiconductor wafer are The cutting piece is attached to the opposite side.

切割片80亦可具有與保護膜形成用複合片101中之支撐片10同樣的構成。 此處，表示對於使用了切割片80之情形，製造方法(2)之中，例如亦可使用僅由基材所構成之切割片等切割片80以外的公知的切割片。 The dicing sheet 80 may have the same structure as the support sheet 10 in the protective film forming composite sheet 101 . Here, it is shown that the dicing blade 80 is used. In the manufacturing method (2), a known dicing blade other than the dicing blade 80 such as a dicing blade composed only of a base material may be used.

切割片80對保護膜13’之貼附能夠以公知的方法進行，例如能夠在製造方法(1)之前述貼附步驟中，以與保護膜形成用複合片101對半導體晶圓9之貼附之情形相同方法進行。The dicing sheet 80 can be attached to the protective film 13' by a known method. For example, the protective film forming composite sheet 101 can be attached to the semiconductor wafer 9 in the above-mentioned attachment step of the manufacturing method (1). The situation is carried out in the same way.

製造方法(2)之中，前述切割片貼附步驟以後，除了替代上述之具備支撐片10之具保護膜之半導體晶圓901’而改為使用具備切割片80之具保護膜之半導體晶圓901’的方面以外，能夠以與製造方法(1)之情形相同方法進行加工步驟、拾取步驟以及接合步驟，製造目標之半導體裝置。In the manufacturing method (2), after the aforementioned dicing sheet attaching step, in addition to replacing the above-mentioned semiconductor wafer with a protective film 901' provided with the support sheet 10, a semiconductor wafer with a protective film provided with the dicing sheet 80 is used instead. Except for the aspect 901', the processing step, the picking up step, and the bonding step can be performed in the same manner as in the case of the manufacturing method (1), and the target semiconductor device can be manufactured.

[加工步驟] 例如，製造方法(2)之前述印字步驟(前述切割片貼附步驟)之後，前述加工步驟之中，如圖5E所示，藉由於切割片80上，將半導體晶圓9分割成半導體晶片90，沿著半導體晶圓9的分割部位來切斷保護膜13’，製作具保護膜之半導體晶片913’。藉此所獲得之具保護膜之半導體晶片913’係與製造方法(1)中具保護膜之半導體晶片913’相同。製造方法(2)的加工步驟之中，與具保護膜之半導體晶片913’一起製作多個具保護膜之半導體晶片913’被固定在切割片80上整齊排列而構成之具保護膜之半導體晶片群903。 [Processing steps] For example, after the aforementioned printing step (the aforementioned dicing sheet attaching step) in the manufacturing method (2), during the aforementioned processing step, as shown in FIG. 5E , the semiconductor wafer 9 is divided into semiconductor wafers 90 by using the dicing sheet 80 , cut the protective film 13' along the divided portions of the semiconductor wafer 9 to produce a semiconductor wafer 913' with a protective film. The semiconductor wafer 913' with a protective film obtained in this way is the same as the semiconductor wafer 913' with a protective film in the manufacturing method (1). In the processing step of the manufacturing method (2), together with the semiconductor wafer 913' having a protective film, a plurality of semiconductor wafers 913' having a protective film are fixed on the dicing sheet 80 and arranged in an orderly manner to form a semiconductor wafer with a protective film. Group 903.

製造方法(2)中，如前文所說明，使用保護膜形成膜中，相對於保護膜形成膜的總質量，填充材(D)的含量的比率為50質量%以上者作為保護膜形成膜13之情形時，具保護膜之半導體晶圓901’之中，保護膜130’具有高的保護性能，半導體晶片90的保護功效高。例如，具保護膜之半導體晶片913’之中，碎屑得到抑制。In the manufacturing method (2), as described above, a protective film-forming film in which the content ratio of the filler (D) is 50 mass % or more relative to the total mass of the protective film-forming film is used as the protective film-forming film 13 In this case, in the semiconductor wafer 901' with a protective film, the protective film 130' has high protective performance, and the semiconductor wafer 90 has a high protective effect. For example, in the semiconductor chip 913' with a protective film, debris is suppressed.

[拾取步驟] 例如，於製造方法(2)的前述加工步驟之後，於前述拾取步驟之中，如圖5F所示般，將具保護膜之半導體晶片913’自切割片80扯離而進行拾取。 於製造方法(2)的前述拾取步驟之中，在具保護膜之半導體晶片913’中的保護膜130’的第二面130b’與切割片80中的黏著劑層82的第一面82a之間產生剝離。 [Pickup steps] For example, after the aforementioned processing step of the manufacturing method (2), in the aforementioned pickup step, as shown in FIG. 5F , the semiconductor wafer 913' with the protective film is pulled away from the dicing sheet 80 and picked up. In the aforementioned pickup step of the manufacturing method (2), between the second surface 130b' of the protective film 130' in the semiconductor wafer 913' with a protective film and the first surface 82a of the adhesive layer 82 in the dicing sheet 80 peeling occurs.

製造方法(2)在前述拾取步驟所拾取之具保護膜之半導體晶片913’係與製造方法(1)在前述拾取步驟所拾取之具保護膜之半導體晶片913’相同。因此，製造方法(2)在這之後之前述接合步驟等各步驟係與製造方法(1)之前述接合步驟等各步驟相同，能夠以與製造方法(1)之情形同樣的方式製造目標之半導體裝置。The semiconductor wafer 913' with a protective film picked up in the aforementioned pickup step of the manufacturing method (2) is the same as the semiconductor wafer 913' with a protective film picked up in the aforementioned pickup step of the manufacturing method (1). Therefore, the manufacturing method (2) and subsequent steps such as the bonding step are the same as the manufacturing method (1), and the target semiconductor can be manufactured in the same manner as in the manufacturing method (1). device.

[半導體裝置之製造方法的變形例] 本實施形態之半導體裝置之製造方法，在不損及本發明的功效之範圍內，亦可具有不相當於前述貼附步驟、前述熱硬化步驟、前述印字步驟、前述切割片貼附步驟、前述加工步驟、前述拾取步驟、前述接合步驟中任一步驟之其他步驟。 前述其他步驟可根據目的而任意選擇，並無特別限定。 進行前述其他步驟之時機，能夠根據前述其他步驟的內容而適當選擇。 [Modification of the method of manufacturing a semiconductor device] The method of manufacturing a semiconductor device according to this embodiment may include steps other than the above-mentioned attaching step, the above-mentioned thermal hardening step, the above-mentioned printing step, the above-mentioned dicing sheet attaching step, and the above-mentioned step, within the scope that does not impair the effect of the present invention. Other steps of any of the processing steps, the aforementioned picking up steps, and the aforementioned bonding steps. The aforementioned other steps can be selected arbitrarily according to the purpose and are not particularly limited. The timing of performing the aforementioned other steps can be appropriately selected based on the contents of the aforementioned other steps.

作為前述半導體裝置之製造方法中前述其他步驟之一例，可列舉如下之步驟：在前述貼附步驟之前，於前述半導體晶圓的電路面貼附背面研磨帶之背面研磨帶貼附步驟；在前述背面研磨帶貼附步驟之後且前述貼附步驟之前，自前述半導體晶圓的電路面移除背面研磨帶之背面研磨帶去除步驟。 前述背面研磨帶可為公知之背面研磨帶，前述背面研磨帶貼附至半導體晶圓之電路面、以及自半導體晶圓的電路面去除背面研磨帶，係能夠以公知的方法進行。 As an example of the other steps in the manufacturing method of the semiconductor device, the following steps can be cited: before the above attaching step, a back polishing tape attaching step is attached to the circuit surface of the semiconductor wafer; After the back polishing tape attaching step and before the aforementioned attaching step, there is a back polishing tape removing step of removing the back polishing tape from the circuit surface of the semiconductor wafer. The back polishing tape can be a known back polishing tape. The back polishing tape can be attached to the circuit surface of the semiconductor wafer and removed from the circuit surface of the semiconductor wafer by known methods.

本說明書之中，單純「貼附步驟」之記載，意指不相當於「切割片貼附步驟」、「背面研磨帶貼附步驟」中之任一者中之將上述之前述保護膜形成膜、或是前述保護膜形成用複合片中之保護膜形成膜貼附於半導體晶圓的內面之步驟。In this specification, the description of "attaching step" simply means that it does not correspond to any of the "cutting sheet attaching step" and the "back polishing tape attaching step" to form the above-mentioned protective film into a film. , or a step of attaching the protective film forming film in the protective film forming composite sheet to the inner surface of the semiconductor wafer.

至此為止，作為前述製造方法(1)，對於使用圖2所示之保護膜形成用複合片101之情形進行說明，但本實施形態的半導體裝置之製造方法之中，亦可使用以如圖3之保護膜形成用複合片102等為首之其他保護膜形成用複合片。 在使用前述其他保護膜形成用複合片之情形時，根據前述其他保護膜形成用複合片與圖2所示之保護膜形成用複合片101在構成的差異，本實施形態之半導體裝置之製造方法亦可具有在任一時機進行之前述其他步驟。 [實施例] So far, the case where the protective film forming composite sheet 101 shown in FIG. 2 is used as the manufacturing method (1) has been described. However, in the manufacturing method of the semiconductor device of this embodiment, the method as shown in FIG. 3 can also be used. Other protective film forming composite sheets including the protective film forming composite sheet 102 and the like. When the other composite sheet for protective film formation is used, the manufacturing method of the semiconductor device of this embodiment is based on the difference in structure between the composite sheet for other protective film formation and the composite sheet 101 for protective film formation shown in FIG. 2 . Other steps described above may also be performed at any time. [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.

[樹脂之製造原料] 本實施例以及比較例中縮寫之樹脂之製造原料的正式名稱係如下所示。 BA：丙烯酸正丁酯 MA：丙烯酸甲酯 GMA：甲基丙烯酸縮水甘油酯 HEA：丙烯酸-2-羥乙酯 [Resin manufacturing raw materials] The official names of the raw materials for producing the resins abbreviated in the present Examples and Comparative Examples are as follows. BA: n-butyl acrylate MA: Methyl acrylate GMA: glycidyl methacrylate HEA: 2-hydroxyethyl acrylate

[保護膜形成用組成物之製造原料] 用於保護膜形成用組成物之製造之原料係如以下所示。 [聚合物成分(A)] (A)-1：BA(10質量份)、MA(70質量份)、GMA(5質量份)以及HEA(15質量份)共聚而成之丙烯酸聚合物(重量平均分子量400000，玻璃轉移溫度－1℃) [環氧樹脂(B1)] (B1)-1：液狀雙酚A型環氧樹脂(三菱化學公司製「jER828」，環氧當量184g/eq至194g/eq) (B1)-2：固形雙酚A型環氧樹脂(三菱化學公司製「jER1055」，環氧當量800g/eq至900g/eq) (B1)-3：二環戊二烯型環氧樹脂(DIC公司製「EPICLON HP-7200HH」，環氧當量274g/eq至284g/eq) [熱硬化劑(B2)] (B2)-1：二氰二胺(熱活性潛伏性環氧樹脂硬化劑，三菱化學公司製「DICY7」) [硬化促進劑(C)] (C)-1：2-苯基-4-甲基-5-羥甲基咪唑(四國化成工業公司製「Curezol(註冊商標)2P4MHZ-PW」) (C)-2：咪唑系硬化促進劑(1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮與6-2-(2-甲基-1H-咪唑-1-基)乙基-1,3,5-三嗪-2,4-二胺之1：1的混合物，四國化成工業公司製「Curezol(註冊商標)2MAOK-PW」) (C)-3：2-十七烷基咪唑(四國化成工業公司製「Curezol(註冊商標)C17Z」) (C)-4：2-苯基-4,5-二羥甲基咪唑(四國化成工業公司製「Curezol(註冊商標)2PHZ-PW」) [填充材(D)] (D)-1：二氧化矽填料(Admatechs公司製「SC2050MA」，以環氧系化合物進行表面修飾之球狀二氧化矽填料，平均粒徑0.5μm) [偶合劑(E)] (E)-1：3-縮水甘油氧基丙基三甲氧基矽烷(矽烷偶合劑、信越Silicone公司製「KBM403」，甲氧基當量12.7mmol/g，分子量236.3) [著色劑(I)] (I)-1：有機系黑色顏料(大日精化工業公司製「6377 BLACK」) [Raw materials for manufacturing compositions for forming protective films] The raw materials used for manufacturing the protective film forming composition are as follows. [Polymer component (A)] (A)-1: Acrylic polymer (weight average molecular weight 400000, glass transition temperature - 1℃) [Epoxy resin (B1)] (B1)-1: Liquid bisphenol A-type epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184g/eq to 194g/eq) (B1)-2: Solid bisphenol A type epoxy resin ("jER1055" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 800g/eq to 900g/eq) (B1)-3: Dicyclopentadiene-type epoxy resin ("EPICLON HP-7200HH" manufactured by DIC Corporation, epoxy equivalent 274g/eq to 284g/eq) [Thermal hardener (B2)] (B2)-1: Dicyanodiamine (heat-active latent epoxy resin hardener, "DICY7" manufactured by Mitsubishi Chemical Corporation) [Harding accelerator (C)] (C)-1: 2-phenyl-4-methyl-5-hydroxymethylimidazole ("Curezol (registered trademark) 2P4MHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd.) (C)-2: Imidazole hardening accelerator (1,3,5-triazine-2,4,6(1H,3H,5H)-trione and 6-2-(2-methyl-1H-imidazole) -1:1 mixture of 1-yl)ethyl-1,3,5-triazine-2,4-diamine, "Curezol (registered trademark) 2MAOK-PW" manufactured by Shikoku Chemical Industry Co., Ltd.) (C)-3: 2-Heptadecylimidazole ("Curezol (registered trademark) C17Z" manufactured by Shikoku Chemical Industry Co., Ltd.) (C)-4: 2-phenyl-4,5-dihydroxymethylimidazole ("Curezol (registered trademark) 2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd.) [Filling material (D)] (D)-1: Silica filler ("SC2050MA" manufactured by Admatechs, spherical silica filler surface-modified with an epoxy compound, average particle size 0.5 μm) [Coupling agent (E)] (E)-1: 3-glycidoxypropyltrimethoxysilane (silane coupling agent, "KBM403" manufactured by Shin-Etsu Silicone Co., Ltd., methoxy equivalent 12.7 mmol/g, molecular weight 236.3) [Color(I)] (I)-1: Organic black pigment ("6377 BLACK" manufactured by Dainichi Seika Industrial Co., Ltd.)

[實施例1] [保護膜形成膜之製造] [保護膜形成用組成物(III)之製造] 將聚合物成分(A)-1(18.45質量份)、環氧樹脂(B1)-1(11.07質量份)、環氧樹脂(B1)-2(1.85質量份)、環氧樹脂(B1)-3(5.54質量份)、熱硬化劑(B2)-1(0.37質量份)、硬化促進劑(C)-1(0.37質量份)、填充材(D)-1(59.04質量份)、偶合劑(E)-1(0.37質量份)以及著色劑(I)-1(2.95質量份)溶解或是分散於甲基乙基酮，在23℃進行攪拌，藉此獲得溶媒以外的所有成分的合計濃度為50質量%之熱硬化性的保護膜形成用組成物(III)-1。此處所示之甲基乙基酮以外的成分的調配量皆為不含溶媒之目標物的調配量。 [Example 1] [Manufacture of protective film forming film] [Production of protective film forming composition (III)] Polymer component (A)-1 (18.45 parts by mass), epoxy resin (B1)-1 (11.07 parts by mass), epoxy resin (B1)-2 (1.85 parts by mass), epoxy resin (B1)- 3 (5.54 parts by mass), thermal hardener (B2)-1 (0.37 parts by mass), hardening accelerator (C)-1 (0.37 parts by mass), filler (D)-1 (59.04 parts by mass), coupling agent (E)-1 (0.37 parts by mass) and coloring agent (I)-1 (2.95 parts by mass) are dissolved or dispersed in methyl ethyl ketone, and stirred at 23°C to obtain the total of all components except the solvent. Thermosetting composition (III)-1 for forming a protective film at a concentration of 50% by mass. The amounts of components other than methyl ethyl ketone shown here are the amounts of the target product without the solvent.

[保護膜形成膜之製造] 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剝離處理之剝離膜(第二剝離膜，琳得科公司製「SP-PET502150」，厚度50μm)，於前述剝離處理面塗敷上述所獲得之保護膜形成用組成物(III)-1，以100℃乾燥2分鐘，藉此製造厚度25μm的熱硬化性的保護膜形成膜。 [Manufacture of protective film forming film] A release film (second release film, "SP-PET502150" manufactured by Lintec Co., Ltd., thickness 50 μm) made of polyethylene terephthalate and subjected to release treatment with polysiloxane on one side was peeled off as mentioned above. The protective film-forming composition (III)-1 obtained above was applied to the treated surface and dried at 100° C. for 2 minutes, thereby producing a thermosetting protective film-forming film with a thickness of 25 μm.

進而，藉由在所獲得之保護膜形成膜中不具備第二剝離膜之側之露出面，在貼附速度2m/min、貼附溫度60℃、貼附壓力0.5MPa的條件下，貼合剝離膜(第一剝離膜，琳得科公司製「SP-PET381031」、厚度38μm)的剝離處理面，以製造具備保護膜形成膜、設置於前述保護膜形成膜其中一面之第一剝離膜、以及設置於前述保護膜形成膜的另一面之第二剝離膜所構成之具剝離膜之保護膜形成膜。Furthermore, by having no exposed surface on the side of the second release film in the obtained protective film-forming film, lamination was performed under the conditions of an adhesion speed of 2 m/min, an adhesion temperature of 60°C, and an adhesion pressure of 0.5 MPa. The release-treated surface of the release film (the first release film, "SP-PET381031" manufactured by Lintec Co., Ltd., thickness 38 μm) is used to produce a protective film-forming film and a first release film provided on one side of the protective film-forming film, and a protective film-forming film with a release film composed of a second release film provided on the other side of the protective film-forming film.

[保護膜形成膜之評價] [發熱起始溫度的測定] 使用上述所獲得之多片具剝離膜之保護膜形成膜，藉由一邊移除這些具剝離膜之保護膜形成膜的第一剝離膜或第二剝離膜，一邊將保護膜形成膜的露出面彼此依序貼合，製作第二剝離膜、多片保護膜形成膜、以及第二剝離膜依此順序積層而構成之積層物。然後，從該積層物切成切片。 然後，自該切片移除最表面的2片的第二剝離膜，將所獲得之切片作為試片。該試片的質量約5g。 然後，使用差示掃描熱析儀(日立High-Tech Science公司製「DSC-600」)藉由DSC法，以升溫速度10℃/min，將前述試片自23℃升溫至300℃為止，測定此時此時的發熱起始溫度。結果如表1所示。 [Evaluation of protective film forming film] [Measurement of fever onset temperature] Using the plurality of protective film-forming films with release films obtained above, the exposed surface of the protective film-forming film is removed while removing the first release film or the second release film of these protective film-forming films with release films. They are laminated together in order to produce a laminate in which a second release film, a plurality of protective film-forming films, and the second release film are laminated in this order. Then, slices were cut from the laminated product. Then, the two outermost second release films were removed from the slice, and the obtained slice was used as a test piece. The mass of the test piece is about 5g. Then, the aforementioned test piece was heated from 23°C to 300°C by the DSC method using a differential scanning calorimeter ("DSC-600" manufactured by Hitachi High-Tech Science Co., Ltd.) at a temperature rising rate of 10°C/min, and then measured. The starting temperature of heating at this time. The results are shown in Table 1.

[常溫之保存穩定性(貼附性)之評價] 將上述所獲得之具剝離膜之保護膜形成膜在大氣下、23℃的溫度條件下保存30日。 然後，藉由使用貼片機(琳得科公司製「RAD-3600F/12」)，對於12吋矽晶圓(厚度300μm)的＃2000研磨面，將該保存後的具剝離膜之保護膜形成膜以貼附速度50mm/s、輥溫度60℃、台溫度80℃、貼附壓力0.25MPa的條件，一邊移除一側的剝離膜(第一剝離膜)一邊進行貼附，藉此製作剝離膜(第二剝離膜)、保護膜形成膜、以及矽晶圓依序於這些層之厚度方向積層而構成之具備剝離膜之具保護膜形成膜之矽晶圓。 [Evaluation of storage stability (adhesiveness) at room temperature] The protective film-forming film with the release film obtained above was stored in the atmosphere at a temperature of 23° C. for 30 days. Then, by using a mount machine ("RAD-3600F/12" manufactured by Lintec Corporation), the preserved protective film with release film was placed on the #2000 polished surface of the 12-inch silicon wafer (thickness 300 μm). The formed film was produced by removing the peeling film (first peeling film) on one side and attaching it under the conditions of attaching speed of 50mm/s, roller temperature of 60°C, table temperature of 80°C, and attaching pressure of 0.25MPa. A release film (second release film), a protective film-forming film, and a silicon wafer are sequentially laminated in the thickness direction of these layers to form a silicon wafer with a release film and a protective film-forming film.

然後，自具保護膜形成膜之矽晶圓將剝離膜進行剝離。此時，以使剝離膜與保護膜形成膜相接之面彼此成為180°的角度的方式，將剝離膜自保護膜形成膜剝離(進行180°剝離)。然後，以目視觀察保護膜形成膜對矽晶圓之貼附狀態(貼附性)，依據下述基準，評價保護膜形成膜在常溫之保存穩定性。結果如表1所示。 (評價基準) A：保護膜形成膜完全沒有自矽晶圓浮起，保護膜形成膜密接於矽晶圓，保護膜形成膜的常溫之保存穩定性高。 B：矽晶圓的外周附近之一部分的區域與保護膜形成膜之間存在氣泡，保護膜形成膜的常溫之保存穩定性較A差。 C：保護膜形成膜與剝離膜一起自矽晶圓剝落，保護膜形成膜的常溫之保存穩定性低。 Then, the release film is peeled off from the silicon wafer with the protective film-formed film. At this time, the release film is peeled off from the protective film-forming film (180° peeling is performed) so that the contact surfaces of the release film and the protective film-forming film form an angle of 180° with each other. Then, the adhesion state (adhesion) of the protective film-forming film to the silicon wafer was visually observed, and the storage stability of the protective film-forming film at room temperature was evaluated based on the following criteria. The results are shown in Table 1. (evaluation criteria) A: The protective film-forming film does not float from the silicon wafer at all. The protective film-forming film is closely connected to the silicon wafer. The protective film-forming film has high storage stability at room temperature. B: There are air bubbles between a part of the area near the outer periphery of the silicon wafer and the protective film forming film. The storage stability of the protective film forming film at room temperature is worse than A. C: The protective film-forming film peels off from the silicon wafer together with the release film, and the storage stability of the protective film-forming film at room temperature is low.

[抑制在具保護膜之矽晶圓之翹曲的功效之評價] 以與上述的保護膜形成膜的常溫之保存穩定性(貼附性)之評價時相同方法，藉由對於12吋矽晶圓(厚度300μm)的＃2000研磨面，貼附上述所獲得之保護膜形成膜，製作具備剝離膜之具保護膜形成膜之矽晶圓。 然後，自具保護膜形成膜之矽晶圓將剝離膜進行剝離之後，藉由將該具保護膜形成膜之矽晶圓裝入烘箱的內部，以130℃加熱2小時，使保護膜形成膜熱硬化，製作具保護膜之矽晶圓。 [Evaluation of the effect of suppressing warpage of silicon wafers with protective films] The protection obtained above was applied to the #2000 polished surface of a 12-inch silicon wafer (thickness 300 μm) in the same manner as in the evaluation of storage stability (adhesion) at room temperature of the above-mentioned protective film-forming film. The film forming film is used to produce a silicon wafer with a peeling film and a protective film forming film. Then, after peeling off the release film from the silicon wafer with the protective film forming film, the silicon wafer with the protective film forming film is placed inside the oven and heated at 130° C. for 2 hours to form the protective film. Heat hardening to produce a silicon wafer with a protective film.

然後，將所獲得之具保護膜之矽晶圓從烘箱的內部取出，在常溫下放置冷卻之後，裝載於台的平坦面。此時，使具保護膜之矽晶圓中之矽晶圓面對台的平坦面。具保護膜之矽晶圓中之矽晶圓側之面在具保護膜之矽晶圓發生翹曲之情形時成為凸面。然後，在具保護膜之矽晶圓的外周部的任意的3部位測定台的平坦面與具保護膜之矽晶圓之間的距離，採用平均值作為具保護膜之矽晶圓的翹曲量。進而，根據下述基準，評價抑制在具保護膜之矽晶圓之翹曲的功效。結果如表1所示。 (評價基準) A：翹曲量為0mm，翹曲得到抑制。 B：翹曲量為超過0mm至2mm以下，抑制翹曲的功效較A差，但保護膜形成膜可供實際使用。 C：翹曲量為超過2mm，抑制翹曲的功效低，保護膜形成膜無法供於實際使用。 此處，保護膜形成膜可供於實際使用，意指在保護膜形成膜的熱硬化後(形成保護膜之後)，例如能夠無問題地貼附切割片、進行具保護膜之半導體晶圓的切割等通常的步驟。 Then, the obtained silicon wafer with the protective film is taken out from the inside of the oven, left to cool at normal temperature, and then placed on the flat surface of the table. At this time, the silicon wafer among the silicon wafers with the protective film is made to face the flat surface of the table. The surface on the silicon wafer side of the silicon wafer with the protective film becomes a convex surface when the silicon wafer with the protective film is warped. Then, the distance between the flat surface of the table and the silicon wafer with protective film is measured at three arbitrary locations on the outer periphery of the silicon wafer with protective film, and the average value is used as the warpage of the silicon wafer with protective film. quantity. Furthermore, based on the following criteria, the effect of suppressing warpage of the silicon wafer provided with the protective film was evaluated. The results are shown in Table 1. (evaluation criteria) A: The amount of warpage is 0mm, and warpage is suppressed. B: The amount of warpage is between more than 0 mm and less than 2 mm. The effect of inhibiting warpage is worse than A, but the protective film forming film can be used in practice. C: The amount of warpage exceeds 2 mm, the effect of suppressing warpage is low, and the protective film forming film cannot be used for actual use. Here, the protective film-forming film is ready for actual use, which means that after the protective film-forming film is thermally cured (after the protective film is formed), for example, a dicing sheet can be attached without any problem, and semiconductor wafers with a protective film can be processed. Cutting and other usual steps.

[抑制在具保護膜之矽晶片之碎屑的功效之評價] 使用在上述之抑制在具保護膜之矽晶圓之翹曲的功效之評價所製作之具保護膜之矽晶圓，對於其中保護膜的露出面(與矽晶圓側為相反側之面)，使用貼帶機(琳得科公司製「Adwill RAD-2510F/12)貼附切割帶(琳得科公司製「Adwill D-686H)的黏著劑層側之面。貼附條件設為貼附速度30mm/s、輥溫度23℃、台溫度23℃、貼附壓力0.25MPa。 然後，藉由使用切割裝置(DISCO公司製「DFD6361」)切割具保護膜之矽晶圓，將矽晶圓分割成大小為5mm×5mm的矽晶片，並且將保護膜切斷成與矽晶片相同大小，製作多個具保護膜之矽晶片。此時，將切割刀片(DISCO公司製「Z05-SD2000-N1-90 CC」)的移動速度設為30mm/sec，轉數設為45000rpm，高度設為65μm。 然後，將這些具保護膜之矽晶片自切割片轉印至黏著片(琳得科公司製「Adwill D-210)，對其中任意的10個具保護膜之矽晶片使用數位顯微鏡進行觀察，確認碎屑(矽晶片的破裂或缺損)的最大值。然後，依據下述基準由最大值來評價抑制在具保護膜之矽晶片之碎屑的功效。結果如表1所示。 (評價基準) A：碎屑的最大值為20μm以下，抑制碎屑的功效高。 B：碎屑的最大值超過20μm至50μm以下，較A差但碎屑得到抑制。 C：碎屑的最大值超過50μm，碎屑未被抑制。 [Evaluation of the effectiveness of suppressing chips on silicon wafers with protective films] For the silicon wafer with protective film produced by the above-mentioned evaluation of the effect of suppressing warpage of silicon wafer with protective film, the exposed surface of the protective film (the side opposite to the side of the silicon wafer) , use a taping machine (Adwill RAD-2510F/12 manufactured by Lintec Corporation) to attach the adhesive layer side of the cutting tape (Adwill D-686H manufactured by Lintec Corporation). The attachment condition is set to "Adhesion" The speed is 30mm/s, the roller temperature is 23℃, the table temperature is 23℃, and the attachment pressure is 0.25MPa. Then, by cutting the silicon wafer with the protective film using a cutting device ("DFD6361" manufactured by DISCO Corporation), the silicon wafer is divided into silicon wafers with a size of 5 mm × 5 mm, and the protective film is cut into the same size as the silicon wafer. size, making multiple silicon wafers with protective films. At this time, the moving speed of the cutting blade ("Z05-SD2000-N1-90 CC" manufactured by DISCO) was set to 30 mm/sec, the number of revolutions was set to 45000 rpm, and the height was set to 65 μm. Then, these silicon wafers with a protective film were transferred from the dicing sheet to an adhesive sheet ("Adwill D-210 manufactured by Lindec Co., Ltd."), and any 10 silicon wafers with a protective film were observed using a digital microscope to confirm The maximum value of debris (cracking or chipping of the silicon wafer). Then, the effectiveness of suppressing debris on the silicon wafer with the protective film was evaluated based on the maximum value based on the following criteria. The results are shown in Table 1. (evaluation criteria) A: The maximum value of debris is 20 μm or less, and the debris suppression effect is high. B: The maximum value of debris exceeds 20 μm and is less than 50 μm, which is worse than A but debris is suppressed. C: The maximum value of debris exceeds 50 μm, and debris is not suppressed.

[保護膜形成膜之製造以及評價] [實施例2至實施例6、比較例1至比較例2] 除了保護膜形成膜的含有成分與含量以成為表1或表2所示的方式變更調配成分的種類以及量中任一者或兩者的方面以外，以與實施例1之情形相同方法製造保護膜形成膜並進行評價。結果如表1或表2所示。 [Production and evaluation of protective film forming films] [Example 2 to Example 6, Comparative Example 1 to Comparative Example 2] A protective film-forming film was produced in the same manner as in Example 1, except that any one or both of the types and amounts of the ingredients were changed as shown in Table 1 or Table 2. Films were formed and evaluated. The results are shown in Table 1 or Table 2.

[表1] 實施例 1 2 3 4 保護膜形成膜的 含有成分 (含量(質量份)) 聚合物成分(A) (A)-1 18.45 18.48 24.75 16.08 環氧樹脂(B1) (B1)-1 11.07 11.09 14.85 9.65 (B1)-2 1.85 1.85 2.48 1.61 (B1)-3 5.54 5.55 7.43 4.82 熱硬化劑(B2) (B2)-1 0.37 0.37 0.5 0.32 硬化促進劑(C) (C)-1 0.37 0.18 0.5 0.32 (C)-2 - - - - (C)-3 - - - - (C)-4 - - - - 填充材(D) (D)-1 59.04 59.15 45.05 64.31 偶合劑(E) (E)-1 0.37 0.37 0.5 0.32 著色劑(I) (I)-1 2.95 2.96 3.96 2.57 評價結果 發熱起始溫度(℃) 174.4 182.1 173.9 174.9 在常溫之保存穩定性(貼附性) A A A A 抑制翹曲的功效 A A A B 抑制碎屑的功效 A A B A [Table 1] Example 1 2 3 4 Ingredients contained in the protective film-forming film (content (parts by mass)) Polymer component (A) (A)-1 18.45 18.48 24.75 16.08 Epoxy resin (B1) (B1)-1 11.07 11.09 14.85 9.65 (B1)-2 1.85 1.85 2.48 1.61 (B1)-3 5.54 5.55 7.43 4.82 Thermal hardener (B2) (B2)-1 0.37 0.37 0.5 0.32 Hardening accelerator (C) (C)-1 0.37 0.18 0.5 0.32 (C)-2 - - - - (C)-3 - - - - (C)-4 - - - - Filling material (D) (D)-1 59.04 59.15 45.05 64.31 Coupling agent (E) (E)-1 0.37 0.37 0.5 0.32 Colorants (I) (I)-1 2.95 2.96 3.96 2.57 Evaluation results Fever starting temperature (℃) 174.4 182.1 173.9 174.9 Storage stability at room temperature (adhesion) A A A A The effect of inhibiting warpage A A A B Effectiveness in inhibiting debris A A B A

[表2] 實施例 比較例 5 6 1 2 保護膜形成膜的 含有成分 (含量(質量份)) 聚合物成分(A) (A)-1 18.48 18.45 25.91 18.45 環氧樹脂(B1) (B1)-1 11.09 11.07 10 11.07 (B1)-2 1.85 1.85 - 1.85 (B1)-3 5.55 5.54 - 5.54 熱硬化劑(B2) (B2)-1 0.37 0.37 - 0.37 硬化促進劑(C) (C)-1 0.09 - - - (C)-2 - - 1.1 0.37 (C)-3 - 0.37 (C)-4 0.09 填充材(D) (D)-1 59.15 59.04 60.01 59.04 偶合劑(E) (E)-1 0.37 0.37 - 0.37 著色劑(I) (I)-1 2.96 2.95 2.98 2.95 評價結果 發熱起始溫度(℃) 188 170.6 150 149.3 在常溫之保存穩定性(貼附性) A A B C 抑制翹曲的功效 A A - - 抑制碎屑的功效 A A - - [Table 2] Example Comparative example 5 6 1 2 Ingredients contained in the protective film-forming film (content (parts by mass)) Polymer component (A) (A)-1 18.48 18.45 25.91 18.45 Epoxy resin (B1) (B1)-1 11.09 11.07 10 11.07 (B1)-2 1.85 1.85 - 1.85 (B1)-3 5.55 5.54 - 5.54 Thermal hardener (B2) (B2)-1 0.37 0.37 - 0.37 Hardening accelerator (C) (C)-1 0.09 - - - (C)-2 - - 1.1 0.37 (C)-3 - 0.37 (C)-4 0.09 Filling material (D) (D)-1 59.15 59.04 60.01 59.04 Coupling agent (E) (E)-1 0.37 0.37 - 0.37 Colorants (I) (I)-1 2.96 2.95 2.98 2.95 Evaluation results Fever starting temperature (℃) 188 170.6 150 149.3 Storage stability at room temperature (adhesion) A A B C The effect of inhibiting warpage A A - - Debris suppression effect A A - -

由上述結果可明顯看出，於實施例1至實施例6之中，保護膜形成膜對矽晶圓之貼附性良好，確認到保護膜形成膜的常溫之保存穩定性高。在實施例1至實施例6之中，在DSC法之試片的發熱起始溫度為170.6℃以上而充分地高。It is apparent from the above results that in Examples 1 to 6, the protective film-forming film has good adhesion to the silicon wafer, and it is confirmed that the protective film-forming film has high storage stability at room temperature. Among Examples 1 to 6, the heat generation onset temperature of the test piece in the DSC method was 170.6° C. or higher, which was sufficiently high.

進而，在實施例1至實施例6之中，抑制在具保護膜之矽晶圓之翹曲的功效與抑制在具保護膜之矽晶片之碎屑的功效皆良好，保護膜形成膜具有良好的特性。 其中，在實施例1、實施例2、實施例5、實施例6之中，抑制在具保護膜之矽晶圓之翹曲的功效與抑制在具保護膜之矽晶片之碎屑的功效皆特別優異，保護膜形成膜具有特別優異的特性。實施例1、實施例2、實施例5、實施例6之中，保護膜形成膜中，相對於保護膜形成膜的總質量，填充材(D)的含量的比率在50質量%至63質量%的範圍內。 Furthermore, in Examples 1 to 6, the effect of suppressing the warpage of the silicon wafer with the protective film and the effect of suppressing the chipping of the silicon wafer with the protective film are both good, and the protective film forming film has good characteristics. Among them, in Example 1, Example 2, Example 5, and Example 6, the effect of suppressing the warpage of the silicon wafer with the protective film and the effect of suppressing the chipping of the silicon wafer with the protective film are both. Particularly excellent, the protective film-forming film has particularly excellent properties. In Example 1, Example 2, Example 5, and Example 6, in the protective film-forming film, the content ratio of the filler (D) in the protective film-forming film is from 50 mass % to 63 mass % relative to the total mass of the protective film-forming film. within the range of %.

相對於此，比較例1至比較例2之中，保護膜形成膜對矽晶圓之貼附性差，保護膜形成膜在常溫之保存穩定性差。特別在比較例2之中，保護膜形成膜在常溫之保存穩定性低。比較例1至比較例2之中，在DSC法之試片的發熱起始溫度為150℃以下而不充分。 比較例1至比較例2之中，由於無法將保護膜形成膜正常地貼附至矽晶圓，故未對於抑制在具保護膜之矽晶圓之翹曲的功效以及抑制在具保護膜之矽晶片之碎屑的功效進行評價。 [產業可利用性] In contrast, in Comparative Examples 1 to 2, the adhesion of the protective film-forming film to the silicon wafer was poor, and the storage stability of the protective film-forming film at room temperature was poor. Especially in Comparative Example 2, the storage stability of the protective film-forming film at normal temperature was low. In Comparative Examples 1 to 2, the heat generation starting temperature of the test piece in the DSC method was 150° C. or lower, which was insufficient. In Comparative Examples 1 to 2, since the protective film-forming film cannot be attached to the silicon wafer normally, the effect of suppressing the warpage of the silicon wafer with the protective film and the effect of suppressing the warpage of the silicon wafer with the protective film are not evaluated. Evaluate the efficacy of silicon wafer chips. [Industrial Availability]

本發明可用於半導體裝置之製造。The present invention can be used in the manufacture of semiconductor devices.

7:扯離手段 9:半導體晶圓 9a:半導體晶圓的電路面 9b:半導體晶圓的內面 10:支撐片 10a:支撐片之一面(第一面) 11,81:基材 11a:基材之一面(第一面) 12:黏著劑層 12a:黏著劑層之一面(第一面) 13,23:保護膜形成膜 13a,23a:保護膜形成膜之一面(第一面) 13b,23b:保護膜形成膜另一面(第二面) 13’:保護膜 13a':保護膜之一面(第一面) 13b':保護膜另一面(第二面) 15:剝離膜 16:治具用接著劑層 16a:治具用接著劑層之一面(第一面) 80:切割片 80a:切割片之一面(第一面) 82:黏著劑層 82a:黏著劑層之一面(第一面) 90:半導體晶片 90a:半導體晶片的電路面 90b:半導體晶片的內面 101,102:保護膜形成用複合片 101':熱硬化後的保護膜形成用複合片 130':切斷後的保護膜 130a':切斷後的保護膜之一面(第一面) 130b':切斷後的保護膜另一面(第二面) 151:第一剝離膜 152:第二剝離膜 901:具保護膜形成膜之半導體晶圓 901':具保護膜之半導體晶圓 902:具保護膜之半導體晶片群 903:具保護膜的半導體晶片群 913':具保護膜之半導體晶片 7: Separate means 9:Semiconductor wafer 9a: Circuit surface of semiconductor wafer 9b: Inner surface of semiconductor wafer 10:Support piece 10a: One side of the support piece (first side) 11,81:Substrate 11a: One side of the base material (first side) 12: Adhesive layer 12a: One side of the adhesive layer (first side) 13,23: Protective film forming film 13a, 23a: Protective film forms one side of the film (first side) 13b, 23b: Protective film forms the other side of the film (second side) 13’:Protective film 13a': One side of the protective film (first side) 13b': The other side of the protective film (second side) 15: Peel off film 16: Adhesive layer for fixtures 16a: One side of the adhesive layer for the jig (the first side) 80: Cutting piece 80a: One side of the cutting piece (first side) 82: Adhesive layer 82a: One side of the adhesive layer (first side) 90:Semiconductor wafer 90a: Circuit surface of semiconductor wafer 90b: Inner surface of semiconductor wafer 101,102: Composite sheet for protective film formation 101': Composite sheet for forming protective film after thermal hardening 130':Protective film after cutting 130a': One side of the cut protective film (first side) 130b': The other side of the protective film after cutting (the second side) 151: First peeling film 152:Second peeling film 901: Semiconductor wafer with protective film forming film 901': Semiconductor wafer with protective film 902: Semiconductor chip group with protective film 903: Semiconductor chip group with protective film 913': Semiconductor chip with protective film

[圖1]係示意性地表示本發明之一實施形態之保護膜形成膜之一例之剖面圖。 [圖2]係示意性地表示本發明之一實施形態之保護膜形成用複合片之一例之剖面圖。 [圖3]係示意性地表示本發明之一實施形態之保護膜形成用複合片之另一例之剖面圖。 [圖4A]係用以示意性地說明本發明之一實施形態之半導體裝置之製造方法之一例之剖面圖。 [圖4B]係用以示意性地說明本發明之一實施形態之半導體裝置之製造方法之一例之剖面圖。 [圖4C]係用以示意性地說明本發明之一實施形態之半導體裝置之製造方法之一例之剖面圖。 [圖4D]係用以示意性地說明本發明之一實施形態之半導體裝置之製造方法之一例之剖面圖。 [圖4E]係用以示意性地說明本發明之一實施形態之半導體裝置之製造方法之一例之剖面圖。 [圖5A]係用以示意性地說明本發明之一實施形態之半導體裝置之製造方法之另一例之剖面圖。 [圖5B]係用以示意性地說明本發明之一實施形態之半導體裝置之製造方法之另一例之剖面圖。 [圖5C]係用以示意性地說明本發明之一實施形態之半導體裝置之製造方法之另一例之剖面圖。 [圖5D]係用以示意性地說明本發明之一實施形態之半導體裝置之製造方法之另一例之剖面圖。 [圖5E]係用以示意性地說明本發明之一實施形態之半導體裝置之製造方法之另一例之剖面圖。 [圖5F]係用以示意性地說明本發明之一實施形態之半導體裝置之製造方法之另一例之剖面圖。 [Fig. 1] is a cross-sectional view schematically showing an example of a protective film-forming film according to an embodiment of the present invention. [Fig. 2] is a cross-sectional view schematically showing an example of a composite sheet for forming a protective film according to an embodiment of the present invention. [Fig. 3] is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to one embodiment of the present invention. [Fig. 4A] is a cross-sectional view schematically illustrating an example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 4B] is a cross-sectional view schematically illustrating an example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 4C] is a cross-sectional view schematically illustrating an example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 4D] is a cross-sectional view schematically illustrating an example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 4E] is a cross-sectional view schematically illustrating an example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 5A] is a cross-sectional view schematically illustrating another example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. 5B is a cross-sectional view schematically illustrating another example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 5C] is a cross-sectional view schematically illustrating another example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 5D] is a cross-sectional view schematically illustrating another example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. 5E is a cross-sectional view schematically illustrating another example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. [Fig. 5F] is a cross-sectional view schematically illustrating another example of a method of manufacturing a semiconductor device according to an embodiment of the present invention.

10:支撐片 10:Support piece

10a:支撐片之一面(第一面) 10a: One side of the support piece (first side)

11:基材 11:Substrate

11a:基材之一面(第一面) 11a: One side of the base material (first side)

12:黏著劑層 12: Adhesive layer

12a:黏著劑層之一面(第一面) 12a: One side of the adhesive layer (first side)

13:保護膜形成膜 13: Protective film forming film

13a:保護膜形成膜之一面(第一面) 13a: Protective film forms one side of the film (first side)

13b:保護膜形成膜另一面(第二面) 13b: Protective film forms the other side of the film (second side)

15:剝離膜 15: Peel off film

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

16a:治具用接著劑層之一面(第一面) 16a: One side of the adhesive layer for the jig (the first side)

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

Claims (9)

一種保護膜形成膜，係熱硬化性； 藉由差示掃描熱量分析法，將前述保護膜形成膜的試片以升溫速度10℃/min、自23℃升溫至300℃為止時的發熱起始溫度為160℃以上。 A protective film-forming film that is thermosetting; By differential scanning calorimetry, it was found that the heat generation onset temperature when the temperature was raised from 23°C to 300°C at a heating rate of 10°C/min on a test piece formed with the aforementioned protective film was 160°C or above. 如請求項1所記載之保護膜形成膜，其中前述保護膜形成膜含有填充材(D)； 前述保護膜形成膜之中，相對於前述保護膜形成膜的總質量，前述填充材(D)的含量的比率為63質量%以下。 The protective film-forming film according to claim 1, wherein the protective film-forming film contains a filler (D); In the protective film-forming film, a content ratio of the filler (D) is 63 mass % or less relative to the total mass of the protective film-forming film. 如請求項1或2所記載之保護膜形成膜，其中前述保護膜形成膜含有填充材(D)； 前述保護膜形成膜之中，相對於前述保護膜形成膜的總質量，前述填充材(D)的含量的比率為50質量%以上。 The protective film-forming film according to claim 1 or 2, wherein the protective film-forming film contains a filler (D); In the protective film-forming film, a content ratio of the filler (D) is 50 mass % or more relative to the total mass of the protective film-forming film. 如請求項1至3中任一項所記載之保護膜形成膜，其中前述發熱起始溫度為170℃以上。The protective film-forming film according to any one of claims 1 to 3, wherein the heat generation starting temperature is 170° C. or higher. 一種保護膜形成用複合片，係具備支撐片、以及設置於前述支撐片的一面上之保護膜形成膜； 前述保護膜形成膜係如請求項1至4中任一項所記載之保護膜形成膜。 A composite sheet for forming a protective film, which is provided with a support sheet and a protective film-forming film provided on one side of the support sheet; The aforementioned protective film-forming film is the protective film-forming film described in any one of claims 1 to 4. 一種半導體裝置之製造方法，係用於製造半導體裝置； 前述製造方法係具有如下步驟： 貼附步驟，將如請求項1至4中任一項所記載之保護膜形成膜之一面或是如請求項5所記載之保護膜形成用複合片中之保護膜形成膜的露出面貼附於半導體晶圓的內面； 熱硬化步驟，在前述貼附步驟之後，使前述保護膜形成膜熱硬化而形成保護膜； 印字步驟，在前述熱硬化步驟之後，於使用前述保護膜形成用複合片之情形時，在前述保護膜形成用複合片中的前述保護膜的前述支撐片側之面進行雷射印字，於使用未構成前述保護膜形成用複合片之前述保護膜形成膜之情形時，在前述保護膜的另一面進行雷射印字； 加工步驟，在前述印字步驟之後，於使用前述保護膜形成用複合片之情形時，在前述保護膜形成用複合片中之前述支撐片上，將前述半導體晶圓分割成半導體晶片，沿著前述半導體晶圓的分割部位來切斷前述保護膜，於使用未構成前述保護膜形成用複合片之前述保護膜形成膜之情形時，在前述保護膜的另一面貼附切割片之後，在前述切割片上，將前述半導體晶圓分割成半導體晶片，沿著前述半導體晶圓的分割部位來切斷前述保護膜，藉此製作具備前述半導體晶片以及設置於前述半導體晶片的內面之切斷後的前述保護膜之具保護膜之半導體晶片； 拾取步驟，在前述加工步驟之後，將前述具保護膜之半導體晶片自前述切割片或支撐片扯離而進行拾取。 A method for manufacturing a semiconductor device, which is used to manufacture the semiconductor device; The aforementioned manufacturing method has the following steps: The step of attaching is to attach one side of the protective film-forming film as described in any one of Claims 1 to 4 or the exposed surface of the protective film-forming film in the protective film-forming composite sheet as described in Claim 5 On the inner surface of the semiconductor wafer; Thermal hardening step: after the aforementioned attaching step, the aforementioned protective film-forming film is thermally hardened to form a protective film; In the printing step, after the thermal curing step, when the composite sheet for forming a protective film is used, laser printing is performed on the surface of the supporting sheet side of the protective film in the composite sheet for forming a protective film. When the protective film is formed into a film forming the protective film-forming composite sheet, laser printing is performed on the other side of the protective film; In the processing step, after the printing step, when the protective film forming composite sheet is used, the semiconductor wafer is divided into semiconductor wafers on the supporting sheet in the protective film forming composite sheet, and the semiconductor wafer is divided into semiconductor wafers along the semiconductor wafers. The protective film is cut at the dividing portion of the wafer, and when the protective film forming film is used without forming the protective film forming composite sheet, a dicing sheet is attached to the other side of the protective film, and then a dicing sheet is attached to the other side of the protective film. The semiconductor wafer is divided into semiconductor wafers, and the protective film is cut along the divided parts of the semiconductor wafer, thereby producing the semiconductor wafer and the cut protective film provided on the inner surface of the semiconductor wafer. Semiconductor chips with protective films; In the picking up step, after the aforementioned processing step, the aforementioned semiconductor wafer with the protective film is pulled away from the aforementioned cutting piece or the supporting piece and picked up. 如請求項6所記載之半導體裝置之製造方法，其中將前述保護膜形成用複合片、或是未構成前述保護膜形成用複合片之前述保護膜形成膜以常溫保存30日之後，用於前述貼附步驟。The manufacturing method of a semiconductor device according to claim 6, wherein the protective film-forming composite sheet or the protective film-forming film that does not constitute the protective film-forming composite sheet is stored at room temperature for 30 days before being used in the above-mentioned Attach steps. 一種保護膜形成膜之使用，係用以貼附於半導體晶圓中與電路面為相反側之內面，且於分割前述半導體晶圓所獲得之半導體晶片的內面形成保護膜； 前述保護膜形成膜係如請求項1至4中任一項所記載之保護膜形成膜。 The use of a protective film-forming film, which is used to adhere to the inner surface of a semiconductor wafer on the opposite side to the circuit surface, and to form a protective film on the inner surface of the semiconductor wafer obtained by dividing the aforementioned semiconductor wafer; The aforementioned protective film-forming film is the protective film-forming film described in any one of claims 1 to 4. 如請求項8所記載之保護膜形成膜之使用，其中將前述保護膜形成膜以常溫保存30日之後，貼附於前述半導體晶圓的前述內面。The use of the protective film-forming film as described in claim 8, wherein the protective film-forming film is stored at room temperature for 30 days and then attached to the inner surface of the semiconductor wafer.
TW112109095A 2022-03-30 2023-03-13 Protective film-forming film, composite sheet for forming protective film, method of manufacturing semiconductor device, and use of protective film-forming film providing a protective film-forming composite sheet including a support sheet and the protective film-forming film provided on one surface of the support sheet TW202348757A (en)

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