TWI822917B - Composite sheet for protective film formation, and method of manufacturing semiconductor wafer - Google Patents
Composite sheet for protective film formation, and method of manufacturing semiconductor wafer Download PDFInfo
- Publication number
- TWI822917B TWI822917B TW108144032A TW108144032A TWI822917B TW I822917 B TWI822917 B TW I822917B TW 108144032 A TW108144032 A TW 108144032A TW 108144032 A TW108144032 A TW 108144032A TW I822917 B TWI822917 B TW I822917B
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- TW
- Taiwan
- Prior art keywords
- protective film
- forming
- antistatic
- composite sheet
- film
- Prior art date
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- 230000001681 protective effect Effects 0.000 title claims abstract description 959
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/025—Electric or magnetic properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
- H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Dicing (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
- Physical Vapour Deposition (AREA)
Abstract
本發明的保護膜形成用複合片(101)具備支撐片(10)、及形成於支撐片(10)的第1面(10a)上之保護膜形成用膜(13)，並且保護膜形成用複合片(101)中之支撐片(10)側的最表層的表面電阻率為1.0×1011 Ω/□以下，於使保護膜形成用膜(13)熱硬化而形成保護膜後，前述支撐片(10)側的最表層的表面電阻率亦為1.0×1011 Ω/□以下。The protective film-forming composite sheet (101) of the present invention includes a support sheet (10) and a protective film-forming film (13) formed on the first surface (10a) of the support sheet (10). The surface resistivity of the outermost layer on the support sheet (10) side of the composite sheet (101) is 1.0×10 11 Ω/□ or less. After the protective film-forming film (13) is thermally cured to form a protective film, the aforementioned support The surface resistivity of the outermost layer on the sheet (10) side is also 1.0×10 11 Ω/□ or less.
Description
本發明係關於一種保護膜形成用複合片、以及半導體晶片之製造方法。 本申請案基於2018年12月5日在日本提出申請之特願2018-228528號主張優先權，且將該申請案的內容引用至本文中。The present invention relates to a composite sheet for forming a protective film and a manufacturing method of a semiconductor wafer. This application claims priority based on Special Application No. 2018-228528 filed in Japan on December 5, 2018, and the contents of this application are incorporated into this article.
近年來，業界應用稱為所謂的倒裝(face down)方式之安裝方法而製造半導體裝置。倒裝方式中，使用於電路面上具有凸塊等電極之半導體晶片，將前述電極與基板接合。因此，有時半導體晶片中的與電路面為相反側的背面裸露。In recent years, the industry has used a so-called face down mounting method to manufacture semiconductor devices. In the flip-chip method, a semiconductor chip with electrodes such as bumps on the circuit surface is used, and the electrodes are bonded to the substrate. Therefore, the back surface of the semiconductor wafer opposite to the circuit surface may be exposed.
有時於該裸露的半導體晶片的背面，形成含有有機材料之樹脂膜作為保護膜，以附保護膜之半導體晶片之形式組入至半導體裝置中。保護膜係用以防止在切割步驟或封裝之後半導體晶片產生龜裂。Sometimes, a resin film containing organic material is formed on the back side of the exposed semiconductor wafer as a protective film, and is incorporated into the semiconductor device in the form of a semiconductor wafer with a protective film. The protective film is used to prevent cracks in the semiconductor wafer after the dicing step or packaging.
為了形成此種保護膜，例如使用於支撐片上具備用以形成保護膜之保護膜形成用膜而構成之保護膜形成用複合片。保護膜形成用膜可藉由硬化而形成保護膜。另外，支撐片可用於將背面具備保護膜形成用膜或保護膜之半導體晶圓分割為半導體晶片時，固定半導體晶圓。進而，支撐片亦可用作切割片，且保護膜形成用複合片亦可用作保護膜形成用膜與切割片形成為一體之複合片。In order to form such a protective film, for example, a protective film-forming composite sheet including a protective film-forming film for forming a protective film on a support sheet is used. The protective film-forming film can be cured to form a protective film. In addition, the support sheet can be used to fix the semiconductor wafer having a protective film forming film or a protective film on its back surface when the semiconductor wafer is divided into semiconductor wafers. Furthermore, the support sheet can also be used as a dicing sheet, and the protective film-forming composite sheet can also be used as a composite sheet in which the protective film-forming film and the dicing sheet are integrated.
更具體而言，保護膜形成用複合片係以如下之方式進行使用。 亦即，首先，於半導體晶圓的前述背面，貼附保護膜形成用複合片中的保護膜形成用膜，獲得積層體(以下，簡稱為「分割前積層體」)。More specifically, the composite sheet for protective film formation is used in the following manner. That is, first, the protective film forming film in the protective film forming composite sheet is attached to the back surface of the semiconductor wafer to obtain a laminate (hereinafter simply referred to as "pre-dividing laminate").
繼而，使前述分割前積層體中的保護膜形成用膜硬化而形成保護膜，將該積層體(以下，簡稱為「已硬化的積層體」)固定於切割台上。或者，不使前述分割前積層體中的保護膜形成用膜硬化而以原有的狀態，將前述分割前積層體固定於切割台上。Next, the protective film-forming film in the pre-dividing laminated body is cured to form a protective film, and the laminated body (hereinafter, simply referred to as the "cured laminated body") is fixed on the cutting table. Alternatively, the pre-dividing laminated body may be fixed to the cutting table in its original state without curing the protective film-forming film in the pre-dividing laminated body.
繼而，於前述已硬化的積層體之情形時，於固定於切割台上之狀態的該積層體中，分割半導體晶圓，切斷保護膜，獲得於支撐片上依序具備切斷後的保護膜、及分割後的半導體晶圓(亦即半導體晶片)之積層體(以下，簡稱為「硬化及已分割的積層體」)。或者，於前述分割前積層體之情形時，於固定於切割台上之狀態的該積層體中，分割半導體晶圓，切斷保護膜形成用膜，獲得於支撐片上依序具備切斷後的保護膜形成用膜、及半導體晶片之積層體(未硬化及已分割的積層體)。此處所進行的皆係成為主流之刀片切割。Next, in the case of the above-mentioned hardened laminated body, in the state of being fixed on the cutting table, the semiconductor wafer is divided into the laminated body, and the protective film is cut to obtain the cut protective film, and a laminated body of divided semiconductor wafers (ie, semiconductor wafers) (hereinafter referred to as "hardened and divided laminated body"). Alternatively, in the case of the laminated body before dividing as described above, in the laminated body fixed on the cutting table, the semiconductor wafer is divided, the film for forming the protective film is cut, and the protection after cutting is obtained sequentially on the support sheet. Films for film formation, and laminates of semiconductor wafers (unhardened and divided laminates). What is done here is blade cutting that has become mainstream.
另一方面，於將保護膜形成用複合片如前述般貼附於半導體晶圓的背面之步驟中，有時於自保護膜形成用複合片中的保護膜形成用膜移除剝離膜時，保護膜形成用複合片會帶電。帶電的保護膜形成用複合片在貼附於半導體晶圓之前的階段，於該保護膜形成用複合片的保護膜形成用膜上容易吸附小的異物，因此於保護膜形成用膜與半導體晶圓之間容易混入異物。On the other hand, in the step of attaching the protective film-forming composite sheet to the back surface of the semiconductor wafer as described above, there may be a case where the peeling film is removed from the protective film-forming film in the protective film-forming composite sheet, The composite sheet for forming a protective film is charged. In the stage before the charged protective film-forming composite sheet is attached to the semiconductor wafer, small foreign matter is easily adsorbed on the protective film-forming film of the protective film-forming composite sheet. Therefore, there is a gap between the protective film-forming film and the semiconductor wafer. It is easy for foreign matter to get mixed in between the circles.
另外，於使用半導體晶圓及前述保護膜形成用複合片來製造背面具備保護膜之半導體晶片之過程中，製作支撐片、切斷後的保護膜或保護膜形成用膜、及半導體晶片依序積層而構成之積層體。並且，操作該積層體時，使該積層體成為固定於台上之狀態，繼而，進行自台上的固定面扯離之操作，但將前述積層體自台扯離時積層體容易帶電。若積層體帶電，則有電路遭破壞之虞。In addition, in the process of manufacturing a semiconductor wafer having a protective film on its back using a semiconductor wafer and the composite sheet for forming a protective film, a supporting sheet, a cut protective film or a film for forming a protective film, and the semiconductor wafer are sequentially laminated The layered body composed of it. When handling the laminated body, the laminated body is fixed to the table and then pulled away from the fixed surface of the table. However, the laminated body is easily charged when the laminated body is pulled away from the table. If the laminated body becomes electrified, the circuit may be damaged.
作為抑制剝離帶電之半導體加工用片，例如於專利文獻1中揭示有一種切割帶一體型接著片，具有於基材上積層有黏著劑層之切割帶(相當於前述支撐片)、及形成於前述黏著劑層上之接著片，特徵在於：藉由剝離速度10m/分鐘、剝離角度150°之條件將前述黏著劑層與前述接著片剝離時的剝離帶電壓的絕對值為0.5kV以下，含有高分子型抗靜電劑，任一表面中的表面固有電阻值為1.0×1011 Ω以下。 [先前技術文獻] [專利文獻]As a sheet for semiconductor processing that suppresses peeling charging, for example, Patent Document 1 discloses a dicing tape-integrated adhesive sheet, which has a dicing tape (equivalent to the aforementioned support sheet) laminated with an adhesive layer on a base material, and is formed on The adhesive sheet on the adhesive layer is characterized in that the absolute value of the peeling voltage when the adhesive layer and the adhesive sheet are peeled off under the conditions of a peeling speed of 10 m/min and a peeling angle of 150° is 0.5 kV or less, and contains A polymer-type antistatic agent with a surface inherent resistance value of 1.0×10 11 Ω or less on any surface. [Prior art documents] [Patent documents]
[專利文獻1]日本專利第6322317號公報。[Patent Document 1] Japanese Patent No. 6322317.
[發明所欲解決之課題][Problem to be solved by the invention]
於上述切割中，將前述已硬化的積層體或前述分割前積層體(以下，簡稱為「前述已硬化的積層體等」)固定於切割台上時，有時會因靜電等的影響而於前述已硬化的積層體等中之保護膜形成用複合片側的最外層附著異物，因靜電等的影響而於前述已硬化的積層體等與切割台之間(保護膜形成用複合片與切割台之間)混入異物，無法水平地載置前述已硬化的積層體等，因此有時會產生碎屑(微小的缺損)。In the above-mentioned cutting, when the aforementioned hardened laminated body or the aforementioned pre-divided laminated body (hereinafter, simply referred to as “the aforementioned hardened laminated body, etc.”) is fixed on the cutting table, there may be cases where it is damaged due to the influence of static electricity, etc. Foreign matter adheres to the outermost layer of the composite sheet side for forming a protective film in the cured laminated body, etc., and due to the influence of static electricity, etc., foreign matter is trapped between the cured laminated body, etc. and the cutting table (the composite sheet for forming a protective film and the cutting table (between), and the hardened laminated body cannot be placed horizontally, so chips (microscopic defects) may occur.
專利文獻1中所揭示之切割帶一體型接著片，目的在於抑制於接著片與切割帶之間產生靜電(剝離帶電)，抑制該靜電所致之半導體元件上的電路的破壞。另外，特徵在於切割帶一體型接著片的任一表面中的表面固有電阻值為1.0×1011 Ω以下，而並非控制與切割台接觸之面的表面電阻值，因此尚不確定能否防止如上文所說明之碎屑之產生。進而，尚不確定使切割帶一體型半導體背面用膜經熱硬化後的切割帶一體型接著片的任一表面中的表面固有電阻值是否亦為1.0×1011 Ω以下。The purpose of the dicing tape-integrated adhesive sheet disclosed in Patent Document 1 is to suppress the generation of static electricity (peeling charge) between the adhesive sheet and the dicing tape, and to suppress damage to the circuit on the semiconductor element caused by the static electricity. In addition, it is characterized in that the surface inherent resistance value of any surface of the cutting tape integrated connecting piece is 1.0×10 11 Ω or less, and the surface resistance value of the surface in contact with the cutting table is not controlled, so it is not certain whether it can prevent the above The generation of debris described in the article. Furthermore, it is not yet certain whether the surface specific resistance value of any surface of the dicing tape-integrated adhesive sheet after thermally curing the dicing tape-integrated semiconductor back surface film is also 1.0×10 11 Ω or less.
本發明的目的在於提供一種保護膜形成用複合片、以及使用前述保護膜形成用複合片之半導體晶片之製造方法，前述保護膜形成用複合片具備支撐片及保護膜形成用膜，並且防止於切割中因靜電等的影響而於前述已硬化的積層體等與切割台之間混入異物，結果防止產生碎屑。 [用以解決課題之手段]An object of the present invention is to provide a composite sheet for forming a protective film, which is provided with a supporting sheet and a film for forming a protective film, and a method for manufacturing a semiconductor wafer using the composite sheet for forming a protective film. During cutting, foreign matter is mixed between the hardened laminate and the cutting table due to the influence of static electricity, etc., thereby preventing the generation of chips. [Means used to solve problems]
本實施形態係一種保護膜形成用複合片，具備支撐片、及形成於前述支撐片的一面上之保護膜形成用膜，並且前述熱硬化性保護膜形成用膜之加熱硬化前，前述保護膜形成用複合片中之前述支撐片側的最表層的表面電阻率為1.0×1011 Ω/□以下，前述熱硬化性保護膜形成用膜之加熱硬化後，前述保護膜形成用複合片中之前述支撐片側的最表層的表面電阻率為1.0×1011 Ω/□以下。This embodiment is a composite sheet for protective film formation, including a support sheet and a protective film forming film formed on one side of the support sheet, and before the thermosetting protective film forming film is heated and cured, the protective film The surface resistivity of the outermost layer on the side of the supporting sheet in the composite sheet for formation is 1.0×10 11 Ω/□ or less, and after the heat-curing of the thermosetting protective film-forming film, the composite sheet for forming protective film The surface resistivity of the outermost layer on the support sheet side is 1.0×10 11 Ω/□ or less.
本實施形態的保護膜形成用複合片中，較佳為前述支撐片具備基材、及形成於前述基材的單面或雙面上之抗靜電層，或者前述支撐片具備具有抗靜電性之基材作為抗靜電層。 本實施形態的保護膜形成用複合片中，較佳為形成於前述基材的單面或雙面上之抗靜電層的厚度為100nm以下。In the composite sheet for forming a protective film according to this embodiment, it is preferable that the support sheet has a base material and an antistatic layer formed on one or both sides of the base material, or that the support sheet has an antistatic layer. The base material acts as an antistatic layer. In the composite sheet for forming a protective film according to this embodiment, it is preferable that the thickness of the antistatic layer formed on one or both sides of the base material is 100 nm or less.
本實施形態的保護膜形成用複合片中，較佳為前述支撐片的全光線透過率為80%以上。 本實施形態的保護膜形成用複合片中，較佳為亦可於具有面積為2cm×2cm且為平面狀之按壓面之按壓機構的前述按壓面被覆法蘭絨布，將被覆有前述法蘭絨布之前述按壓面壓抵於前述抗靜電層的表面，於該狀態下一邊藉由前述按壓機構對前述抗靜電層施加125g/cm2 之荷重而進行按壓，一邊使前述按壓機構以10cm之直線距離往返運動10次，藉此摩擦前述抗靜電層之後，目視觀察前述抗靜電層的該摩擦面中面積為2cm×2cm之區域時，未確認到傷痕。In the composite sheet for forming a protective film according to this embodiment, it is preferable that the total light transmittance of the support sheet is 80% or more. In the composite sheet for forming a protective film of this embodiment, it is preferable that the pressing surface of the pressing mechanism having a flat pressing surface with an area of 2 cm × 2 cm is covered with flannel cloth. The pressing surface is pressed against the surface of the antistatic layer. In this state, the pressing mechanism exerts a load of 125 g/cm 2 on the antistatic layer and presses the antistatic layer at a straight line distance of 10 cm. After the antistatic layer was rubbed by reciprocating 10 times, when an area of 2 cm × 2 cm on the friction surface of the antistatic layer was visually observed, no scratches were confirmed.
另外，本實施形態提供一種半導體晶片之製造方法，具有以下之步驟：將上述保護膜形成用複合片中的熱硬化性保護膜形成用膜貼附於半導體晶圓之步驟；使貼附於前述半導體晶圓後的前述熱硬化性保護膜形成用膜硬化而形成保護膜之步驟；分割前述半導體晶圓，切斷前述保護膜或熱硬化性保護膜形成用膜，獲得具備切斷後的保護膜或熱硬化性保護膜形成用膜之多個半導體晶片之步驟；以及將前述具備切斷後的保護膜或熱硬化性保護膜形成用膜之半導體晶片自前述支撐片扯離而進行拾取之步驟。 [發明功效]In addition, this embodiment provides a method for manufacturing a semiconductor wafer, which includes the following steps: affixing the thermosetting protective film-forming film in the protective film-forming composite sheet to the semiconductor wafer; The step of curing the thermosetting protective film forming film after the semiconductor wafer to form a protective film; dividing the semiconductor wafer, cutting the protective film or the thermosetting protective film forming film to obtain a protective film after cutting or a plurality of semiconductor wafers with a thermosetting protective film-forming film; and a step of picking up the semiconductor wafers with the cut protective film or the thermosetting protective film-forming film from the supporting sheet. [Invention effect]
根據本發明，提供一種保護膜形成用複合片、以及使用前述保護膜形成用複合片之半導體晶片之製造方法，前述保護膜形成用複合片具備支撐片及熱硬化性保護膜形成用膜，並且防止於切割中因靜電等的影響而於前述已硬化的積層體等與切割台之間混入異物，結果防止產生碎屑。According to the present invention, there is provided a composite sheet for forming a protective film, and a method of manufacturing a semiconductor wafer using the composite sheet for forming a protective film, wherein the composite sheet for forming a protective film is provided with a support sheet and a thermosetting film for forming a protective film, and This prevents foreign matter from being mixed between the hardened laminate and the cutting table due to the influence of static electricity during cutting, and consequently prevents the generation of chips.
◇保護膜形成用複合片 本發明的一實施形態的保護膜形成用複合片具備支撐片、及形成於前述支撐片的一面上之熱硬化性保護膜形成用膜，並且前述熱硬化性保護膜形成用膜之加熱硬化前，前述保護膜形成用複合片中之前述支撐片側的最表層的表面電阻率為1.0×1011 Ω/□以下，前述熱硬化性保護膜形成用膜之加熱硬化後，前述保護膜形成用複合片中之前述支撐片側的最表層的表面電阻率為1.0×1011 Ω/□以下。◇ Composite sheet for protective film formation The composite sheet for protective film formation according to one embodiment of the present invention includes a support sheet and a thermosetting protective film forming film formed on one side of the support sheet, and the thermosetting protective film Before the film for forming a film is heated and cured, the surface resistivity of the outermost layer on the side of the supporting sheet in the composite sheet for forming a protective film is 1.0×10 11 Ω/□ or less, and after the film for forming a thermosetting protective film is cured by heating , the surface resistivity of the outermost layer on the side of the supporting sheet in the composite sheet for forming a protective film is 1.0×10 11 Ω/□ or less.
前述保護膜形成用複合片如此般前述表面電阻率為1.0×1011 Ω/□以下。因此，能夠防止因靜電等的影響而於保護膜形成用複合片中之支撐片側的最表層附著異物。結果，能夠防止於切割時產生碎屑。The composite sheet for forming a protective film has a surface resistivity of 1.0×10 11 Ω/□ or less. Therefore, it is possible to prevent foreign matter from adhering to the outermost surface layer on the support sheet side of the composite sheet for protective film formation due to the influence of static electricity or the like. As a result, generation of chips during cutting can be prevented.
另外，前述表面電阻率於前述熱硬化性保護膜形成用膜之加熱硬化前後均為1.0×1011 Ω/□以下，故無論是於使前述熱硬化性保護膜形成用膜加熱硬化前進行切割之情形、亦或是於使前述熱硬化性保護膜形成用膜加熱硬化後進行切割之情形，均能夠防止因靜電等的影響而於前述保護膜形成用複合片中之前述支撐片側的最表層附著異物。結果，能夠防止於切割時產生碎屑。In addition, the surface resistivity is 1.0×10 11 Ω/□ or less before and after heating and curing of the thermosetting protective film-forming film. Therefore, whether cutting is performed before heating and curing the thermosetting protective film-forming film or cutting after heating and curing the thermosetting protective film-forming film, it is possible to prevent the outermost layer on the support sheet side of the protective film-forming composite sheet from being affected by static electricity, etc. Foreign matter attached. As a result, generation of chips during cutting can be prevented.
此外，本說明書中，所謂「保護膜形成用複合片的表面電阻率」，只要無特別說明，則意指上述之保護膜形成用複合片中之支撐片側的最表層的表面電阻率。 另外，本說明書中，所謂「保護膜形成用膜」，只要無特別說明，則意指熱硬化性保護膜形成用膜。In addition, in this specification, the "surface resistivity of the composite sheet for protective film formation" means the surface resistivity of the outermost layer on the support sheet side in the above-mentioned composite sheet for protective film formation, unless otherwise specified. In addition, in this specification, "film for protective film formation" means a thermosetting film for protective film formation unless otherwise specified.
本實施形態的保護膜形成用複合片例如藉由該保護膜形成用複合片中的任一層含有抗靜電劑，而具有平常時帶電的抑制效果。 前述保護膜形成用複合片中，平常時帶電的抑制效果的程度、換言之前述表面電阻率的高低例如可藉由選定含有抗靜電劑之層(本說明書中，有時概括性地稱為「抗靜電層」)中的抗靜電劑的種類以及／或者調整含量而進行調節。The composite sheet for forming a protective film according to this embodiment has an effect of suppressing normal charging because, for example, any layer of the composite sheet for forming a protective film contains an antistatic agent. In the composite sheet for forming a protective film, the degree of the normal charge-suppressing effect, in other words, the level of the surface resistivity, can be determined, for example, by selecting a layer containing an antistatic agent (in this specification, it may be generally referred to as "antistatic"). Adjust the type and/or content of the antistatic agent in the "static layer").
[保護膜形成用膜之加熱硬化前的保護膜形成用複合片中之支撐片側的最表層的表面電阻率] 保護膜形成用複合片中的保護膜形成用膜熱硬化前，保護膜形成用複合片的前述表面電阻率為1.0×1011 Ω/□以下。其中，較佳為9.5×1010 Ω/□以下，例如可為5.0×1010 Ω/□以下、6.0×109 Ω/□以下、以及1.0×109 Ω/□以下之任一者。藉由前述表面電阻率為前述上限值以下，能夠防止因靜電等的影響而於前述保護膜形成用複合片中之前述支撐片側的最表層附著異物。結果，能夠防止於切割時產生碎屑。[Surface resistivity of the outermost layer on the supporting sheet side in the composite sheet for protective film formation before heat curing of the protective film forming film] Before heat curing of the protective film forming film in the protective film forming composite sheet, for protective film formation The aforementioned surface resistivity of the composite sheet is 1.0×10 11 Ω/□ or less. Among them, it is preferably 9.5×10 10 Ω/□ or less, and for example, it may be any one of 5.0×10 10 Ω/□ or less, 6.0× 10 9 Ω/□ or less, and 1.0×10 9 Ω/□ or less. When the surface resistivity is equal to or less than the upper limit, it is possible to prevent foreign matters from adhering to the outermost surface layer on the side of the support sheet in the protective film-forming composite sheet due to the influence of static electricity or the like. As a result, generation of chips during cutting can be prevented.
保護膜形成用膜於熱硬化前，保護膜形成用複合片的前述表面電阻率的下限值越小越佳，並無特別限定。例如，熱硬化前的前述表面電阻率為1.0×105 Ω/□以上之保護膜形成用複合片能夠更容易地製造。Before the protective film forming film is thermally cured, the lower limit value of the surface resistivity of the protective film forming composite sheet is preferably as small as possible, and is not particularly limited. For example, a composite sheet for forming a protective film whose surface resistivity before thermal curing is 1.0×10 5 Ω/□ or more can be more easily produced.
保護膜形成用膜於熱硬化前，保護膜形成用複合片的前述表面電阻率可適宜調節為將上述之較佳的下限值及上限值任意組合而設定之範圍內。例如，一實施形態中，熱硬化前的前述表面電阻率較佳為1.0×105 Ω/□至5.0×1010 Ω/□，例如可為1.0×105 Ω/□至6.0×109 Ω/□、1.0×105 Ω/□至5.0×108 Ω/□、以及1.0×105 Ω/□至3.0×108 Ω/□之任一者。但這些為熱硬化前的前述表面電阻率的一例。Before the protective film-forming film is thermally cured, the surface resistivity of the protective film-forming composite sheet can be appropriately adjusted to a range set by any combination of the above-mentioned preferred lower limit values and upper limit values. For example, in one embodiment, the surface resistivity before thermal hardening is preferably 1.0×10 5 Ω/□ to 5.0×10 10 Ω/□, for example, it can be 1.0×10 5 Ω/□ to 6.0×10 9 Ω. /□, 1.0× 10 5 Ω/□ to 5.0×10 8 Ω/□, and any one of 1.0×10 5 Ω/□ to 3.0×10 8 Ω/□. However, these are examples of the aforementioned surface resistivity before thermal hardening.
[保護膜形成用膜之加熱硬化後，保護膜形成用複合片中之支撐片側的最表層的表面電阻率] 保護膜形成用複合片中的保護膜形成用膜經熱硬化後，保護膜形成用複合片的前述表面電阻率為1.0×1011 Ω/□以下。另外，較佳為滿足上述之表面電阻率之條件(例如較佳的上限值以及／或者下限值)，該情形時的保護膜形成用複合片較佳為該保護膜形成用複合片中的保護膜形成用膜於130℃熱硬化2小時。亦即，作為此種保護膜形成用複合片的一實施形態，可列舉保護膜形成用複合片中的保護膜形成用膜於130℃熱硬化2小時後的前述表面電阻率為1.0×1011 Ω/□以下之保護膜形成用複合片。 但這係滿足上述之表面電阻率之條件之保護膜形成用複合片的一例。 藉由前述表面電阻率為前述上限值以下，於保護膜形成用複合片中的保護膜形成用膜熱硬化後，亦能夠防止因靜電等的影響而異物附著於保護膜形成用複合片中之支撐片側的最表層。結果，能夠防止於切割時產生碎屑。[Surface resistivity of the outermost layer on the supporting sheet side in the composite sheet for protective film formation after heat-curing of the protective film-forming film] After heat-curing of the protective film-forming film in the protective film-forming composite sheet, a protective film is formed The aforementioned surface resistivity of the composite sheet is 1.0×10 11 Ω/□ or less. In addition, it is preferable to satisfy the above-mentioned surface resistivity conditions (for example, a preferable upper limit value and/or a lower limit value). In this case, the composite sheet for protective film formation is preferably among the composite sheets for protective film formation. The protective film forming film is thermally cured at 130°C for 2 hours. That is, as one embodiment of the protective film forming composite sheet, the protective film forming film in the protective film forming composite sheet has the aforementioned surface resistivity of 1.0×10 11 after thermal curing at 130° C. for 2 hours. Composite sheet for protective film formation with Ω/□ or less. However, this is an example of a composite sheet for forming a protective film that satisfies the above-mentioned surface resistivity conditions. By having the surface resistivity below the upper limit, even after the protective film-forming film in the protective film-forming composite sheet is thermally cured, it is possible to prevent foreign matter from adhering to the protective film-forming composite sheet due to the influence of static electricity, etc. The outermost layer of the supporting piece side. As a result, generation of chips during cutting can be prevented.
前述保護膜形成用複合片的前述表面電阻率如於後文實施例中所述，可將保護膜形成用複合片中之支撐片側的最表層設為測定對象，使用表面電阻率計，將施加電壓設為100V而進行測定。The surface resistivity of the protective film-forming composite sheet is as described in the Examples below. The outermost surface layer on the supporting sheet side of the protective film-forming composite sheet can be used as the measurement object, and a surface resistivity meter is used to measure the surface resistivity. The voltage was set to 100V and measured.
本實施形態的保護膜形成用複合片較佳為一併滿足上述之保護膜形成用膜熱硬化後的前述表面電阻率的條件、及保護膜形成用膜熱硬化前的前述表面電阻率的條件。The protective film-forming composite sheet of the present embodiment preferably satisfies both the above-mentioned surface resistivity conditions after the protective film-forming film is thermally cured and the above-mentioned surface resistivity conditions before the protective film-forming film is thermally cured. .
以下，對構成前述保護膜形成用複合片之各層詳細地進行說明。Hereinafter, each layer constituting the composite sheet for forming a protective film will be described in detail.
◎支撐片 前述支撐片可由1層(單層)所構成，亦可由2層以上之多層所構成。於支撐片由多層所構成之情形時，這些多層的構成材料及厚度相互可相同亦可不同，這些多層的組合只要無損本發明的效果，則並無特別限定。◎Support piece The aforementioned support sheet may be composed of one layer (single layer), or may be composed of two or more layers. When the support sheet is composed of multiple layers, the constituent materials and thicknesses of these multiple layers may be the same or different from each other. The combination of these multiple layers is not particularly limited as long as the effects of the present invention are not impaired.
此外，本說明書中，並不限於支撐片之情形，所謂「多層相互可相同亦可不同」，意指「可全部層相同，亦可全部層皆不同，還可僅一部分層相同」，進而，所謂「多層相互不同」，意指「各層的構成材料及厚度的至少一者相互不同」。In addition, in this specification, it is not limited to the case of the support sheet. The so-called "multiple layers can be the same or different from each other" means "all the layers can be the same, all the layers can be different, or only some of the layers can be the same." Furthermore, The term "multiple layers are different from each other" means that "at least one of the constituent materials and thickness of each layer is different from each other."
支撐片可為透明，亦可為不透明，還可根據目的而著色。 例如，為了對保護膜形成用複合片中的保護膜形成用膜經由支撐片進行光學檢查，支撐片較佳為透明。The support sheet can be transparent or opaque, and can be colored according to the purpose. For example, in order to optically inspect the film for protective film formation in the composite sheet for protective film formation via the support sheet, the support sheet is preferably transparent.
作為支撐片，例如可列舉：具備基材、及形成於前述基材上之黏著劑層之支撐片；僅由基材所構成之支撐片等。Examples of the support sheet include a support sheet including a base material and an adhesive layer formed on the base material; a support sheet consisting only of the base material; and the like.
另一方面，如上所述，前述保護膜形成用複合片中，可將該保護膜形成用複合片中的任一層設為抗靜電層。 此種情形時，作為較佳的前述支撐片，例如可列舉：具備基材、以及抗靜電層(於保護膜形成用複合片中，形成於前述基材中之位於前述保護膜形成用膜側之相反側的面上)(本說明書中，有時簡稱為「背面抗靜電層」)之支撐片；具備具有抗靜電性之基材(本說明書中，有時簡稱為「抗靜電性基材」)作為抗靜電層之支撐片；具備基材、以及抗靜電層(於保護膜形成用複合片中，形成於前述基材中之位於前述保護膜形成用膜側的面上)(本說明書中，有時簡稱為「表面抗靜電層」)之支撐片。前述抗靜電層(背面抗靜電層、抗靜電性基材及表面抗靜電層)均含有抗靜電劑。On the other hand, as mentioned above, in the composite sheet for forming a protective film, any layer in the composite sheet for forming a protective film may be used as an antistatic layer. In this case, a preferred supporting sheet includes, for example, a base material and an antistatic layer (in the composite sheet for protective film formation, formed on the side of the film for protective film formation in the base material). a support sheet on the opposite side) (sometimes referred to as the "back antistatic layer" in this specification); a base material with antistatic properties (sometimes referred to as the "antistatic base material in this specification ”) as a support sheet for the antistatic layer; provided with a base material, and an antistatic layer (in the composite sheet for protective film formation, formed on the surface of the base material on the side of the film for protective film formation) (this specification (sometimes referred to as "surface antistatic layer") support sheet. The aforementioned antistatic layers (back antistatic layer, antistatic base material, and surface antistatic layer) all contain antistatic agents.
亦即，作為較佳的前述保護膜形成用複合片，可列舉：前述支撐片具備基材、及形成於前述基材的單面或雙面上之抗靜電層之保護膜形成用複合片；前述支撐片具備具有抗靜電性之基材(亦即，抗靜電性基材)作為抗靜電層之保護膜形成用複合片。 本說明書中，所謂「形成於基材的單面上之抗靜電層」，意指「前述背面抗靜電層或表面抗靜電層」。並且，所謂「形成於基材的雙面上之抗靜電層」，意指「前述背面抗靜電層及表面抗靜電層之組合」。 這些之中，更佳為前述支撐片具備前述基材及背面抗靜電層之保護膜形成用複合片、或者前述支撐片具備前述抗靜電性基材之保護膜形成用複合片。That is, preferred examples of the protective film-forming composite sheet include: a protective film-forming composite sheet in which the support sheet includes a base material and an antistatic layer formed on one or both sides of the base material; The support sheet is a composite sheet for forming a protective film having an antistatic base material (that is, an antistatic base material) as an antistatic layer. In this specification, "the antistatic layer formed on one side of the base material" means "the aforementioned backside antistatic layer or surface antistatic layer". Moreover, the so-called "antistatic layer formed on both sides of the substrate" means "the combination of the aforementioned backside antistatic layer and surface antistatic layer". Among these, a composite sheet for forming a protective film in which the support sheet is provided with the base material and an antistatic layer on the back surface, or a composite sheet for forming a protective film in which the support sheet is provided with the antistatic base material, is more preferred.
作為前述保護膜形成用複合片，亦可列舉：具備不符合前述背面抗靜電層、前述抗靜電性基材、及前述表面抗靜電層之任一者之層作為抗靜電層之片。 例如，抗靜電層可設置於保護膜形成用膜中之與支撐片側為相反側的面上，亦可保護膜形成用膜具有抗靜電性。但是，於使用此種保護膜形成用複合片，一邊充分地抑制剝離帶電、一邊製造半導體裝置之情形時，經由抗靜電層(亦即，設置於保護膜形成用膜中之與支撐片側為相反側的面上之抗靜電層、或者具有抗靜電性之保護膜形成用膜)被貼附於半導體晶片之狀態，將抗靜電層組入至半導體裝置。此種情形時，於製造半導體裝置之過程中，有可能無法穩定地維持經由抗靜電層將保護膜形成用膜或保護膜貼附於半導體晶圓或半導體晶片之狀態、以及／或者將具有抗靜電性之保護膜形成用膜或保護膜貼附於半導體晶圓或半導體晶片之狀態。另外，半導體裝置中，抗靜電層有可能會對半導體裝置的結構的穩定性、或半導體裝置的性能造成不良影響。 另外，例如抗靜電層亦可設置於保護膜形成用膜中之支撐片側的面上。但是，於使用此種保護膜形成用複合片製造半導體裝置之情形時，將貼附有保護膜形成用膜或保護膜之半導體晶片自支撐片上的抗靜電層扯離而進行拾取時，有可能因介存有抗靜電層而產生步驟異常。 另一方面，藉由使用前述背面抗靜電層、前述抗靜電性基材或前述表面抗靜電層作為抗靜電層，不僅於將剝離膜自保護膜形成用膜移除時，而且於保護膜形成用複合片的製造過程以及／或者保存過程中的更多情況下，能夠抑制因帶電而產生不良情況。 就如上之觀點而言，前述保護膜形成用複合片較佳為具備前述背面抗靜電層、前述抗靜電性基材或前述表面抗靜電層作為抗靜電層。The composite sheet for forming a protective film may also include a sheet having a layer that does not conform to any one of the back antistatic layer, the antistatic base material, and the surface antistatic layer as an antistatic layer. For example, the antistatic layer may be provided on the surface of the protective film-forming film opposite to the support sheet side, or the protective film-forming film may have antistatic properties. However, when a semiconductor device is manufactured using such a composite sheet for protective film formation while fully suppressing peeling charge, the antistatic layer (that is, provided in the film for protective film formation on the side opposite to the support sheet) The antistatic layer on the side surface or a protective film forming film with antistatic properties) is attached to the semiconductor wafer, and the antistatic layer is incorporated into the semiconductor device. In this case, during the manufacturing process of the semiconductor device, it may be impossible to stably maintain the state in which the protective film forming film or the protective film is attached to the semiconductor wafer or the semiconductor wafer via the antistatic layer, and/or the resistivity may be lost. The state in which an electrostatic protective film-forming film or protective film is attached to a semiconductor wafer or semiconductor chip. In addition, in a semiconductor device, the antistatic layer may adversely affect the structural stability of the semiconductor device or the performance of the semiconductor device. In addition, for example, an antistatic layer may be provided on the surface of the film for forming a protective film on the support sheet side. However, when manufacturing a semiconductor device using such a protective film-forming composite sheet, there is a possibility that the semiconductor wafer to which the protective film-forming film or the protective film is attached is peeled off from the antistatic layer on the supporting sheet and picked up. Abnormal steps occur due to the presence of an antistatic layer. On the other hand, by using the aforementioned backside antistatic layer, the aforementioned antistatic base material, or the aforementioned surface antistatic layer as the antistatic layer, not only when the release film is removed from the protective film forming film, but also when the protective film is formed In many cases during the manufacturing process and/or storage process of the composite sheet, it is possible to suppress defects caused by charging. From the above viewpoint, the composite sheet for forming a protective film preferably includes the back surface antistatic layer, the antistatic base material, or the surface antistatic layer as an antistatic layer.
以下，按照抗靜電層的每種配置形態，一邊參照圖式一邊說明前述保護膜形成用複合片的整體構成的示例。此外，以下之說明中所使用之圖中，為了易於理解本實施形態的特徵，方便起見，有時將成為主要部分之部分放大表示，而並不限於各構成要素的尺寸比率等與實際相同。Hereinafter, an example of the overall structure of the protective film-forming composite sheet will be described for each arrangement form of the antistatic layer with reference to the drawings. In addition, in the drawings used in the following description, in order to make it easier to understand the characteristics of the present embodiment and for the sake of convenience, the main parts may be enlarged and shown, and the dimensional ratio of each component is not necessarily the same as the actual one. .
首先，先對具備前述背面抗靜電層作為抗靜電層之保護膜形成用複合片進行說明。First, a composite sheet for forming a protective film having the aforementioned backside antistatic layer as an antistatic layer will be described.
圖1係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。
此處所示之保護膜形成用複合片101具備支撐片10、及形成於支撐片10的一面(本說明書中，有時稱為「第1面」)10a上之保護膜形成用膜13。FIG. 1 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
The protective film-forming
支撐片10具備基材11、形成於基材11的一面(本說明書中，有時稱為「第1面」)11a上之黏著劑層12、及形成於基材11的另一面(本說明書中，有時稱為「第2面」)11b上之背面抗靜電層17。亦即，支撐片10係背面抗靜電層17、基材11及黏著劑層12依序於這些層的厚度方向上積層而構成。
換言之，支撐片10的第1面10a係黏著劑層12中之與基材11側為相反側的面(本說明書中，有時稱為「第1面」)12a。The
亦即，保護膜形成用複合片101係背面抗靜電層17、基材11、黏著劑層12及保護膜形成用膜13依序於這些層的厚度方向上積層而構成。另外，保護膜形成用複合片101進而於保護膜形成用膜13上具備剝離膜15。That is, the protective film-forming
保護膜形成用複合片101中，於黏著劑層12的第1面12a的整面或大致整面積層有保護膜形成用膜13，於保護膜形成用膜13中之與黏著劑層12側為相反側的面(本說明書中，有時稱為「第1面」)13a的一部分、亦即周緣部附近的區域積層有治具用接著劑層16，於保護膜形成用膜13的第1面13a中未積層有治具用接著劑層16之面及治具用接著劑層16中之與黏著劑層12側為相反側的面(本說明書中，有時稱為「第1面」)16a積層有剝離膜15。In the protective film-forming
保護膜形成用複合片101中，亦可於剝離膜15與和該剝離膜15直接接觸之層之間產生一部分間隙。
例如，此處表示於治具用接著劑層16的側面16c接觸(積層)有剝離膜15之狀態，但亦有於前述側面16c未接觸有剝離膜15之情況。另外，此處表示於保護膜形成用膜13的第1面13a中治具用接著劑層16的附近區域接觸(積層)有剝離膜15之狀態，但亦有於前述區域未接觸有剝離膜15之情況。
另外，亦有無法明確區別治具用接著劑層16的第1面16a及側面16c之邊界之情形。這些於具備治具用接著劑層之其他實施形態的保護膜形成用複合片中亦相同。In the
支撐片中所使用之加工前的基材中，通常該基材的單面或雙面成為具有凹凸形狀之凹凸面。原因在於，若不具有此種凹凸面，則於將基材捲取成捲筒時，基材彼此的接觸面貼附而黏連，使用變得困難。若基材彼此的接觸面中至少一面為凹凸面，則接觸面的面積變小，因此能夠抑制黏連。
因此，保護膜形成用複合片101中，基材11的第1面11a及第2面11b之任一面或兩面可為凹凸面。並且，於基材11的第1面11a及第2面11b之僅任一面為凹凸面之情形時，哪個面為凹凸面皆可。該情形時，另一面成為凹凸度低之平滑面。
此種凹凸面及平滑面的條件於具備基材11之其他保護膜形成用複合片中亦相同。In the base material before processing used for the support sheet, one or both sides of the base material usually have an uneven surface having an uneven shape. The reason is that if the base material does not have such an uneven surface, when the base material is wound into a roll, the contact surfaces of the base materials will stick to each other and stick to each other, making use difficult. If at least one of the contact surfaces between the base materials has an uneven surface, the area of the contact surface becomes smaller, so adhesion can be suppressed.
Therefore, in the protective film forming
治具用接著劑層16係用以將保護膜形成用複合片101固定於環狀框架等治具。
治具用接著劑層16例如可具有含有接著劑成分之單層結構，亦可具有於成為芯材之片的雙面積層有含有接著劑成分之層之多層結構。The
背面抗靜電層17含有抗靜電劑。藉此，保護膜形成用複合片101中之支撐片10側的最表層的表面電阻率為1.0×1011
Ω/□以下。另外，於使保護膜形成用膜13熱硬化而形成保護膜後，前述支撐片10側的最表層的表面電阻率亦為1.0×1011
Ω/□以下。藉此，能夠防止因靜電等的影響而於保護膜形成用複合片101附著異物。結果，能夠防止於切割時產生碎屑。
此外，符號17a表示背面抗靜電層17中之基材11側的面(本說明書中，有時稱為「第1面」)。The backside
保護膜形成用複合片101係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜13的第1面13a貼附半導體晶圓(省略圖示)的內面，進而將治具用接著劑層16的第1面16a貼附於環狀框架等治具。The
圖2係以示意方式表示本發明的另一實施形態的保護膜形成用複合片之剖視圖。 此外，於圖2以後的圖中，對與既已說明之圖所示相同的構成要素，標附與該已說明之圖之情形相同的符號，並省略該構成要素之詳細說明。FIG. 2 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment of the present invention. In addition, in the drawings after FIG. 2 , the same components as those shown in the previously described drawings are assigned the same reference numerals as in the previously described drawings, and detailed descriptions of the structural elements are omitted.
此處所示之保護膜形成用複合片102除保護膜形成用膜的形狀及大小不同，且治具用接著劑層積層於黏著劑層的第1面而不積層於保護膜形成用膜的第1面之方面以外，與圖1所示之保護膜形成用複合片101相同。The
更具體而言，保護膜形成用複合片102中，保護膜形成用膜23係積層於黏著劑層12的第1面12a的一部分區域、亦即黏著劑層12的寬度方向(圖2中的左右方向)的中央側的區域。進而，於黏著劑層12的第1面12a中未積層有保護膜形成用膜23之面、亦即周緣部附近的區域積層有治具用接著劑層16。並且，於保護膜形成用膜23中之與黏著劑層12側為相反側的面(本說明書中，有時稱為「第1面」)23a及治具用接著劑層16的第1面16a積層有剝離膜15。More specifically, in the protective film-forming
自上方往下俯視保護膜形成用複合片102時，保護膜形成用膜23的第1面23a的表面積小於黏著劑層12的第1面12a(亦即，合併積層有保護膜形成用膜23之區域與未積層有保護膜形成用膜23之區域所得之區域)，例如具有圓形狀等平面形狀。When the protective film-forming
保護膜形成用複合片102中，亦可於剝離膜15與和該剝離膜15直接接觸之層之間產生一部分間隙。
例如，此處表示於保護膜形成用膜23的側面23c接觸(積層)有剝離膜15之狀態，但亦有於前述側面23c未接觸有剝離膜15之情況。另外，此處表示於黏著劑層12的表面12a中未積層有保護膜形成用膜23及治具用接著劑層16之區域接觸(積層)有剝離膜15之狀態，但亦有於前述區域未接觸有剝離膜15之情況。
另外，亦有無法明確區別保護膜形成用膜23的第1面23a及側面23c之邊界之情形。這些於具備相同的形狀及大小的保護膜形成用膜之其他實施形態的保護膜形成用複合片中亦相同。In the
保護膜形成用複合片102中之支撐片10側的最表層的表面電阻率為1.0×1011
Ω/□以下。另外，於使保護膜形成用膜23熱硬化而形成保護膜後，前述支撐片10側的最表層的表面電阻率亦為1.0×1011
Ω/□以下。藉此，能夠防止因靜電等的影響而於保護膜形成用複合片102附著異物。結果，能夠防止於切割時產生碎屑。The surface resistivity of the outermost layer on the supporting
保護膜形成用複合片102係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜23的第1面23a貼附半導體晶圓(省略圖示)的內面，進而將治具用接著劑層16的第1面16a貼附於環狀框架等治具。The
圖3係以示意方式表示本發明的又一實施形態的保護膜形成用複合片之剖視圖。
此處所示之保護膜形成用複合片103除不具備治具用接著劑層16之方面以外，與圖2所示之保護膜形成用複合片102相同。FIG. 3 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment of the present invention.
The protective film forming
保護膜形成用複合片103中之支撐片10側的最表層的表面電阻率為1.0×1011
Ω/□以下。另外，於使保護膜形成用膜23熱硬化而形成保護膜後，前述支撐片10側的最表層的表面電阻率亦為1.0×1011
Ω/□以下。藉此，能夠防止因靜電等的影響而於保護膜形成用複合片103附著異物。結果，能夠防止於切割時產生碎屑。The surface resistivity of the outermost layer on the
保護膜形成用複合片103係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜23的第1面23a貼附半導體晶圓(省略圖示)的內面，進而將黏著劑層12的第1面12a中未積層有保護膜形成用膜23之區域貼附於環狀框架等治具。The
圖4係以示意方式表示本發明的又一實施形態的保護膜形成用複合片之剖視圖。
此處所示之保護膜形成用複合片104除於黏著劑層12與保護膜形成用膜23之間進而具備中間層18之方面以外，與圖3所示之保護膜形成用複合片103相同。保護膜形成用複合片104於黏著劑層12的第1面12a上具備中間層18。中間層18中之與黏著劑層12側為相反側的面(本說明書中，有時稱為「第1面」)18a係保護膜形成用膜23的積層面。4 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment of the present invention.
The
亦即，保護膜形成用複合片104係背面抗靜電層17、基材11、黏著劑層12、中間層18及保護膜形成用膜23依序於這些層的厚度方向上積層而構成。另外，保護膜形成用複合片104進而於保護膜形成用膜23上具備剝離膜15。That is, the protective film-forming
保護膜形成用複合片104中，中間層18配置於保護膜形成用膜23與黏著劑層12之間，配置於不成為最表層之中間位置。
中間層18只要為於此種配置位置發揮該中間層18的功能之層，則並無特別限定。
作為中間層18，更具體而言，例如可列舉一面經剝離處理之剝離性改善層。前述剝離性改善層具有如下功能：將具備保護膜形成用膜或保護膜之半導體晶片自支撐片扯離(剝離)而進行拾取時，提高該半導體晶片自支撐片之剝離性。In the protective film-forming
中間層18的第1面18a與保護膜形成用膜23中之黏著劑層12側的面(本說明書中，有時稱為「第2面」)23b接觸。
自上方往下俯視保護膜形成用複合片104時，中間層18的形狀(亦即，平面形狀)及大小只要中間層18能夠發揮該中間層18的功能，則並無特別限定。但為了充分地發揮中間層18的功能，較佳為中間層18的第1面18a與保護膜形成用膜23的第2面23b的整面接觸。為此，較佳為中間層18的第1面18a相對於保護膜形成用膜23的第2面23b具有同等以上的面積。另一方面，中間層18中之黏著劑層12側的面(本說明書中，有時稱為「第2面」)18b可與黏著劑層12的第1面12a的整面接觸，亦可僅與黏著劑層12的第1面12a的一部分區域接觸。但為了充分地發揮中間層18的功能，較佳為黏著劑層12的第1面12a與中間層18的第2面18b的整面接觸。
作為較佳的中間層18，例如可列舉該中間層18的第1面18a的面積及形狀與保護膜形成用膜23的第2面23b的面積及形狀同等。The
保護膜形成用複合片104中，亦可於剝離膜15與和該剝離膜15直接接觸之層之間產生一部分間隙。
例如，此處表示於中間層18的側面18c接觸(積層)有剝離膜15之狀態，但亦有於前述側面18c未接觸有剝離膜15之情況。另外，此處表示於黏著劑層12的第1面12a中未積層有中間層18之區域中，包括中間層18的附近區域在內接觸(積層)有剝離膜15之狀態，但亦有於前述第1面12a中的中間層18的附近區域未接觸有剝離膜15之情況。
另外，亦有無法明確區別中間層18的第1面18a及側面18c之邊界之情形。In the
保護膜形成用複合片104中之支撐片10側的最表層的表面電阻率為1.0×1011
Ω/□以下。另外，於使保護膜形成用膜23熱硬化而形成保護膜後，前述支撐片10側的最表層的表面電阻率亦為1.0×1011
Ω/□以下。藉此，能夠防止因靜電等的影響而於保護膜形成用複合片104附著異物。結果，能夠防止於切割時產生碎屑。The surface resistivity of the outermost layer on the supporting
保護膜形成用複合片104係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜23的第1面23a貼附半導體晶圓(省略圖示)的內面，進而將黏著劑層12的第1面12a中未積層有中間層18之區域貼附於環狀框架等治具。The
圖5係以示意方式表示本發明的又一實施形態的保護膜形成用複合片之剖視圖。
此處所示之保護膜形成用複合片105除不具備黏著劑層12之方面以外，與圖1所示之保護膜形成用複合片101相同。換言之，保護膜形成用複合片105除具備不具備黏著劑層12之支撐片20代替支撐片10之方面以外，與保護膜形成用複合片101相同。換言之，基材11的第1面11a係支撐片20中之保護膜形成用膜13側的面(本說明書中，有時稱為「第1面」)20a。FIG. 5 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment of the present invention.
The protective film forming
保護膜形成用複合片105中之支撐片20側的最表層的表面電阻率為1.0×1011
Ω/□以下。另外，於使保護膜形成用膜13熱硬化而形成保護膜後，前述支撐片20側的最表層的表面電阻率亦為1.0×1011
Ω/□以下。藉此，能夠防止因靜電等的影響而於保護膜形成用複合片105附著異物。結果，能夠防止於切割時產生碎屑。The surface resistivity of the outermost layer on the supporting
保護膜形成用複合片105係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜13的第1面13a貼附半導體晶圓(省略圖示)的內面，進而將治具用接著劑層16的第1面16a貼附於環狀框架等治具。The
具備前述背面抗靜電層作為抗靜電層之保護膜形成用複合片並不限定於圖1至圖5所示之保護膜形成用複合片。例如，本實施形態的保護膜形成用複合片亦可在無損本發明的效果之範圍內，將圖1至圖5所示之保護膜形成用複合片的一部分構成變更或刪除，或者對圖1至圖5所示之保護膜形成用複合片進而追加其他構成。The composite sheet for forming a protective film having the aforementioned backside antistatic layer as an antistatic layer is not limited to the composite sheet for forming a protective film shown in FIGS. 1 to 5 . For example, in the protective film-forming composite sheet of this embodiment, a part of the structure of the protective film-forming composite sheet shown in FIGS. 1 to 5 may be changed or deleted within the scope that does not impair the effects of the present invention, or the structure of FIG. 1 may be changed. Further, other structures are added to the protective film forming composite sheet shown in FIG. 5 .
圖5所示之保護膜形成用複合片不具備黏著劑層。作為不具備黏著劑層之本實施形態的保護膜形成用複合片，除此以外，例如亦可列舉於圖2至圖4所示之保護膜形成用複合片中，省略了黏著劑層之複合片。The composite sheet for forming a protective film shown in Figure 5 does not have an adhesive layer. As a composite sheet for protective film formation according to this embodiment without an adhesive layer, for example, the composite sheet for protective film formation shown in FIGS. 2 to 4 may be used, in which the lamination of the adhesive layer is omitted. piece.
另外，圖1、圖2及圖5所示之保護膜形成用複合片具備治具用接著劑層。作為具備治具用接著劑層之本實施形態的保護膜形成用複合片，除這些以外，例如亦可列舉於圖4所示之保護膜形成用複合片中，於黏著劑層的第1面新設置有治具用接著劑層之複合片。該情形時，於前述第1面上的治具用接著劑層的配置位置可與圖1、圖2及圖5所示之保護膜形成用複合片之情形相同。Moreover, the composite sheet for protective film formation shown in FIG. 1, FIG. 2, and FIG. 5 is equipped with the adhesive layer for a jig. As the protective film-forming composite sheet of this embodiment having an adhesive layer for a jig, in addition to these, for example, the protective film-forming composite sheet shown in FIG. 4 may be provided on the first surface of the adhesive layer. A new composite sheet with an adhesive layer for fixtures is installed. In this case, the arrangement position of the adhesive layer for the jig on the first surface may be the same as the case of the protective film forming composite sheet shown in FIGS. 1 , 2 and 5 .
另外，圖3及圖4所示之保護膜形成用複合片不具備治具用接著劑層。 作為不具備治具用接著劑層之本實施形態的保護膜形成用複合片，除這些以外，例如亦可列舉於圖1及圖5所示之保護膜形成用複合片中，省略了治具用接著劑層之複合片。In addition, the composite sheet for protective film formation shown in FIGS. 3 and 4 does not have an adhesive layer for a jig. As the composite sheet for protective film formation of this embodiment which does not have an adhesive layer for a jig, other than these, for example, the composite sheet for protective film formation shown in FIGS. 1 and 5 can also be exemplified, in which the jig is omitted. Composite sheet with adhesive layer.
另外，圖4所示之保護膜形成用複合片具備中間層。作為具備中間層之本實施形態的保護膜形成用複合片，除此以外，例如亦可列舉於圖1、圖2及圖5所示之保護膜形成用複合片中，於保護膜形成用膜的第2面側新設置有中間層之複合片。該情形時，於前述第2面上的中間層的配置形態可與引用圖4進行說明之情形相同。In addition, the composite sheet for protective film formation shown in FIG. 4 is provided with an intermediate layer. Examples of the composite sheet for protective film formation including the intermediate layer of this embodiment include the composite sheet for protective film formation shown in FIGS. 1 , 2 and 5 , and the film for protective film formation. A new composite sheet with an intermediate layer is installed on the second side. In this case, the arrangement of the intermediate layer on the second surface may be the same as that described with reference to FIG. 4 .
另外，圖1至圖5所示之保護膜形成用複合片中，除背面抗靜電層、基材、保護膜形成用膜及剝離膜以外，不具備任何層，或僅具備黏著劑層，或者僅具備黏著劑層及中間層。作為本實施形態的保護膜形成用複合片，除這些以外，例如亦可列舉於圖1至圖5所示之保護膜形成用複合片中，具備不符合背面抗靜電層、基材、黏著劑層、中間層、保護膜形成用膜及剝離膜之任一者之其他層之複合片。In addition, the composite sheet for protective film formation shown in Figures 1 to 5 does not have any layer other than the back antistatic layer, the base material, the film for protective film formation, and the release film, or only has an adhesive layer, or It only has an adhesive layer and an intermediate layer. In addition to these, examples of the composite sheet for protective film formation in this embodiment include the composite sheet for protective film formation shown in FIGS. 1 to 5 , which includes a non-compliant back antistatic layer, a substrate, and an adhesive. A composite sheet of any one of the layers, the intermediate layer, the film for forming a protective film, and the release film.
另外，本實施形態的保護膜形成用複合片中，各層的大小或形狀可根據目的任意調節。In addition, in the protective film-forming composite sheet of this embodiment, the size or shape of each layer can be arbitrarily adjusted according to the purpose.
其次，對具備前述抗靜電性基材作為抗靜電層之保護膜形成用複合片進行說明。Next, a composite sheet for forming a protective film including the antistatic base material as an antistatic layer will be described.
圖6係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。
此處所示之保護膜形成用複合片201具備支撐片30、及形成於支撐片30的一面(本說明書中，有時稱為「第1面」)30a上之保護膜形成用膜13。FIG. 6 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
The protective film-forming
支撐片30具備抗靜電性基材11'、及形成於抗靜電性基材11'的一面(本說明書中，有時稱為「第1面」)11a'上之黏著劑層12。亦即，支撐片30係抗靜電性基材11'及黏著劑層12於這些層的厚度方向上積層而構成。換言之，支撐片30的第1面30a係黏著劑層12的第1面12a。此外，符號11b'表示抗靜電性基材11'的另一面(本說明書中，有時稱為「第2面」)。The
亦即，保護膜形成用複合片201係抗靜電性基材11'、黏著劑層12及保護膜形成用膜13依序於這些層的厚度方向上積層而構成。另外，保護膜形成用複合片201進而於保護膜形成用膜13上具備剝離膜15。That is, the protective film-forming
保護膜形成用複合片201中，於黏著劑層12的第1面12a的整面或大致整面積層有保護膜形成用膜13，於保護膜形成用膜13的第1面13a的一部分、亦即周緣部附近的區域積層有治具用接著劑層16，於保護膜形成用膜13的第1面13a中未積層有治具用接著劑層16之面及治具用接著劑層16的第1面16a積層有剝離膜15。In the protective film-forming
保護膜形成用複合片201除具備抗靜電性基材11'代替背面抗靜電層17及基材11之積層物之方面以外，與圖1所示之保護膜形成用複合片101相同。The
抗靜電性基材11'含有抗靜電劑。藉此，保護膜形成用複合片201中之支撐片30側的最表層的表面電阻率成為1.0×1011
Ω/□以下。另外，於使保護膜形成用膜13熱硬化而形成保護膜後，前述支撐片30側的最表層的表面電阻率亦為1.0×1011
Ω/□以下。藉此，能夠防止因靜電等的影響而於保護膜形成用複合片201附著異物。結果，能夠防止於切割時產生碎屑。The
作為抗靜電性基材11'，例如可列舉除進而含有抗靜電劑之方面以外，與上述之基材11相同的基材。Examples of the
保護膜形成用複合片201係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜13的第1面13a貼附半導體晶圓(省略圖示)的內面，進而將治具用接著劑層16的第1面16a貼附於環狀框架等治具。The
圖7係以示意方式表示本發明的另一實施形態的保護膜形成用複合片之剖視圖。
此處所示之保護膜形成用複合片202除保護膜形成用膜的形狀及大小不同，且治具用接著劑層積層於黏著劑層的第1面而不積層於保護膜形成用膜的第1面之方面以外，與圖6所示之保護膜形成用複合片201相同。
換言之，保護膜形成用複合片202除具備抗靜電性基材11'代替背面抗靜電層17及基材11之積層物之方面以外，與圖2所示之保護膜形成用複合片102相同。7 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment of the present invention.
The
亦即，保護膜形成用複合片202係抗靜電性基材11'、黏著劑層12及保護膜形成用膜23依序於這些層的厚度方向上積層而構成。另外，保護膜形成用複合片202進而於保護膜形成用膜23上具備剝離膜15。That is, the protective film-forming
保護膜形成用複合片202中之支撐片30側的最表層的表面電阻率為1.0×1011
Ω/□以下。另外，於使保護膜形成用膜23熱硬化而形成保護膜後，前述支撐片30側的最表層的表面電阻率亦為1.0×1011
Ω/□以下。藉此，能夠防止因靜電等的影響而於保護膜形成用複合片202附著異物。結果，能夠防止於切割時產生碎屑。The surface resistivity of the outermost layer on the
保護膜形成用複合片202係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜23的第1面23a貼附半導體晶圓(省略圖示)的內面，進而將治具用接著劑層16的第1面16a貼附於環狀框架等治具。The
圖8係以示意方式表示本發明的又一實施形態的保護膜形成用複合片之剖視圖。
此處所示之保護膜形成用複合片203除不具備治具用接著劑層16之方面以外，與圖7所示之保護膜形成用複合片202相同。
換言之，保護膜形成用複合片203除具備抗靜電性基材11'代替背面抗靜電層17及基材11之積層物之方面以外，與圖3所示之保護膜形成用複合片103相同。FIG. 8 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment of the present invention.
The protective film forming
保護膜形成用複合片203中之支撐片30側的最表層的表面電阻率為1.0×1011
Ω/□以下。另外，於使保護膜形成用膜23熱硬化而形成保護膜後，前述支撐片30側的最表層的表面電阻率亦為1.0×1011
Ω/□以下。藉此，能夠防止因靜電等的影響而於保護膜形成用複合片203附著異物。結果，能夠防止於切割時產生碎屑。The surface resistivity of the outermost layer on the
保護膜形成用複合片203係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜23的第1面23a貼附半導體晶圓(省略圖示)的內面，進而將黏著劑層12的第1面12a中未積層有保護膜形成用膜23之區域貼附於環狀框架等治具。The
圖9係以示意方式表示本發明的又一實施形態的保護膜形成用複合片之剖視圖。
此處所示之保護膜形成用複合片204除於黏著劑層12與保護膜形成用膜23之間進而具備中間層18之方面以外，與圖8所示之保護膜形成用複合片203相同。9 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment of the present invention.
The
亦即，保護膜形成用複合片204係抗靜電性基材11'、黏著劑層12、中間層18及保護膜形成用膜23依序於這些層的厚度方向上積層而構成。另外，保護膜形成用複合片204進而於保護膜形成用膜23上具備剝離膜15。That is, the protective film-forming
換言之，保護膜形成用複合片204除具備抗靜電性基材11'代替背面抗靜電層17及基材11之積層物之方面以外，與圖4所示之保護膜形成用複合片104相同。In other words, the protective film forming
保護膜形成用複合片204中之支撐片30側的最表層的表面電阻率為1.0×1011
Ω/□以下。另外，於使保護膜形成用膜23熱硬化而形成保護膜後，前述支撐片30側的最表層的表面電阻率亦為1.0×1011
Ω/□以下。藉此，能夠防止因靜電等的影響而於保護膜形成用複合片204附著異物。結果，能夠防止於切割時產生碎屑。The surface resistivity of the outermost layer on the
保護膜形成用複合片204係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜23的第1面23a貼附半導體晶圓(省略圖示)的內面，進而將黏著劑層12的第1面12a中未積層有中間層18之區域貼附於環狀框架等治具。The
圖10係以示意方式表示本發明的又一實施形態的保護膜形成用複合片之剖視圖。
此處所示之保護膜形成用複合片205除不具備黏著劑層12之方面以外，與圖6所示之保護膜形成用複合片201相同。換言之，保護膜形成用複合片205除具備不具備黏著劑層12之支撐片40代替支撐片30之方面以外，與保護膜形成用複合片201相同。FIG. 10 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment of the present invention.
The protective film forming
支撐片40僅由抗靜電性基材11'所構成。換言之，此處抗靜電性基材11'的第1面11a'係支撐片40中之保護膜形成用膜13側的面(本說明書中，有時稱為「第1面」)40a，且係保護膜形成用膜13的積層面。The
亦即，保護膜形成用複合片205係抗靜電性基材11'及保護膜形成用膜13依序積層而構成。另外，保護膜形成用複合片205進而於保護膜形成用膜13上具備剝離膜15。That is, the protective film-forming
進而，換言之，保護膜形成用複合片205除具備抗靜電性基材11'代替背面抗靜電層17及基材11之積層物之方面以外，與圖5所示之保護膜形成用複合片105相同。Furthermore, in other words, the protective film-forming
保護膜形成用複合片205中之支撐片40側的最表層的表面電阻率為1.0×1011
Ω/□以下。另外，於使保護膜形成用膜13熱硬化而形成保護膜後，前述支撐片40側的最表層的表面電阻率亦為1.0×1011
Ω/□以下。藉此，能夠防止因靜電等的影響而於保護膜形成用複合片205附著異物。結果，能夠防止於切割時產生碎屑。The surface resistivity of the outermost layer on the
保護膜形成用複合片205係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜13的第1面13a貼附半導體晶圓(省略圖示)的內面，進而將治具用接著劑層16的第1面16a貼附於環狀框架等治具。The
具備前述抗靜電性基材作為抗靜電層之本實施形態的保護膜形成用複合片並不限定於圖6至圖10所示之保護膜形成用複合片。例如，本實施形態的保護膜形成用複合片亦可在無損本發明的效果之範圍內，將圖6至圖10所示之保護膜形成用複合片的一部分構成變更或刪除，或者對圖6至圖10所示之保護膜形成用複合片進而追加其他構成。The composite sheet for protective film formation according to this embodiment including the antistatic base material as the antistatic layer is not limited to the composite sheet for protective film formation shown in FIGS. 6 to 10 . For example, in the protective film-forming composite sheet of this embodiment, a part of the structure of the protective film-forming composite sheet shown in FIGS. 6 to 10 may be changed or deleted within the scope that does not impair the effects of the present invention, or the structure of FIG. 6 Further, other structures are added to the protective film forming composite sheet shown in FIG. 10 .
圖10所示之保護膜形成用複合片不具備黏著劑層。作為不具備黏著劑層之本實施形態的保護膜形成用複合片，除此以外，例如亦可列舉於圖7至圖9所示之保護膜形成用複合片中，省略了黏著劑層之複合片。The composite sheet for forming a protective film shown in Figure 10 does not have an adhesive layer. As a composite sheet for forming a protective film in this embodiment without an adhesive layer, for example, the composite sheet for forming a protective film shown in FIGS. 7 to 9 is also exemplified, and the composite sheet for forming an adhesive layer is omitted. piece.
另外，圖6、圖7及圖10所示之保護膜形成用複合片具備治具用接著劑層。作為具備治具用接著劑層之本實施形態的保護膜形成用複合片，除這些以外，例如亦可列舉於圖9所示之保護膜形成用複合片中，於黏著劑層的第1面新設置有治具用接著劑層之複合片。該情形時，於前述第1面上的治具用接著劑層的配置位置可與圖6、圖7及圖10所示之保護膜形成用複合片之情形相同。Moreover, the composite sheet for protective film formation shown in FIG. 6, FIG. 7, and FIG. 10 is equipped with the adhesive layer for a jig. As the protective film-forming composite sheet of this embodiment having an adhesive layer for a jig, in addition to these, for example, the protective film-forming composite sheet shown in FIG. 9 can also be used on the first surface of the adhesive layer. A new composite sheet with an adhesive layer for fixtures is installed. In this case, the arrangement position of the adhesive layer for the jig on the first surface may be the same as the case of the protective film forming composite sheet shown in FIGS. 6 , 7 and 10 .
另外，圖8及圖9所示之保護膜形成用複合片不具備治具用接著劑層。 作為不具備治具用接著劑層之本實施形態的保護膜形成用複合片，除這些以外，例如亦可列舉於圖6及圖10所示之保護膜形成用複合片中，省略了治具用接著劑層之複合片。In addition, the composite sheet for protective film formation shown in FIGS. 8 and 9 does not have an adhesive layer for a jig. As the composite sheet for protective film formation of this embodiment which does not have an adhesive layer for a jig, other than these, for example, the composite sheet for protective film formation shown in FIGS. 6 and 10 can also be exemplified, in which the jig is omitted. Composite sheet with adhesive layer.
另外，圖9所示之保護膜形成用複合片具備中間層。作為具備中間層之本實施形態的保護膜形成用複合片，除此以外，例如亦可列舉於圖6、圖7及圖10所示之保護膜形成用複合片中，於保護膜形成用膜的第2面新設置有中間層之複合片。該情形時，於前述第2面上的中間層的配置形態可與引用圖9進行說明之情形相同。In addition, the composite sheet for protective film formation shown in FIG. 9 is provided with an intermediate layer. Examples of the composite sheet for protective film formation including the intermediate layer in this embodiment include the composite sheet for protective film formation shown in FIGS. 6 , 7 and 10 , and the film for protective film formation. The second side is newly equipped with a composite sheet with an intermediate layer. In this case, the arrangement of the intermediate layer on the second surface may be the same as that described with reference to FIG. 9 .
另外，圖6至圖10所示之保護膜形成用複合片中，除抗靜電性基材、保護膜形成用膜及剝離膜以外，不具備任何層，或僅具備黏著劑層，或者僅具備黏著劑層及中間層。作為本實施形態的保護膜形成用複合片，除這些以外，例如亦可列舉於圖6至圖10所示之保護膜形成用複合片中，具備不符合抗靜電性基材、黏著劑層、中間層、保護膜形成用膜及剝離膜之任一者之其他層之複合片。In addition, the composite sheet for protective film formation shown in FIGS. 6 to 10 does not have any layer other than the antistatic base material, the film for protective film formation, and the release film, or it only has an adhesive layer, or it only has an adhesive layer. Adhesive layer and middle layer. In addition to these, the composite sheet for forming a protective film according to this embodiment may also be exemplified by the composite sheet for forming a protective film shown in FIGS. 6 to 10 , which includes a non-antistatic base material, an adhesive layer, A composite sheet of any one of the intermediate layer, the film for forming a protective film, and the release film and the other layer.
另外，本實施形態的保護膜形成用複合片中，亦可於剝離膜與和該剝離膜直接接觸之層之間產生一部分間隙。 另外，本實施形態的保護膜形成用複合片中，各層的大小或形狀可根據目的任意調節。In addition, in the composite sheet for protective film formation of this embodiment, a partial gap may be generated between the release film and the layer in direct contact with the release film. In addition, in the protective film-forming composite sheet of this embodiment, the size or shape of each layer can be arbitrarily adjusted according to the purpose.
其次，對具備前述表面抗靜電層作為抗靜電層之保護膜形成用複合片進行說明。Next, a composite sheet for forming a protective film including the above-mentioned surface antistatic layer as an antistatic layer will be described.
圖11係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。
此處所示之保護膜形成用複合片301具備支撐片50、及形成於支撐片50的一面(本說明書中，有時稱為「第1面」)50a上之保護膜形成用膜13。FIG. 11 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
The protective film-forming
支撐片50具備基材11、形成於基材11的第1面11a上之表面抗靜電層19、及形成於表面抗靜電層19中之與基材11側為相反側的面(本說明書中，有時稱為「第1面」)19a上之黏著劑層12。亦即，支撐片50係基材11、表面抗靜電層19及黏著劑層12依序於這些層的厚度方向上積層而構成。換言之，支撐片50的第1面50a係黏著劑層12的第1面12a。The
亦即，保護膜形成用複合片301係基材11、表面抗靜電層19、黏著劑層12及保護膜形成用膜13依序於這些層的厚度方向上積層而構成。另外，保護膜形成用複合片301進而於保護膜形成用膜13上具備剝離膜15。That is, the protective film-forming
保護膜形成用複合片301中，於黏著劑層12的第1面12a的整面或大致整面積層有保護膜形成用膜13，於保護膜形成用膜13的第1面13a的一部分、亦即周緣部附近的區域積層有治具用接著劑層16，於保護膜形成用膜13的第1面13a中未積層有治具用接著劑層16之面及治具用接著劑層16的第1面16a積層有剝離膜15。In the protective film-forming
保護膜形成用複合片301除於基材11的第2面11b上不具備背面抗靜電層17，且於基材11的第1面11a上、更具體而言於基材11與黏著劑層12之間具備表面抗靜電層19之方面以外，與圖1所示之保護膜形成用複合片101相同。The protective film forming
表面抗靜電層19與上文說明之背面抗靜電層17相同。
亦即，保護膜形成用複合片301可謂為於保護膜形成用複合片101中，將抗靜電層的配置位置自基材11的第2面11b上變更為基材11與黏著劑層12之間之複合片。The surface
表面抗靜電層19含有抗靜電劑。藉此，保護膜形成用複合片301中之支撐片50側的最表層的表面電阻率成為1.0×1011
Ω/□以下。另外，於使保護膜形成用膜13熱硬化而形成保護膜後，前述支撐片50側的最表層的表面電阻率亦為1.0×1011
Ω/□以下。藉此，能夠防止因靜電等的影響而於保護膜形成用複合片301附著異物。結果，能夠防止於切割時產生碎屑。Surface
保護膜形成用複合片301係以下述方式使用，亦即，以移除剝離膜15之狀態，於保護膜形成用膜13的第1面13a貼附半導體晶圓(省略圖示)的內面，進而將治具用接著劑層16的第1面16a貼附於環狀框架等治具。The
具備前述表面抗靜電層作為抗靜電層之保護膜形成用複合片並不限定於圖11所示之保護膜形成用複合片。例如，作為本實施形態的保護膜形成用複合片，亦可列舉於圖2至圖5所示之保護膜形成用複合片中，以不具備背面抗靜電層、且於基材的第1面具備表面抗靜電層之方式構成之複合片(換言之，將抗靜電層的配置位置自基材的第2面變更為基材的第1面之複合片)等。The composite sheet for forming a protective film having the aforementioned surface antistatic layer as an antistatic layer is not limited to the composite sheet for forming a protective film shown in FIG. 11 . For example, as the composite sheet for forming a protective film according to this embodiment, the composite sheet for forming a protective film shown in FIGS. 2 to 5 may also be exemplified, in which the back surface antistatic layer is not provided and the first surface of the base material is A composite sheet composed of a surface antistatic layer (in other words, a composite sheet in which the position of the antistatic layer is changed from the second side of the base material to the first side of the base material), etc.
進而，作為具備前述表面抗靜電層作為抗靜電層之保護膜形成用複合片，並不限定於上述之保護膜形成用複合片，可列舉上文說明之具備背面抗靜電層之保護膜形成用複合片中，將抗靜電層的配置位置自基材的第2面變更為基材的第1面之複合片。Furthermore, the composite sheet for forming a protective film having the aforementioned surface antistatic layer as an antistatic layer is not limited to the above-mentioned composite sheet for forming a protective film. Examples thereof include the composite sheet for forming a protective film having a backside antistatic layer described above. In the composite sheet, the arrangement position of the antistatic layer is changed from the second side of the base material to the first side of the base material.
本實施形態的保護膜形成用複合片中，各層的大小或形狀亦可根據目的任意調節。In the protective film-forming composite sheet of this embodiment, the size or shape of each layer can be arbitrarily adjusted according to the purpose.
前文對具備選自由背面抗靜電層、抗靜電性基材及表面抗靜電層所組成之群組中的僅1種作為抗靜電層之保護膜形成用複合片進行了說明，但本發明的一實施形態的保護膜形成用複合片亦可具備選自由背面抗靜電層、抗靜電性基材及表面抗靜電層所組成之群組中的2種以上(亦即2種或3種)作為抗靜電層。此種保護膜形成用複合片的抗靜電效果特別高，結果保護膜形成用膜與半導體晶圓之間的異物混入的抑制效果特別高。The composite sheet for forming a protective film having only one selected from the group consisting of a back antistatic layer, an antistatic base material, and a surface antistatic layer as an antistatic layer has been described above. However, one aspect of the present invention The composite sheet for forming a protective film according to the embodiment may also include two or more types (that is, two or three types) selected from the group consisting of a back antistatic layer, an antistatic base material, and a surface antistatic layer as antistatic layers. Electrostatic layer. The antistatic effect of this protective film-forming composite sheet is particularly high, and as a result, the effect of suppressing the mixing of foreign matter between the protective film-forming film and the semiconductor wafer is particularly high.
此種保護膜形成用複合片中，作為具備前述背面抗靜電層及抗靜電性基材兩者作為抗靜電層之保護膜形成用複合片，例如可列舉於圖1至圖5所示之保護膜形成用複合片中，將基材11置換為抗靜電性基材(例如圖6至圖10所示之保護膜形成用複合片中的抗靜電性基材11')之複合片。換言之，這些保護膜形成用複合片係於圖6至圖10所示之保護膜形成用複合片中，於抗靜電性基材11'的第2面11b'進而設置有背面抗靜電層(例如圖1至圖5所示之保護膜形成用複合片中的背面抗靜電層17)之複合片。Among such protective film-forming composite sheets, examples of the protective film-forming composite sheet having both the backside antistatic layer and the antistatic base material as antistatic layers include those shown in FIGS. 1 to 5 . In the composite sheet for film formation, the
圖12所示之保護膜形成用複合片401係於圖1所示之保護膜形成用複合片101中，將基材11置換為抗靜電性基材11'之複合片。保護膜形成用複合片401除具備抗靜電性基材11'代替基材11之方面以外，與保護膜形成用複合片101相同。
保護膜形成用複合片401中的支撐片60係背面抗靜電層17、抗靜電性基材11'及黏著劑層12依序於這些層的厚度方向上積層而構成。換言之，支撐片60的一面(本說明書中，有時稱為「第1面」)60a係黏著劑層12的第1面12a。The protective film forming
背面抗靜電層17及抗靜電性基材11'含有抗靜電劑。藉此，保護膜形成用複合片401中之支撐片60側的最表層的表面電阻率成為1.0×1011
Ω/□以下。另外，於使保護膜形成用膜13熱硬化而形成保護膜後，前述支撐片60側的最表層的表面電阻率亦為1.0×1011
Ω/□以下。藉此，能夠防止因靜電等的影響而於保護膜形成用複合片401附著異物。結果，能夠防止於切割時產生碎屑。The back
保護膜形成用複合片401係以與保護膜形成用複合片101及保護膜形成用複合片201之情形相同的方法使用。The protective film forming
具備背面抗靜電層及抗靜電性基材兩者之本實施形態的保護膜形成用複合片中，各層的大小或形狀亦可根據目的任意調節。In the protective film-forming composite sheet of this embodiment including both the back antistatic layer and the antistatic base material, the size or shape of each layer can be adjusted arbitrarily according to the purpose.
另一方面，作為具備前述抗靜電性基材及表面抗靜電層兩者作為抗靜電層之保護膜形成用複合片，例如可列舉：於圖6至圖10所示之保護膜形成用複合片中，於抗靜電性基材11'與於該抗靜電性基材11'的第1面11a'側和抗靜電性基材11'相鄰之層(更具體而言，黏著劑層12或保護膜形成用膜13)之間，進而設置有表面抗靜電層(例如，圖11所示之保護膜形成用複合片301中的表面抗靜電層19)之複合片。On the other hand, examples of the composite sheet for forming a protective film having both the aforementioned antistatic base material and the surface antistatic layer as antistatic layers include: the composite sheet for forming a protective film shown in FIGS. 6 to 10 In the
圖13所示之保護膜形成用複合片501係保護膜形成用複合片的一例，且係於圖11所示之保護膜形成用複合片301中，將基材11置換為抗靜電性基材11'之複合片。保護膜形成用複合片501除具備抗靜電性基材11'代替基材11之方面以外，與保護膜形成用複合片301相同。
保護膜形成用複合片501中的支撐片70係抗靜電性基材11'、表面抗靜電層19及黏著劑層12依序於這些層的厚度方向上積層而構成。換言之，支撐片70的一面(本說明書中，有時稱為「第1面」)70a係黏著劑層12的第1面12a。The protective film forming
抗靜電性基材11'及表面抗靜電層19含有抗靜電劑。藉此，保護膜形成用複合片501中之作為支撐片70側之最表層之抗靜電性基材11'的表面電阻率成為1.0×1011
Ω/□以下。另外，於使保護膜形成用膜13熱硬化而形成保護膜後，前述支撐片70側的最表層的表面電阻率亦為1.0×1011
Ω/□以下。藉此，能夠防止因靜電等的影響而於保護膜形成用複合片501附著異物。結果，能夠防止於切割時產生碎屑。The
保護膜形成用複合片501係以與保護膜形成用複合片301及保護膜形成用複合片201之情形相同的方法使用。The protective film forming
具備抗靜電性基材及表面抗靜電層兩者之本實施形態的保護膜形成用複合片中，各層的大小或形狀亦可根據目的任意調節。In the protective film-forming composite sheet of this embodiment that has both an antistatic base material and a surface antistatic layer, the size or shape of each layer can be arbitrarily adjusted according to the purpose.
本實施形態的保護膜形成用複合片亦可具備前述背面抗靜電層、抗靜電性基材及表面抗靜電層之全部作為抗靜電層。The composite sheet for forming a protective film of this embodiment may include all of the aforementioned backside antistatic layer, antistatic base material, and surface antistatic layer as an antistatic layer.
作為具備背面抗靜電層、抗靜電性基材及表面抗靜電層之全部之保護膜形成用複合片，例如可列舉如下保護膜形成用複合片：具備支撐片、及形成於前述支撐片的一面(亦即第1面)上之保護膜形成用膜，且前述支撐片係背面抗靜電層、抗靜電性基材、表面抗靜電層及黏著劑層依序於這些層的厚度方向上積層而構成，前述黏著劑層朝向前述保護膜形成用膜側而配置。
作為此種保護膜形成用複合片，更具體而言，可列舉於圖12所示之保護膜形成用複合片401中，於抗靜電性基材11'與黏著劑層12之間進而設置有表面抗靜電層(例如圖11所示之表面抗靜電層19)之複合片。Examples of a composite sheet for protective film formation that includes a back antistatic layer, an antistatic base material, and a surface antistatic layer include a composite sheet for protective film formation that includes a support sheet and one side formed on the support sheet. (i.e., the first side), and the supporting sheet is formed by laminating a back antistatic layer, an antistatic base material, a surface antistatic layer, and an adhesive layer in order in the thickness direction of these layers. It is configured that the adhesive layer is disposed toward the protective film forming film side.
As such a protective film forming composite sheet, more specifically, the protective film forming
另外，作為具備背面抗靜電層、抗靜電性基材及表面抗靜電層之全部之保護膜形成用複合片，例如可列舉如下保護膜形成用複合片：具備支撐片、及形成於前述支撐片的一面(亦即第1面)上之保護膜形成用膜，且前述支撐片係背面抗靜電層、抗靜電性基材及表面抗靜電層依序於這些層的厚度方向上積層而構成，前述表面抗靜電層朝向前述保護膜形成用膜側而配置。
作為此種保護膜形成用複合片，更具體而言，可列舉於圖12所示之保護膜形成用複合片401中，設置有表面抗靜電層(例如圖11所示之表面抗靜電層19)代替黏著劑層12之複合片。In addition, as a composite sheet for protective film formation that includes all of a back antistatic layer, an antistatic base material, and a surface antistatic layer, examples of the composite sheet for protective film formation include: a support sheet, and a support sheet formed on the support sheet A film for forming a protective film on one side (that is, the first side), and the support sheet is composed of a back antistatic layer, an antistatic base material, and a surface antistatic layer sequentially laminated in the thickness direction of these layers, The surface antistatic layer is disposed toward the protective film forming film side.
As such a protective film forming composite sheet, more specifically, a protective film forming
但這些係具備背面抗靜電層、抗靜電性基材及表面抗靜電層之全部之保護膜形成用複合片的一例。However, these are examples of protective film-forming composite sheets having all of a back antistatic layer, an antistatic base material, and a surface antistatic layer.
如上所述，具備選自由背面抗靜電層、抗靜電性基材及表面抗靜電層所組成之群組中的2種以上之保護膜形成用複合片相較於具備選自由背面抗靜電層、抗靜電性基材及表面抗靜電層所組成之群組中的僅1種之保護膜形成用複合片，抗靜電性高，能夠進一步防止因靜電等的影響而異物附著。結果，能夠進一步防止於切割時產生碎屑。相對於此，即使具備選自由背面抗靜電層、抗靜電性基材及表面抗靜電層所組成之群組中的僅1種之保護膜形成用複合片，在仍具有充分的抗靜電性、且此種片能夠低價且簡便地製造之方面而言有利。As described above, a composite sheet for forming a protective film having two or more types selected from the group consisting of a back antistatic layer, an antistatic base material, and a surface antistatic layer is more effective than having a back antistatic layer, A composite sheet for forming a protective film that is only one type of a group consisting of an antistatic base material and a surface antistatic layer. It has high antistatic properties and can further prevent the adhesion of foreign matter due to the influence of static electricity, etc. As a result, the generation of chips during cutting can be further prevented. In contrast, even if the composite sheet for forming a protective film is provided with only one type selected from the group consisting of a back antistatic layer, an antistatic base material, and a surface antistatic layer, it still has sufficient antistatic properties. Furthermore, such a sheet is advantageous in that it can be produced easily and cheaply.
前文按照抗靜電層的每種配置形態，對前述保護膜形成用複合片的整體構成進行了說明，以下對支撐片進行說明。The overall structure of the protective film-forming composite sheet has been described above for each arrangement of the antistatic layer. The support sheet will be described below.
[支撐片的全光線透過率] 前述保護膜形成用複合片中的支撐片的全光線透過率並無特別限定，較佳為70%以上，更佳為75%以上，尤佳為80%以上。藉由前述支撐片的全光線透過率為前述下限值以上，保護膜或保護膜形成用膜的雷射印字性及保護膜的印字視認性提高，能夠更高精度地檢查半導體晶片或保護膜的破裂或缺損。[Total light transmittance of support sheet] The total light transmittance of the support sheet in the protective film-forming composite sheet is not particularly limited, but is preferably 70% or more, more preferably 75% or more, and particularly preferably 80% or more. When the total light transmittance of the support sheet is equal to or higher than the lower limit, the laser printability of the protective film or protective film forming film and the print visibility of the protective film are improved, and the semiconductor wafer or protective film can be inspected with higher accuracy. cracked or damaged.
前述保護膜形成用複合片中的支撐片的全光線透過率的上限值並無特別限定，越高越佳。若考慮支撐片的製造容易度、及支撐片的構成自由度的高度等，則支撐片的全光線透過率較佳為99%以下。The upper limit of the total light transmittance of the support sheet in the composite sheet for forming a protective film is not particularly limited, and the higher the value, the better. Taking into account the ease of manufacturing the support sheet and the high degree of freedom of composition of the support sheet, the total light transmittance of the support sheet is preferably 99% or less.
支撐片的全光線透過率亦如後文實施例中所述，可依據JIS K 7375：2008而測定。The total light transmittance of the support sheet can also be measured in accordance with JIS K 7375:2008 as described in the examples below.
[支撐片的霧度] 前述保護膜形成用複合片中的支撐片的霧度並無特別限定，較佳為55%以下，更佳為50%以下，尤佳為45%以下。藉由前述支撐片的霧度為前述上限值以下，保護膜或保護膜形成用膜的雷射印字性、保護膜的印字視認性、半導體晶片或保護膜的破裂或缺損的檢查適性提高。[Haze of support sheet] The haze of the support sheet in the protective film-forming composite sheet is not particularly limited, but is preferably 55% or less, more preferably 50% or less, and particularly preferably 45% or less. When the haze of the support sheet is equal to or less than the upper limit, the laser printability of the protective film or protective film-forming film, the print visibility of the protective film, and the suitability for inspecting cracks or defects of the semiconductor wafer or the protective film are improved.
前述保護膜形成用複合片中的支撐片的霧度的下限值並無特別限定，越低越佳。若考慮支撐片的製造容易度、及支撐片的構成自由度的高度等，則支撐片的霧度亦可為40%以上。The lower limit of the haze of the support sheet in the protective film-forming composite sheet is not particularly limited, and the lower the value, the better. The haze of the support sheet may be 40% or more, taking into consideration the ease of manufacturing the support sheet and the high degree of freedom of composition of the support sheet.
支撐片的霧度可依據JIS K 7136-2000而測定。The haze of the support sheet can be measured in accordance with JIS K 7136-2000.
[抗靜電層的耐擦傷性] 前述保護膜形成用複合片中的抗靜電層的耐擦傷性會對前述複合片的保護膜形成用膜的檢查性造成影響。所謂「抗靜電層的耐擦傷性」，意指藉由其他物品摩擦抗靜電層時，抗靜電層的該摩擦面中不易損傷之程度。 若抗靜電層的耐擦傷性高，則抗靜電層的表面遍及整面，與其他物品接觸時不易損傷。因此，經由抗靜電層，使用感測器或藉由目視，將保護膜形成用複合片中的保護膜形成用膜進行光學檢查時，能夠抑制因檢查部位不同所致之檢查結果之偏差，且能夠高精度地檢查。相對於此，若抗靜電層的耐擦傷性低，則抗靜電層的表面的至少一部分與其他物品接觸時容易損傷。因此，以上述方式檢查保護膜形成用複合片中的保護膜形成用膜時，產生因檢查部位不同所致之檢查結果之偏差，且檢查精度變低。[Scratch resistance of antistatic layer] The scratch resistance of the antistatic layer in the protective film-forming composite sheet affects the inspection properties of the protective film-forming film of the composite sheet. The so-called "scratch resistance of the antistatic layer" means that when the antistatic layer is rubbed by other objects, the friction surface of the antistatic layer is not easily damaged. If the scratch resistance of the antistatic layer is high, the surface of the antistatic layer will cover the entire surface and will not be easily damaged when in contact with other items. Therefore, when the protective film-forming film in the protective film-forming composite sheet is optically inspected through the antistatic layer using a sensor or by visual inspection, it is possible to suppress deviations in the inspection results due to different inspection locations, and Able to inspect with high precision. On the other hand, if the scratch resistance of the antistatic layer is low, at least part of the surface of the antistatic layer will be easily damaged when it comes into contact with another article. Therefore, when the protective film-forming film in the protective film-forming composite sheet is inspected in the above manner, variations in inspection results occur due to differences in inspection locations, and the inspection accuracy becomes low.
抗靜電層的耐擦傷性可利用以下之方法進行評價。 亦即，首先，於用以對抗靜電層施加荷重之按壓機構的表面(以下，稱為「按壓面」)被覆法蘭絨布。此時，前述按壓機構的前述按壓面係設為面積為2cm×2cm之正方形且平面狀之面。另外，法蘭絨布的厚度並無特別限定，例如就評價結果的可靠性極高之方面而言，可為1μm至4μm。被覆於前述按壓面的可為1片法蘭絨布，亦可為2片以上之法蘭絨布於這些布的厚度方向上積層而構成之法蘭絨布之積層片。前述積層片中的各法蘭絨布的厚度可全部相同，亦可全部皆不相同，還可僅一部分相同。於使用前述積層片之情形時，前述積層片的整體的厚度、亦即前述積層片中的各法蘭絨布的厚度的合計可為1μm至4μm。The scratch resistance of the antistatic layer can be evaluated using the following method. That is, first, the surface of the pressing mechanism (hereinafter referred to as "pressing surface") for applying a load to the antistatic layer is covered with flannel cloth. At this time, the pressing surface of the pressing mechanism is a square and planar surface with an area of 2 cm×2 cm. In addition, the thickness of the flannel cloth is not particularly limited. For example, in terms of extremely high reliability of the evaluation results, it may be 1 μm to 4 μm. The pressing surface may be covered with one piece of flannel cloth, or may be a laminated sheet of flannel cloth formed by laminating two or more pieces of flannel cloth in the thickness direction of these cloths. The flannel cloths in the laminated sheet may all have the same thickness, may all have different thicknesses, or may only have the same thickness partially. When using the laminated sheet, the entire thickness of the laminated sheet, that is, the total thickness of each flannel cloth in the laminated sheet, may be 1 μm to 4 μm.
繼而，將被覆有前述法蘭絨布之前述按壓機構的前述按壓面壓抵於前述抗靜電層的表面。
繼而，以如此般經由法蘭絨布將按壓機構壓抵於抗靜電層之狀態，一邊藉由按壓機構對抗靜電層施加125g/cm2
之荷重而進行按壓，一邊使按壓機構以10cm之直線距離往返運動10次。藉此，一邊經由法蘭絨佈施加125g/cm2
之荷重，一邊摩擦抗靜電層。此時，抗靜電層的表面中被法蘭絨布摩擦的是寬度2cm、長度10cm之區域。Then, the pressing surface of the pressing mechanism covered with the flannel cloth is pressed against the surface of the antistatic layer. Then, with the pressing mechanism pressed against the antistatic layer through the flannel cloth, the pressing mechanism is pressed back and forth at a straight line distance of 10cm while applying a load of 125g/cm 2 to the antistatic layer.
繼而，藉由目視觀察抗靜電層中之該經由法蘭絨布摩擦的面中面積為2cm×2cm之區域，確認有無傷痕，可評價抗靜電層的耐擦傷性。例如，若於觀察部位存在傷痕，則確認到條紋狀的傷痕，或確認到觀察面的光反射性降低而光澤降低。若未確認到傷痕，則可判定為耐擦傷性高，若確認到傷痕，則可判定為耐擦傷性低。 抗靜電層的表面中供目視觀察之前述區域可為被法蘭絨布摩擦之寬度2cm、長度10cm之區域中的任一區域，例如可為前述區域中之長度方向上之包含中央部之區域，亦可為相同方向上之包含端部之區域。Then, the scratch resistance of the antistatic layer can be evaluated by visually observing an area of 2 cm × 2 cm in the surface of the antistatic layer rubbed with the flannel cloth to confirm whether there are scratches. For example, if there are scratches in the observation area, stripe-like scratches are observed, or the light reflectivity of the observation surface is reduced and the gloss is reduced. If no scratches are confirmed, the scratch resistance can be determined to be high. If scratches are confirmed, the scratch resistance can be determined to be low. The aforementioned area on the surface of the antistatic layer for visual observation may be any area of 2 cm in width and 10 cm in length that is rubbed by the flannel cloth. For example, it may be the area including the central portion in the length direction of the aforementioned area. It can also be a region including the ends in the same direction.
前述保護膜形成用複合片中的抗靜電層較佳為藉由上述方法評價前述抗靜電層的耐擦傷性時未確認到傷痕。此處，所謂抗靜電層，意指上文說明之背面抗靜電層、抗靜電性基材及表面抗靜電層，作為更佳的保護膜形成用複合片，例如可列舉具備此種具有耐擦傷性之背面抗靜電層或抗靜電性基材之複合片。It is preferable that the antistatic layer in the composite sheet for forming a protective film has no scratches when the scratch resistance of the antistatic layer is evaluated by the above method. Here, the so-called antistatic layer refers to the backside antistatic layer, the antistatic base material and the surface antistatic layer described above. As a more preferable composite sheet for forming a protective film, for example, it can include such a scratch-resistant composite sheet. Antistatic layer on the back or composite sheet of antistatic substrate.
例如，於保護膜形成用複合片具備選自由背面抗靜電層、抗靜電性基材及表面抗靜電層所組成之群組中的2種以上作為抗靜電層之情形時，較佳為至少保護膜形成用複合片的最外層為耐擦傷性的評價對象。 更具體而言，例如於保護膜形成用複合片一併具備背面抗靜電層及抗靜電性基材之情形、及一併具備背面抗靜電層及表面抗靜電層之情形時，較佳為至少背面抗靜電層為耐擦傷性的評價對象。 例如於保護膜形成用複合片一併具備抗靜電性基材及表面抗靜電層之情形時，較佳為至少抗靜電性基材為耐擦傷性的評價對象。例如，於保護膜形成用複合片具備背面抗靜電層、抗靜電性基材及表面抗靜電層之全部之情形時，較佳為至少背面抗靜電層為耐擦傷性的評價對象。For example, when the composite sheet for forming a protective film has two or more types of antistatic layers selected from the group consisting of a back surface antistatic layer, an antistatic base material, and a surface antistatic layer, it is preferable that at least the protective film The outermost layer of the film-forming composite sheet was evaluated for scratch resistance. More specifically, for example, when the composite sheet for forming a protective film is provided with a back antistatic layer and an antistatic base material, and when a back surface antistatic layer and a surface antistatic layer are provided together, it is preferable that at least The backside antistatic layer is evaluated for scratch resistance. For example, when the composite sheet for forming a protective film is provided with both an antistatic base material and a surface antistatic layer, it is preferable that at least the antistatic base material is the subject of evaluation of scratch resistance. For example, when the composite sheet for forming a protective film includes all of a back antistatic layer, an antistatic base material, and a surface antistatic layer, it is preferable that at least the back antistatic layer is the subject of evaluation of scratch resistance.
其次，對構成支撐片之各層更詳細地進行說明。Next, each layer constituting the support sheet will be described in more detail.
○基材 以下，對抗靜電性基材以外的基材進行說明。本說明書中，只要無特別說明，則單純的「基材」意指「抗靜電性基材以外的基材」。○Substrate Next, base materials other than the antistatic base material will be described. In this specification, unless otherwise specified, the simple "base material" means "a base material other than an antistatic base material."
前述基材為片狀或膜狀，作為前述基材的構成材料，例如可列舉各種樹脂。 作為前述樹脂，例如可列舉：低密度聚乙烯(LDPE；Low Density Polyethylene)、直鏈低密度聚乙烯(LLDPE；Linear Low Density Polyethylene)、高密度聚乙烯(HDPE；High Density Polyethylene)等聚乙烯；聚丙烯、聚丁烯、聚丁二烯、聚甲基戊烯、降冰片烯樹脂等聚乙烯以外的聚烯烴；乙烯-乙酸乙烯酯共聚物、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物、乙烯-降冰片烯共聚物等乙烯系共聚物(使用乙烯作為單體而獲得之共聚物)；聚氯乙烯、氯乙烯共聚物等氯乙烯系樹脂(使用氯乙烯作為單體而獲得之樹脂)；聚苯乙烯；聚環烯烴；聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯、聚間苯二甲酸乙二酯、聚-2,6-萘二甲酸乙二酯、全部結構單元具有芳香族環式基之全芳香族聚酯等聚酯；2種以上之前述聚酯之共聚物；聚(甲基)丙烯酸酯；聚胺基甲酸酯；聚丙烯酸胺基甲酸酯；聚醯亞胺；聚醯胺；聚碳酸酯；氟樹脂；聚縮醛；改質聚苯醚；聚苯硫醚；聚碸；聚醚酮等。 另外，作為前述樹脂，例如亦可列舉前述聚酯與前述聚酯以外的樹脂之混合物等聚合物合金。前述聚酯與前述聚酯以外的樹脂之聚合物合金較佳為聚酯以外的樹脂的量為相對較少量。 另外，作為前述樹脂，例如亦可列舉：前文例示之前述樹脂中的1種或2種以上交聯而成之交聯樹脂；使用前文例示之前述樹脂中的1種或2種以上之離子聚合物等改質樹脂。The base material is in the form of a sheet or film, and examples of the constituent material of the base material include various resins. Examples of the aforementioned resin include polyethylene such as low density polyethylene (LDPE; Low Density Polyethylene), linear low density polyethylene (LLDPE; Linear Low Density Polyethylene), and high density polyethylene (HDPE; High Density Polyethylene); Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene- Ethylene-based copolymers such as (meth)acrylate copolymer and ethylene-norbornene copolymer (copolymers obtained using ethylene as a monomer); vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymers (using chlorine Resins obtained from ethylene as a monomer); polystyrene; polycyclic olefins; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate Polyesters such as diester, polyethylene-2,6-naphthalate, fully aromatic polyesters in which all structural units have aromatic ring groups; copolymers of two or more of the above-mentioned polyesters; poly(methyl) ) Acrylate; polyurethane; polyacrylic urethane; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; Polyester; polyetherketone, etc. Examples of the resin include polymer alloys such as mixtures of the polyester and resins other than the polyester. The polymer alloy of the polyester and the resin other than the polyester preferably contains a relatively small amount of the resin other than the polyester. Examples of the resin include cross-linked resins obtained by cross-linking one or more of the above-described resins; ionic polymerization using one or two or more of the above-described resins; Materials and other modified resins.
構成基材之樹脂可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The resin constituting the base material may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily.
基材可由1層(單層)所構成，亦可由2層以上之多層所構成，於由多層所構成之情形時，這些多層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 multiple layers. When it is composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.
基材的厚度較佳為30μm至300μm，更佳為50μm至140μm。藉由基材的厚度為此種範圍，前述保護膜形成用複合片的可撓性、及朝半導體晶圓或半導體晶片之貼附性進一步提高。 此處，所謂「基材的厚度」，意指基材整體的厚度，例如所謂由多層所構成之基材的厚度，意指構成基材之全部層的合計厚度。The thickness of the base material is preferably 30 μm to 300 μm, more preferably 50 μm to 140 μm. When the thickness of the base material is within such a range, the flexibility of the composite sheet for forming a protective film and the adhesion to a semiconductor wafer or a semiconductor wafer are further improved. Here, the "thickness of the base material" means the thickness of the entire base material. For example, the thickness of the base material composed of multiple layers means the total thickness of all the layers constituting the base material.
基材較佳為厚度精度高之基材，亦即較佳為無論部位如何厚度不均皆得到抑制之基材。作為上述之構成材料中可用於構成此種厚度精度高之基材之材料，例如可列舉：聚乙烯、聚乙烯以外的聚烯烴、聚對苯二甲酸乙二酯、乙烯-乙酸乙烯酯共聚物等。The base material is preferably a base material with high thickness accuracy, that is, a base material in which thickness unevenness is suppressed regardless of the location. Among the above-mentioned constituent materials, materials that can be used to form such a base material with high thickness accuracy include, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymer. wait.
基材中，除前述樹脂等主要構成材料以外，亦可含有填充材料、著色劑、抗氧化劑、有機潤滑劑、觸媒、軟化劑(塑化劑)等公知的各種添加劑。In addition to the main constituent materials such as the aforementioned resin, the base material may also contain various known additives such as fillers, colorants, antioxidants, organic lubricants, catalysts, softeners (plasticizers), and the like.
基材可為透明，亦可為不透明，還可根據目的而著色，還可蒸鍍其他層。 例如，為了經由基材將保護膜形成用複合片中的保護膜形成用膜進行光學檢查，基材較佳為透明。The base material can be transparent or opaque, and can be colored according to the purpose, and other layers can be evaporated. For example, in order to optically inspect the protective film-forming film in the protective film-forming composite sheet via the base material, the base material is preferably transparent.
為了提高基材與設置於該基材上之層(例如黏著劑層、中間層或保護膜形成用膜)之接著性，亦可對基材表面實施利用噴砂處理、溶劑處理等之凹凸化處理；電暈放電處理、電子束照射處理、電漿處理、臭氧／紫外線照射處理、火焰處理、鉻酸處理、熱風處理等氧化處理等。另外，亦可對基材表面進行底塗處理。In order to improve the adhesion between the base material and a layer provided on the base material (such as an adhesive layer, an intermediate layer or a film for forming a protective film), the surface of the base material may also be roughened by sand blasting, solvent treatment, etc. ; Corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments, etc. In addition, the substrate surface can also be primed.
基材可利用公知的方法製造。例如，含有樹脂之基材可藉由將含有前述樹脂之樹脂組成物成形而製造。The base material can be produced by a known method. For example, a base material containing a resin can be produced by molding a resin composition containing the aforementioned resin.
○黏著劑層 前述黏著劑層為片狀或膜狀，且含有黏著劑。 作為前述黏著劑，例如可列舉：丙烯酸系樹脂、胺基甲酸酯系樹脂、橡膠系樹脂、聚矽氧系樹脂、環氧系樹脂、聚乙烯醚、聚碳酸酯、酯系樹脂等黏著性樹脂，較佳為丙烯酸系樹脂。○Adhesive layer The aforementioned adhesive layer is in the form of a sheet or film, and contains an adhesive. Examples of the adhesive include acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin and other adhesives. The resin is preferably an acrylic resin.
此外，本說明書中，「黏著性樹脂」包括具有黏著性之樹脂及具有接著性之樹脂兩者。例如，前述黏著性樹脂不僅包括樹脂本身具有黏著性之樹脂，亦包括藉由與添加劑等其他成分併用而顯示黏著性之樹脂、以及藉由存在熱或水等觸發(trigger)而顯示接著性之樹脂等。In addition, in this specification, "adhesive resin" includes both adhesive resin and adhesive resin. For example, the aforementioned adhesive resin includes not only resins that have adhesive properties by themselves, but also resins that exhibit adhesiveness by being used in combination with other components such as additives, and resins that exhibit adhesiveness by the presence of a trigger such as heat or water. Resin etc.
黏著劑層可由1層(單層)所構成，亦可由2層以上之多層所構成，於由多層所構成之情形時，這些多層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 it is composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.
黏著劑層的厚度較佳為1μm至100μm，更佳為1μm至60μm，尤佳為1μm至30μm。 此處，所謂「黏著劑層的厚度」，意指黏著劑層整體的厚度，例如所謂由多層所構成之黏著劑層的厚度，意指構成黏著劑層之全部層的合計厚度。The thickness of the adhesive layer is preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, particularly preferably 1 μm to 30 μm. Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer. For example, the thickness of an adhesive layer composed of multiple layers means the total thickness of all the layers constituting the adhesive layer.
黏著劑層可為透明，亦可為不透明，還可根據目的而著色。 例如，為了經由黏著劑層將保護膜形成用複合片中的保護膜形成用膜進行光學檢查，黏著劑層較佳為透明。The adhesive layer can be transparent or opaque, and can be colored according to the purpose. For example, in order to optically inspect the protective film-forming film in the protective film-forming composite sheet through the adhesive layer, the adhesive layer is preferably transparent.
黏著劑層可使用能量線硬化性黏著劑而形成，亦可使用非能量線硬化性黏著劑而形成。亦即，黏著劑層可為能量線硬化性及非能量線硬化性之任一種。能量線硬化性的黏著劑層能夠容易地調節硬化前及硬化後的物性。The adhesive layer may be formed using an energy ray curable adhesive or a non-energy ray curable adhesive. That is, the adhesive layer may be either energy ray curable or non-energy ray curable. The energy ray curable adhesive layer can easily adjust the physical properties before and after curing.
本說明書中，所謂「能量線」，意指具有能量量子的電磁波或帶電粒子束。作為能量線的示例，可列舉紫外線、放射線、電子束等。紫外線例如可藉由使用高壓水銀燈、熔合燈、氙氣燈、黑光燈或LED(Light Emitting Diode；發光二極體)燈等作為紫外線源進行照射。電子束可照射藉由電子束加速器等產生之電子束。 另外，本說明書中，所謂「能量線硬化性」，意指藉由照射能量線而硬化之性質，所謂「非能量線硬化性」，意指即便照射能量線亦不硬化之性質。In this specification, "energy lines" refer to electromagnetic waves or charged particle beams with energy quanta. Examples of energy rays include ultraviolet rays, radiation, electron beams, and the like. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light lamp, or an LED (Light Emitting Diode) lamp as an ultraviolet source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like. In addition, in this specification, "energy ray hardenability" means the property of being hardened by irradiation with energy rays, and "non-energy ray hardenability" means the property of not being hardened even if energy rays are irradiated.
[黏著劑組成物] 黏著劑層可使用含有黏著劑之黏著劑組成物而形成。例如，於黏著劑層之形成對象面塗敷黏著劑組成物，視需要使之乾燥，藉此可於目標部位形成黏著劑層。黏著劑組成物中的常溫下不會氣化的成分彼此的含量比率通常與黏著劑層中的前述成分彼此的含量比率相同。本說明書中，所謂「常溫」，意指不特別冷或特別熱的溫度，亦即平常的溫度，例如可列舉15℃至25℃之溫度等。 黏著劑層的更具體的形成方法將與其他層的形成方法一起於後文詳細地進行說明。[Adhesive composition] The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the adhesive layer can be formed on the target site by applying the adhesive composition on the surface to be formed and drying it if necessary. The content ratio of components that do not vaporize at room temperature in the adhesive composition is generally the same as the content ratio of the aforementioned components in the adhesive layer. In this specification, "normal temperature" means a temperature that is not particularly cold or hot, that is, an ordinary temperature. For example, a temperature of 15°C to 25°C can be cited. A more specific formation method of the adhesive layer will be described in detail later together with the formation methods of other layers.
利用公知的方法塗敷黏著劑組成物即可，例如可列舉使用以下各種塗佈機之方法：氣刀塗佈機、刮刀塗佈機、棒式塗佈機、凹版塗佈機、輥式塗佈機、輥刀塗佈機、簾幕式塗佈機、模具塗佈機、刀式塗佈機、絲網塗佈機、Meyer棒式塗佈機、輕觸式塗佈機等。The adhesive composition can be coated by any known method. For example, the following methods can be used: air knife coater, blade coater, rod coater, gravure coater, roller coater. Cloth coater, roller knife coater, curtain coater, mold coater, knife coater, screen coater, Meyer rod coater, touch coater, etc.
於基材上設置黏著劑層之情形時，例如只要於基材上塗敷黏著劑組成物，視需要使之乾燥，藉此於基材上積層黏著劑層即可。另外，於基材上設置黏著劑層之情形時，例如亦可於剝離膜上塗敷黏著劑組成物，視需要使之乾燥，藉此於剝離膜上預先形成黏著劑層，使該黏著劑層的露出面與基材的一表面貼合，藉此於基材上積層黏著劑層。該情形時的剝離膜在保護膜形成用複合片的製造過程或使用過程中的任意時間點移除即可。When an adhesive layer is provided on a base material, for example, the adhesive composition is applied on the base material and dried if necessary, thereby laminating the adhesive layer on the base material. In addition, when an adhesive layer is provided on the base material, for example, the adhesive composition can be applied on the release film and dried if necessary, thereby forming an adhesive layer on the release film in advance, so that the adhesive layer The exposed surface is bonded to one surface of the base material, thereby laminating an adhesive layer on the base material. The release film in this case may be removed at any time point during the manufacturing process or use of the protective film-forming composite sheet.
黏著劑組成物的乾燥條件並無特別限定，於黏著劑組成物含有後述溶劑之情形時，較佳為進行加熱乾燥。並且，含有溶劑之黏著劑組成物例如較佳為於70℃至130℃且10秒至5分鐘之條件進行乾燥。The drying conditions of the adhesive composition are not particularly limited. When the adhesive composition contains a solvent described below, it is preferable to perform heat drying. Furthermore, the adhesive composition containing a solvent is preferably dried at 70°C to 130°C for 10 seconds to 5 minutes.
於黏著劑層為能量線硬化性之情形時，作為含有能量線硬化性黏著劑之黏著劑組成物、亦即能量線硬化性的黏著劑組成物，例如可列舉以下之黏著劑組成物等：黏著劑組成物(I-1)，含有非能量線硬化性的黏著性樹脂(I-1a)(以下，有時簡稱為「黏著性樹脂(I-1a)」)、及能量線硬化性化合物；黏著劑組成物(I-2)，含有於非能量線硬化性的黏著性樹脂(I-1a)的側鏈導入有不飽和基之能量線硬化性的黏著性樹脂(I-2a)(以下，有時簡稱為「黏著性樹脂(I-2a)」)；黏著劑組成物(I-3)，含有前述黏著性樹脂(I-2a)及能量線硬化性化合物。When the adhesive layer is energy ray curable, examples of the adhesive composition containing the energy ray curable adhesive, that is, the energy ray curable adhesive composition, include the following adhesive compositions: The adhesive composition (I-1) contains a non-energy ray curable adhesive resin (I-1a) (hereinafter sometimes referred to as "adhesive resin (I-1a)"), and an energy ray curable compound. ; Adhesive composition (I-2), which contains an energy-ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of a non-energy-ray-curable adhesive resin (I-1a) ( Hereinafter, sometimes referred to as "adhesive resin (I-2a)"); the adhesive composition (I-3) contains the aforementioned adhesive resin (I-2a) and an energy ray curable compound.
[黏著劑組成物(I-1)] 如上所述，前述黏著劑組成物(I-1)含有非能量線硬化性的黏著性樹脂(I-1a)、及能量線硬化性化合物。[Adhesive composition (I-1)] As described above, the adhesive composition (I-1) contains a non-energy ray curable adhesive resin (I-1a) and an energy ray curable compound.
[黏著性樹脂(I-1a)] 前述黏著性樹脂(I-1a)較佳為丙烯酸系樹脂。 作為前述丙烯酸系樹脂，例如可列舉至少具有源自(甲基)丙烯酸烷基酯之結構單元之丙烯酸系聚合物。 前述丙烯酸系樹脂所具有之結構單元可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。[Adhesive resin (I-1a)] The adhesive resin (I-1a) is preferably an acrylic resin. Examples of the acrylic resin include an acrylic polymer having at least a structural unit derived from an alkyl (meth)acrylate. The acrylic resin may have only one type of structural unit, or may have two or more types. In the case of two or more types, the combination and ratio of these units may be selected arbitrarily.
作為前述(甲基)丙烯酸烷基酯，例如可列舉構成烷基酯之烷基的碳數為1至20之(甲基)丙烯酸烷基酯，前述烷基較佳為直鏈狀或支鏈狀。 作為(甲基)丙烯酸烷基酯，更具體而言，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯((甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯((甲基)丙烯酸肉豆蔻酯)、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯((甲基)丙烯酸棕櫚酯)、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯((甲基)丙烯酸硬脂酯)、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯等。Examples of the (meth)acrylic acid alkyl ester include (meth)acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester has a carbon number of 1 to 20. The alkyl group is preferably linear or branched. status. More specifically, the (meth)acrylic acid alkyl esters include: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid isopropyl acrylate Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate Hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-octyl (meth)acrylate Nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate) , Tridecyl (meth)acrylate, Myristyl (meth)acrylate (Myristyl (meth)acrylate), Pentadecyl (meth)acrylate, Tendecyl (meth)acrylate Hexalkyl ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), (meth)acrylate Nonadecyl acrylate, eicosanyl (meth)acrylate, etc.
就黏著劑層的黏著力提高之方面而言，前述丙烯酸系聚合物較佳為具有源自前述烷基的碳數為4以上之(甲基)丙烯酸烷基酯之結構單元。並且，就黏著劑層的黏著力進一步提高之方面而言，前述烷基的碳數較佳為4至12，更佳為4至8。另外，前述烷基的碳數為4以上之(甲基)丙烯酸烷基酯較佳為丙烯酸烷基酯。In order to improve the adhesive force of the adhesive layer, the acrylic polymer preferably has a structural unit derived from an alkyl (meth)acrylate having a carbon number of 4 or more in the alkyl group. In addition, in order to further improve the adhesive force of the adhesive layer, the carbon number of the alkyl group is preferably 4 to 12, and more preferably 4 to 8. In addition, the (meth)acrylic acid alkyl ester having a carbon number of 4 or more in the alkyl group is preferably an acrylic acid alkyl ester.
前述丙烯酸系聚合物較佳為除源自(甲基)丙烯酸烷基酯之結構單元以外，進而具有源自含官能基之單體之結構單元。 作為前述含官能基之單體，例如可列舉以下單體：藉由前述官能基與後述交聯劑反應而成為交聯的起點，或者藉由前述官能基與後述含不飽和基之化合物中的不飽和基反應，能夠於丙烯酸系聚合物的側鏈導入不飽和基。The acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from alkyl (meth)acrylate. Examples of the functional group-containing monomer include monomers that become a starting point for crosslinking by reacting with the crosslinking agent described below, or monomers that react with the unsaturated group-containing compound described below. The unsaturated group reaction can introduce unsaturated groups into the side chains of the acrylic polymer.
作為含官能基之單體中的前述官能基，例如可列舉：羥基、羧基、胺基、環氧基等。 亦即，作為含官能基之單體，例如可列舉：含羥基之單體、含羧基之單體、含胺基之單體、含環氧基之單體等。Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxyl group, an amino group, an epoxy group, and the like. That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amine group-containing monomer, an epoxy group-containing monomer, and the like.
作為前述含羥基之單體，例如可列舉：(甲基)丙烯酸羥基甲酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等(甲基)丙烯酸羥基烷基酯；乙烯醇、烯丙醇等非(甲基)丙烯酸系不飽和醇(不具有(甲基)丙烯醯基骨架之不飽和醇)等。Examples of the hydroxyl-containing monomer include: (meth)acrylic acid hydroxymethyl ester, (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester, (meth)acrylic acid 3- Hydroxyalkyl (meth)acrylate, such as hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols such as allyl alcohol (unsaturated alcohols that do not have a (meth)acrylyl skeleton), etc.
作為前述含羧基之單體，例如可列舉：(甲基)丙烯酸、丁烯酸等乙烯性不飽和單羧酸(具有乙烯性不飽和鍵之單羧酸)；富馬酸、衣康酸、馬來酸、檸康酸等乙烯性不飽和二羧酸(具有乙烯性不飽和鍵之二羧酸)；前述乙烯性不飽和二羧酸的酐；甲基丙烯酸2-羧基乙酯等(甲基)丙烯酸羧基烷基酯等。Examples of the carboxyl group-containing monomer include: (meth)acrylic acid, crotonic acid and other ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond); fumaric acid, itaconic acid, Maleic acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids (dicarboxylic acids with ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. base) carboxyalkyl acrylate, etc.
含官能基之單體較佳為含羥基之單體、含羧基之單體，更佳為含羥基之單體。The functional group-containing monomer is preferably a hydroxyl group-containing monomer or a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.
構成前述丙烯酸系聚合物之含官能基之單體可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The functional group-containing monomer constituting the acrylic polymer may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily.
前述丙烯酸系聚合物中，源自含官能基之單體之結構單元的含量相對於結構單元的總量，較佳為1質量%至35質量%，更佳為2質量%至32質量%，尤佳為3質量%至30質量%。In the acrylic polymer, the content of structural units derived from functional group-containing monomers is preferably 1 to 35 mass%, more preferably 2 to 32 mass%, relative to the total amount of structural units. Particularly preferably, it is 3% by mass to 30% by mass.
前述丙烯酸系聚合物亦可除源自(甲基)丙烯酸烷基酯之結構單元、及源自含官能基之單體之結構單元以外，進而具有源自其他單體之結構單元。 前述其他單體只要能夠與(甲基)丙烯酸烷基酯等共聚，則並無特別限定。 作為前述其他單體，例如可列舉：苯乙烯、α-甲基苯乙烯、乙烯基甲苯、甲酸乙烯酯、乙酸乙烯酯、丙烯腈、丙烯醯胺等。The acrylic polymer may further have structural units derived from other monomers in addition to structural units derived from alkyl (meth)acrylate and functional group-containing monomers. The aforementioned other monomers are not particularly limited as long as they can be copolymerized with alkyl (meth)acrylate and the like. Examples of the other monomer include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide, and the like.
構成前述丙烯酸系聚合物之前述其他單體可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The other monomers constituting the acrylic polymer may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily.
前述丙烯酸系聚合物可用作上述之非能量線硬化性的黏著性樹脂(I-1a)。 另一方面，使前述丙烯酸系聚合物中的官能基與具有能量線聚合性不飽和基(能量線聚合性基)之含不飽和基之化合物反應而成之化合物可用作上述之能量線硬化性的黏著性樹脂(I-2a)。The acrylic polymer can be used as the non-energy ray curable adhesive resin (I-1a). On the other hand, a compound obtained by reacting a functional group in the acrylic polymer with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group (energy ray polymerizable group) can be used as the energy ray curing agent. Adhesive resin (I-2a).
黏著劑組成物(I-1)所含有之黏著性樹脂(I-1a)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily. .
黏著劑組成物(I-1)中，黏著性樹脂(I-1a)的含量相對於黏著劑組成物(I-1)的總質量之比例較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為15質量%至90質量%。In the adhesive composition (I-1), the content of the adhesive resin (I-1a) relative to the total mass of the adhesive composition (I-1) is preferably 5 mass% to 99 mass%, more preferably The content is 10 mass% to 95 mass%, particularly preferably 15 mass% to 90 mass%.
[能量線硬化性化合物] 作為黏著劑組成物(I-1)所含有之前述能量線硬化性化合物，可列舉具有能量線聚合性不飽和基、且能夠藉由照射能量線而硬化之單體或低聚物。 能量線硬化性化合物中，作為單體，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇(甲基)丙烯酸酯等多元(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲酸酯；聚酯(甲基)丙烯酸酯；聚醚(甲基)丙烯酸酯；環氧(甲基)丙烯酸酯等。 能量線硬化性化合物中，作為低聚物，例如可列舉上述例示之單體聚合而成之低聚物等。 就分子量相對較大，不易使黏著劑層的儲存彈性模數降低之方面而言，能量線硬化性化合物較佳為(甲基)丙烯酸胺基甲酸酯、(甲基)丙烯酸胺基甲酸酯低聚物。[Energy ray curing compound] Examples of the energy ray curable compound contained in the adhesive composition (I-1) include monomers or oligomers that have an energy ray polymerizable unsaturated group and can be cured by irradiation with energy rays. Among the energy ray curable compounds, examples of monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate and other poly(meth)acrylates; (meth)acrylic acid aminomethyl Acid ester; polyester (meth)acrylate; polyether (meth)acrylate; epoxy (meth)acrylate, etc. Among the energy ray curable compounds, examples of the oligomer include oligomers obtained by polymerizing the monomers exemplified above. Since the molecular weight is relatively large and the storage elastic modulus of the adhesive layer is not easily reduced, the energy ray curable compound is preferably (meth)acrylic urethane or (meth)acrylic urethane. Ester oligomers.
黏著劑組成物(I-1)所含有之前述能量線硬化性化合物可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The adhesive composition (I-1) may contain only one type of the aforementioned energy ray curable compound, or may contain two or more types. In the case of two or more types, the combination and ratio of these compounds may be selected arbitrarily.
前述黏著劑組成物(I-1)中，前述能量線硬化性化合物的含量相對於黏著劑組成物(I-1)的總質量之比例較佳為1質量%至95質量%，更佳為5質量%至90質量%，尤佳為10質量%至85質量%。In the adhesive composition (I-1), the content of the energy ray curable compound relative to the total mass of the adhesive composition (I-1) is preferably 1 mass % to 95 mass %, more preferably 5% by mass to 90% by mass, particularly preferably 10% by mass to 85% by mass.
[交聯劑] 於使用除源自(甲基)丙烯酸烷基酯之結構單元以外、進而具有源自含官能基之單體之結構單元之前述丙烯酸系聚合物作為黏著性樹脂(I-1a)之情形時，黏著劑組成物(I-1)較佳為進而含有交聯劑。[Cross-linking agent] When the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from alkyl (meth)acrylate is used as the adhesive resin (I-1a), The adhesive composition (I-1) preferably further contains a cross-linking agent.
前述交聯劑例如與前述官能基反應而使黏著性樹脂(I-1a)彼此交聯。 作為交聯劑，例如可列舉：甲苯二異氰酸酯、六亞甲基二異氰酸酯、苯二甲基二異氰酸酯、這些二異氰酸酯之加合物等異氰酸酯系交聯劑(具有異氰酸酯基之交聯劑)；乙二醇縮水甘油醚等環氧系交聯劑(具有縮水甘油基之交聯劑)；六[1-(2-甲基)-氮丙啶基]三磷醯基三嗪等氮丙啶系交聯劑(具有氮丙啶基之交聯劑)；鋁螯合物等金屬螯合物系交聯劑(具有金屬螯合物結構之交聯劑)；異氰脲酸酯系交聯劑(具有異氰脲酸骨架之交聯劑)等。 就提高黏著劑的凝聚力而提高黏著劑層的黏著力之方面、及容易獲取等方面而言，交聯劑較佳為異氰酸酯系交聯劑。For example, the crosslinking agent reacts with the functional group to crosslink the adhesive resins (I-1a). Examples of the cross-linking agent include isocyanate-based cross-linking agents (cross-linking agents having an isocyanate group) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; Epoxy cross-linking agents (cross-linking agents with glycidyl group) such as ethylene glycol glycidyl ether; aziridines such as hexa[1-(2-methyl)-aziridinyl]triphosphonyltriazine It is a cross-linking agent (a cross-linking agent with an aziridine group); metal chelates such as aluminum chelates are a cross-linking agent (a cross-linking agent with a metal chelate structure); isocyanurate is a cross-linking agent Agent (cross-linking agent with isocyanuric acid skeleton), etc. The cross-linking agent is preferably an isocyanate-based cross-linking agent in terms of improving the cohesion of the adhesive and improving the adhesion of the adhesive layer and being easy to obtain.
黏著劑組成物(I-1)所含有之交聯劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The cross-linking agent contained in the adhesive composition (I-1) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily.
前述黏著劑組成物(I-1)中，交聯劑的含量相對於黏著性樹脂(I-1a)的含量100質量份，較佳為0.01質量份至50質量份，更佳為0.1質量份至20質量份，尤佳為0.3質量份至15質量份。In the aforementioned adhesive composition (I-1), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass, and more preferably 0.1 parts by mass relative to 100 parts by mass of the adhesive resin (I-1a). to 20 parts by mass, preferably 0.3 to 15 parts by mass.
[光聚合起始劑] 黏著劑組成物(I-1)亦可進而含有光聚合起始劑。含有光聚合起始劑之黏著劑組成物(I-1)即便照射紫外線等相對較低能量的能量線，亦充分地進行硬化反應。[Photopolymerization initiator] The adhesive composition (I-1) may further contain a photopolymerization initiator. Even if the adhesive composition (I-1) containing a photopolymerization initiator is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction proceeds sufficiently.
作為前述光聚合起始劑，例如可列舉：安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚、安息香苯甲酸、安息香苯甲酸甲酯、安息香二甲基縮酮等安息香化合物；苯乙酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等苯乙酮化合物；雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦等醯基氧化膦化合物；苄基苯基硫醚、一硫化四甲基秋蘭姆等硫醚化合物；1-羥基環己基苯基酮等α-酮醇化合物；偶氮雙異丁腈等偶氮化合物；二茂鈦等二茂鈦化合物；噻噸酮等噻噸酮化合物；過氧化物化合物；二乙醯等二酮化合物；苯偶醯；二苯偶醯；二苯甲酮；2,4-二乙基噻噸酮；1,2-二苯基甲烷；2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮；2-氯蒽醌等醌化合物。 另外，作為前述光聚合起始劑，例如亦可使用1-氯蒽醌等醌化合物；胺等光增感劑等。Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. ; Acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one and other phenylethanes Ketone compounds; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and other hydroxyphosphine oxide compounds; benzyl Phylphenyl sulfide, tetramethylthiuram monosulfide and other sulfide compounds; 1-hydroxycyclohexyl phenyl ketone and other α-ketol compounds; azo bisisobutyronitrile and other azo compounds; titanocene and other dioxins Titanocene compounds; thioxanthone and other thioxanthone compounds; peroxide compounds; diethyl and other diketone compounds; benzil; diphenyl; benzophenone; 2,4-diethylthioxanthone ; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2-chloroanthraquinone and other quinone compounds. In addition, as the photopolymerization initiator, for example, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines, etc. can also be used.
黏著劑組成物(I-1)所含有之光聚合起始劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The photopolymerization initiator contained in the adhesive composition (I-1) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily.
黏著劑組成物(I-1)中，光聚合起始劑的含量相對於前述能量線硬化性化合物的含量100質量份，較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, and more preferably 0.03 to 20 parts by mass relative to 100 parts by mass of the energy ray curable compound. 10 parts by mass, preferably 0.05 to 5 parts by mass.
[其他添加劑] 黏著劑組成物(I-1)亦可在無損本發明的效果之範圍內，含有不符合上述任一種成分之其他添加劑。 作為前述其他添加劑，例如可列舉：抗靜電劑、抗氧化劑、軟化劑(塑化劑)、填充材料(填料)、防銹劑、著色劑(顏料、染料)、增感劑、黏著賦予劑、反應延遲劑、交聯促進劑(觸媒)、層間轉移抑制劑等公知的添加劑。[Other additives] The adhesive composition (I-1) may also contain other additives that do not meet any of the above ingredients within a range that does not impair the effects of the present invention. Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and adhesion-imparting agents. Well-known additives such as reaction retardants, cross-linking accelerators (catalysts), and interlayer transfer inhibitors.
此外，所謂反應延遲劑，例如係指用以抑制因混入至黏著劑組成物(I-1)中的觸媒的作用，而使保存中的黏著劑組成物(I-1)中進行目標外的交聯反應之成分。作為反應延遲劑，例如可列舉藉由針對觸媒之螯合物而形成螯合物錯合物之反應延遲劑，更具體而言，可列舉1分子中具有2個以上之羰基(-C(=O)-)之反應延遲劑。 另外，所謂層間轉移抑制劑，例如係指用以抑制保護膜形成用膜等之與黏著劑層相鄰之層中所含有之成分朝黏著劑層轉移之成分。作為層間轉移抑制劑，可列舉與轉移抑制對象相同的成分，例如於轉移抑制對象為保護膜形成用膜中的環氧樹脂之情形時，可使用同種的環氧樹脂。In addition, the so-called reaction delaying agent refers to, for example, a substance used to inhibit the action of a catalyst mixed into the adhesive composition (I-1), causing the adhesive composition (I-1) during storage to undergo unintended processes. components of the cross-linking reaction. Examples of the reaction retardant include those that form a chelate complex by chelating the catalyst, and more specifically, those having two or more carbonyl groups (-C( =O)-) reaction delay agent. In addition, the interlayer transfer inhibitor refers to a component for inhibiting the transfer of a component contained in a layer adjacent to an adhesive layer such as a protective film forming film to the adhesive layer, for example. Examples of the interlayer transfer inhibitor include the same components as the transfer inhibitor. For example, when the transfer inhibitor is the epoxy resin in the film for forming a protective film, the same type of epoxy resin can be used.
黏著劑組成物(I-1)所含有之其他添加劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The other additives contained in the adhesive composition (I-1) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these additives may be selected arbitrarily.
黏著劑組成物(I-1)中的其他添加劑的含量並無特別限定，根據該其他添加劑的種類適宜選擇即可。The content of other additives in the adhesive composition (I-1) is not particularly limited and may be appropriately selected according to the types of the other additives.
[溶劑] 黏著劑組成物(I-1)亦可含有溶劑。黏著劑組成物(I-1)藉由含有溶劑，對塗敷對象面之塗敷適性提高。[Solvent] The adhesive composition (I-1) may also contain a solvent. By containing a solvent, the adhesive composition (I-1) improves its coating suitability for the surface to be coated.
前述溶劑較佳為有機溶劑，作為前述有機溶劑，例如可列舉：甲基乙基酮、丙酮等酮；乙酸乙酯等酯(羧酸酯)；四氫呋喃、二噁烷等醚；環己烷、正己烷等脂肪族烴；甲苯、二甲苯等芳香族烴；1-丙醇、2-丙醇等醇等。The aforementioned solvent is preferably an organic solvent. Examples of the aforementioned organic solvent include ketones such as methyl ethyl ketone and acetone; esters (carboxylic acid esters) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; cyclohexane, Aliphatic hydrocarbons such as n-hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol, etc.
作為前述溶劑，例如可將製造黏著性樹脂(I-1a)時所使用之溶劑不自黏著性樹脂(I-1a)去除而直接於黏著劑組成物(I-1)中使用，亦可於製造黏著劑組成物(I-1)時另外添加與製造黏著性樹脂(I-1a)時所使用之溶劑相同或不同種類的溶劑。As the aforementioned solvent, for example, the solvent used in manufacturing the adhesive resin (I-1a) can be used directly in the adhesive composition (I-1) without being removed from the adhesive resin (I-1a), or it can be used in the adhesive composition (I-1). When producing the adhesive composition (I-1), a solvent that is the same or different from the solvent used when producing the adhesive resin (I-1a) is additionally added.
黏著劑組成物(I-1)所含有之溶劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The solvent contained in the adhesive composition (I-1) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these solvents may be selected arbitrarily.
黏著劑組成物(I-1)中的溶劑的含量並無特別限定，適宜調節即可。The content of the solvent in the adhesive composition (I-1) is not particularly limited and can be adjusted appropriately.
[黏著劑組成物(I-2)] 如上所述，前述黏著劑組成物(I-2)含有於非能量線硬化性的黏著性樹脂(I-1a)的側鏈導入有不飽和基之能量線硬化性的黏著性樹脂(I-2a)。[Adhesive composition (I-2)] As described above, the adhesive composition (I-2) contains the energy ray curable adhesive resin (I-1a) in which an unsaturated group is introduced into the side chain of the non-energy ray curable adhesive resin (I-1a). 2a).
[黏著性樹脂(I-2a)] 前述黏著性樹脂(I-2a)例如藉由使黏著性樹脂(I-1a)中的官能基與具有能量線聚合性不飽和基之含不飽和基之化合物反應而獲得。[Adhesive resin (I-2a)] The adhesive resin (I-2a) is obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy-beam polymerizable unsaturated group.
前述含不飽和基之化合物係除前述能量線聚合性不飽和基以外，進而具有藉由與黏著性樹脂(I-1a)中的官能基反應而能夠與黏著性樹脂(I-1a)鍵結之基之化合物。 作為前述能量線聚合性不飽和基，例如可列舉(甲基)丙烯醯基、乙烯基(次乙基)、烯丙基(2-丙烯基)等，較佳為(甲基)丙烯醯基。 作為能夠與黏著性樹脂(I-1a)中的官能基鍵結之基，例如可列舉：能夠與羥基或胺基鍵結之異氰酸酯基及縮水甘油基、以及能夠與羧基或環氧基鍵結之羥基及胺基等。The aforementioned unsaturated group-containing compound, in addition to the aforementioned energy-beam polymerizable unsaturated group, further has the ability to bond with the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a). The base compound. Examples of the energy-beam polymerizable unsaturated group include (meth)acrylyl, vinyl (ethylidene), allyl (2-propenyl), and the like, with (meth)acrylyl being preferred. . Examples of the group that can be bonded to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amine group, and a carboxyl group or an epoxy group. hydroxyl and amine groups, etc.
作為前述含不飽和基之化合物，例如可列舉：異氰酸(甲基)丙烯醯氧基乙酯、(甲基)丙烯醯基異氰酸酯、(甲基)丙烯酸縮水甘油酯等。Examples of the unsaturated group-containing compound include (meth)acryloxyethyl isocyanate, (meth)acrylyl isocyanate, glycidyl (meth)acrylate, and the like.
黏著劑組成物(I-2)所含有之黏著性樹脂(I-2a)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily. .
黏著劑組成物(I-2)中，黏著性樹脂(I-2a)的含量相對於黏著劑組成物(I-2)的總質量之比例較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為10質量%至90質量%。In the adhesive composition (I-2), the content of the adhesive resin (I-2a) relative to the total mass of the adhesive composition (I-2) is preferably 5 mass% to 99 mass%, more preferably It is 10 mass % to 95 mass %, and it is especially preferable that it is 10 mass % to 90 mass %.
[交聯劑] 例如於使用與黏著性樹脂(I-1a)中的丙烯酸系聚合物相同的具有源自含官能基之單體之結構單元之前述丙烯酸系聚合物作為黏著性樹脂(I-2a)之情形時，黏著劑組成物(I-2)亦可進而含有交聯劑。[Cross-linking agent] For example, when the acrylic polymer having the same structural unit derived from a functional group-containing monomer as the acrylic polymer in the adhesive resin (I-1a) is used as the adhesive resin (I-2a) , the adhesive composition (I-2) may further contain a cross-linking agent.
作為黏著劑組成物(I-2)中的前述交聯劑，可列舉與黏著劑組成物(I-1)中的交聯劑相同的化合物。 黏著劑組成物(I-2)所含有之交聯劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。Examples of the cross-linking agent in the adhesive composition (I-2) include the same compounds as the cross-linking agents in the adhesive composition (I-1). The cross-linking agent contained in the adhesive composition (I-2) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily.
前述黏著劑組成物(I-2)中，交聯劑的含量相對於黏著性樹脂(I-2a)的含量100質量份，較佳為0.01質量份至50質量份，更佳為0.1質量份至20質量份，尤佳為0.3質量份至15質量份。In the aforementioned adhesive composition (I-2), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass, and more preferably 0.1 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a). to 20 parts by mass, preferably 0.3 to 15 parts by mass.
[光聚合起始劑] 黏著劑組成物(I-2)亦可進而含有光聚合起始劑。含有光聚合起始劑之黏著劑組成物(I-2)即便照射紫外線等相對較低能量的能量線，硬化反應亦充分地進行。[Photopolymerization initiator] The adhesive composition (I-2) may further contain a photopolymerization initiator. Even if the adhesive composition (I-2) containing a photopolymerization initiator is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction proceeds sufficiently.
作為黏著劑組成物(I-2)中的前述光聚合起始劑，可列舉與黏著劑組成物(I-1)中的光聚合起始劑相同的化合物。 黏著劑組成物(I-2)所含有之光聚合起始劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。Examples of the photopolymerization initiator in the adhesive composition (I-2) include the same compounds as the photopolymerization initiator in the adhesive composition (I-1). The photopolymerization initiator contained in the adhesive composition (I-2) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily.
黏著劑組成物(I-2)中，光聚合起始劑的含量相對於黏著性樹脂(I-2a)的含量100質量份，較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, and more preferably 0.03 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a). parts by mass to 10 parts by mass, preferably 0.05 parts by mass to 5 parts by mass.
[其他添加劑、溶劑] 黏著劑組成物(I-2)亦可在無損本發明的效果之範圍內含有不符合上述任一種成分之其他添加劑。 另外，黏著劑組成物(I-2)亦可以與黏著劑組成物(I-1)之情形相同的目的含有溶劑。 作為黏著劑組成物(I-2)中的前述其他添加劑及溶劑，可列舉分別與黏著劑組成物(I-1)中的其他添加劑及溶劑相同的化合物。 黏著劑組成物(I-2)所含有之其他添加劑及溶劑分別可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。 黏著劑組成物(I-2)中的其他添加劑及溶劑的含量分別無特別限定，根據該其他添加劑及溶劑的種類適宜選擇即可。[Other additives, solvents] The adhesive composition (I-2) may also contain other additives that do not meet any of the above ingredients within a range that does not impair the effects of the present invention. In addition, the adhesive composition (I-2) may contain a solvent for the same purpose as the adhesive composition (I-1). Examples of the other additives and solvents in the adhesive composition (I-2) include the same compounds as the other additives and solvents in the adhesive composition (I-1). The other additives and solvents contained in the adhesive composition (I-2) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily. The contents of other additives and solvents in the adhesive composition (I-2) are not particularly limited, and may be appropriately selected according to the types of the other additives and solvents.
[黏著劑組成物(I-3)] 如上所述，前述黏著劑組成物(I-3)含有前述黏著性樹脂(I-2a)、及能量線硬化性化合物。[Adhesive composition (I-3)] As described above, the adhesive composition (I-3) contains the adhesive resin (I-2a) and an energy ray curable compound.
黏著劑組成物(I-3)中，黏著性樹脂(I-2a)的含量相對於黏著劑組成物(I-3)的總質量之比例較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為15質量%至90質量%。In the adhesive composition (I-3), the content of the adhesive resin (I-2a) relative to the total mass of the adhesive composition (I-3) is preferably 5 mass% to 99 mass%, more preferably The content is 10 mass% to 95 mass%, particularly preferably 15 mass% to 90 mass%.
[能量線硬化性化合物] 作為黏著劑組成物(I-3)所含有之前述能量線硬化性化合物，可列舉具有能量線聚合性不飽和基，且能夠藉由照射能量線而硬化之單體及低聚物，可列舉與黏著劑組成物(I-1)所含有之能量線硬化性化合物相同的化合物。 黏著劑組成物(I-3)所含有之前述能量線硬化性化合物可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。[Energy ray curing compound] Examples of the energy ray curable compound contained in the adhesive composition (I-3) include monomers and oligomers that have an energy ray polymerizable unsaturated group and can be cured by irradiation with energy rays. The same compound as the energy ray curing compound contained in the adhesive composition (I-1). The adhesive composition (I-3) may contain only one type of the aforementioned energy ray curable compound, or may contain two or more types. In the case of two or more types, the combination and ratio of these compounds may be selected arbitrarily.
前述黏著劑組成物(I-3)中，前述能量線硬化性化合物的含量相對於黏著性樹脂(I-2a)的含量100質量份，較佳為0.01質量份至300質量份，更佳為0.03質量份至200質量份，尤佳為0.05質量份至100質量份。In the adhesive composition (I-3), the content of the energy ray curable compound is preferably 0.01 to 300 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a), and more preferably 0.03 parts by mass to 200 parts by mass, particularly preferably 0.05 parts by mass to 100 parts by mass.
[光聚合起始劑] 黏著劑組成物(I-3)亦可進而含有光聚合起始劑。含有光聚合起始劑之黏著劑組成物(I-3)即便照射紫外線等相對較低能量的能量線，硬化反應亦充分地進行。[Photopolymerization initiator] The adhesive composition (I-3) may further contain a photopolymerization initiator. Even if the adhesive composition (I-3) containing a photopolymerization initiator is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction proceeds sufficiently.
作為黏著劑組成物(I-3)中的前述光聚合起始劑，可列舉與黏著劑組成物(I-1)中的光聚合起始劑相同的化合物。 黏著劑組成物(I-3)所含有之光聚合起始劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。Examples of the photopolymerization initiator in the adhesive composition (I-3) include the same compounds as the photopolymerization initiator in the adhesive composition (I-1). The photopolymerization initiator contained in the adhesive composition (I-3) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily.
黏著劑組成物(I-3)中，光聚合起始劑的含量相對於黏著性樹脂(I-2a)及前述能量線硬化性化合物的總含量100質量份，較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。In the adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total content of the adhesive resin (I-2a) and the aforementioned energy ray curable compound. Parts by mass, more preferably 0.03 to 10 parts by mass, even more preferably 0.05 to 5 parts by mass.
[其他添加劑、溶劑] 黏著劑組成物(I-3)亦可在無損本發明的效果之範圍內含有不符合上述任一種成分之其他添加劑。 另外，黏著劑組成物(I-3)亦可以與黏著劑組成物(I-1)之情形相同的目的含有溶劑。 作為黏著劑組成物(I-3)中的前述其他添加劑及溶劑，可列舉分別與黏著劑組成物(I-1)中的其他添加劑及溶劑相同的化合物。 黏著劑組成物(I-3)所含有之其他添加劑及溶劑分別可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。 黏著劑組成物(I-3)中的其他添加劑及溶劑的含量分別無特別限定，根據該其他添加劑及溶劑的種類適宜選擇即可。[Other additives, solvents] The adhesive composition (I-3) may also contain other additives that do not meet any of the above ingredients within a range that does not impair the effects of the present invention. In addition, the adhesive composition (I-3) may contain a solvent for the same purpose as the adhesive composition (I-1). Examples of the other additives and solvents in the adhesive composition (I-3) include the same compounds as the other additives and solvents in the adhesive composition (I-1). The other additives and solvents contained in the adhesive composition (I-3) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily. The contents of other additives and solvents in the adhesive composition (I-3) are not particularly limited, and may be appropriately selected according to the types of the other additives and solvents.
[黏著劑組成物(I-1)至黏著劑組成物(I-3)以外的黏著劑組成物] 前文主要對黏著劑組成物(I-1)、黏著劑組成物(I-2)及黏著劑組成物(I-3)進行了說明，但作為這些黏著劑組成物的含有成分所說明之化合物亦可同樣地用於這些3種黏著劑組成物以外的所有的黏著劑組成物(本說明書中，稱為「黏著劑組成物(I-1)至黏著劑組成物(I-3)以外的黏著劑組成物」)。[Adhesive compositions other than adhesive composition (I-1) to adhesive composition (I-3)] The above has mainly explained the adhesive composition (I-1), the adhesive composition (I-2) and the adhesive composition (I-3). However, the compounds described as components of these adhesive compositions The same can be applied to all adhesive compositions other than these three types of adhesive compositions (referred to as "adhesive composition (I-1) to adhesive composition (I-3) in this specification"). Adhesive composition").
作為黏著劑組成物(I-1)至黏著劑組成物(I-3)以外的黏著劑組成物，除能量線硬化性的黏著劑組成物以外，亦可列舉非能量線硬化性的黏著劑組成物。 作為非能量線硬化性的黏著劑組成物，例如可列舉含有丙烯酸系樹脂、胺基甲酸酯系樹脂、橡膠系樹脂、聚矽氧系樹脂、環氧系樹脂、聚乙烯醚、聚碳酸酯、酯系樹脂等非能量線硬化性的黏著性樹脂(I-1a)之黏著劑組成物(I-4)，較佳為含有丙烯酸系樹脂之黏著劑組成物。As the adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3), in addition to the energy ray curable adhesive composition, non-energy ray curable adhesives can also be cited. composition. Examples of the non-energy ray curable adhesive composition include acrylic resin, urethane resin, rubber resin, polysiloxy resin, epoxy resin, polyvinyl ether, and polycarbonate. The adhesive composition (I-4) of non-energy ray curable adhesive resin (I-1a) such as ester resin and the like is preferably an adhesive composition containing an acrylic resin.
黏著劑組成物(I-1)至黏著劑組成物(I-3)以外的黏著劑組成物較佳為含有1種或2種以上之交聯劑，該交聯劑的含量可設為與上述黏著劑組成物(I-1)等情形相同。The adhesive compositions other than the adhesive composition (I-1) to the adhesive composition (I-3) preferably contain one or more cross-linking agents, and the content of the cross-linking agent can be set to The same applies to the adhesive composition (I-1) described above.
[黏著劑組成物(I-4)] 作為較佳的黏著劑組成物(I-4)，例如可列舉含有前述黏著性樹脂(I-1a)、及交聯劑之黏著劑組成物。[Adhesive composition (I-4)] As a preferable adhesive composition (I-4), the adhesive composition containing the said adhesive resin (I-1a) and a crosslinking agent is mentioned, for example.
[黏著性樹脂(I-1a)] 作為黏著劑組成物(I-4)中的黏著性樹脂(I-1a)，可列舉與黏著劑組成物(I-1)中的黏著性樹脂(I-1a)相同的化合物。 黏著劑組成物(I-4)所含有之黏著性樹脂(I-1a)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。[Adhesive resin (I-1a)] Examples of the adhesive resin (I-1a) in the adhesive composition (I-4) include the same compounds as the adhesive resin (I-1a) in the adhesive composition (I-1). The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily. .
黏著劑組成物(I-4)中，黏著性樹脂(I-1a)的含量相對於黏著劑組成物(I-4)的總質量之比例較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為15質量%至90質量%。In the adhesive composition (I-4), the content of the adhesive resin (I-1a) relative to the total mass of the adhesive composition (I-4) is preferably 5 mass% to 99 mass%, more preferably The content is 10 mass% to 95 mass%, particularly preferably 15 mass% to 90 mass%.
[交聯劑] 於使用除源自(甲基)丙烯酸烷基酯之結構單元以外、進而具有源自含官能基之單體之結構單元之前述丙烯酸系聚合物作為黏著性樹脂(I-1a)之情形時，黏著劑組成物(I-4)較佳為進而含有交聯劑。[Cross-linking agent] When the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from alkyl (meth)acrylate is used as the adhesive resin (I-1a), The adhesive composition (I-4) preferably further contains a cross-linking agent.
作為黏著劑組成物(I-4)中的交聯劑，可列舉與黏著劑組成物(I-1)中的交聯劑相同的化合物。 黏著劑組成物(I-4)所含有之交聯劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。Examples of the crosslinking agent in the adhesive composition (I-4) include the same compounds as the crosslinking agent in the adhesive composition (I-1). The cross-linking agent contained in the adhesive composition (I-4) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily.
前述黏著劑組成物(I-4)中，交聯劑的含量相對於黏著性樹脂(I-1a)的含量100質量份，較佳為0.01質量份至50質量份，更佳為0.1質量份至47質量份，尤佳為0.3質量份至44質量份。In the aforementioned adhesive composition (I-4), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass, and more preferably 0.1 parts by mass relative to 100 parts by mass of the adhesive resin (I-1a). to 47 parts by mass, preferably 0.3 to 44 parts by mass.
[其他添加劑、溶劑] 黏著劑組成物(I-4)亦可在無損本發明的效果之範圍內含有不符合上述任一種成分之其他添加劑。 另外，黏著劑組成物(I-4)亦可以與黏著劑組成物(I-1)之情形相同的目的含有溶劑。 作為黏著劑組成物(I-4)中的前述其他添加劑及溶劑，可列舉分別與黏著劑組成物(I-1)中的其他添加劑及溶劑相同的化合物。 黏著劑組成物(I-4)所含有之其他添加劑及溶劑分別可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。 黏著劑組成物(I-4)中的其他添加劑及溶劑的含量分別無特別限定，根據該其他添加劑及溶劑的種類適宜選擇即可。[Other additives, solvents] The adhesive composition (I-4) may also contain other additives that do not meet any of the above ingredients within a range that does not impair the effects of the present invention. In addition, the adhesive composition (I-4) may contain a solvent for the same purpose as the adhesive composition (I-1). Examples of the other additives and solvents in the adhesive composition (I-4) include the same compounds as the other additives and solvents in the adhesive composition (I-1). The other additives and solvents contained in the adhesive composition (I-4) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily. The contents of other additives and solvents in the adhesive composition (I-4) are not particularly limited, and may be appropriately selected according to the types of the other additives and solvents.
此處，對黏著劑層為非能量線硬化性之情形的效果進行了說明，但即便為支撐片中之與保護膜形成用膜直接接觸之層為黏著劑層以外的層，只要該層為非能量線硬化性，則亦發揮相同的效果。Here, the effect is explained when the adhesive layer is non-energy ray hardenable. However, even if the layer in the support sheet that is in direct contact with the protective film forming film is a layer other than the adhesive layer, as long as the layer is Non-energy ray hardening properties also exert the same effect.
[黏著劑組成物之製造方法] 黏著劑組成物(I-1)至黏著劑組成物(I-3)、或黏著劑組成物(I-4)等黏著劑組成物(I-1)至黏著劑組成物(I-3)以外的黏著劑組成物係藉由調配前述黏著劑及視需要的前述黏著劑以外的成分等用以構成黏著劑組成物之各成分而獲得。 調配各成分時的添加順序並無特別限定，亦可同時添加2種以上之成分。 於使用溶劑之情形時，可藉由下述方式使用：將溶劑與溶劑以外的任一種調配成分混合而將該調配成分預先稀釋；或是，不將溶劑以外的任一種調配成分預先稀釋而將溶劑與這些調配成分混合。 調配時混合各成分之方法並無特別限定，自以下公知的方法中適宜選擇即可：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機進行混合之方法；施加超音波進行混合之方法等。 關於添加及混合各成分時的溫度及時間，只要不使各調配成分劣化，則並無特別限定，適宜調節即可，溫度較佳為15℃至30℃。[Production method of adhesive composition] Adhesive compositions (I-1) to adhesive compositions (I-3), or adhesive compositions (I-4) and other adhesive compositions (I-1) to adhesive compositions (I-3) The adhesive composition other than the adhesive composition is obtained by blending the above-mentioned adhesive and optional components other than the above-mentioned adhesive, etc. to form each component of the adhesive composition. The order in which each component is added is not particularly limited, and two or more components may be added at the same time. When using a solvent, it can be used by mixing the solvent with any preparation ingredient other than the solvent and diluting the preparation ingredients in advance; or by not diluting any preparation ingredient other than the solvent in advance. Solvents are mixed with these formulation ingredients. The method of mixing each component during preparation is not particularly limited, and can be appropriately selected from the following known methods: mixing by rotating a stirrer or stirring blade, mixing with a mixer, and mixing by applying ultrasonic waves. methods, etc. The temperature and time when adding and mixing each component are not particularly limited as long as the components are not deteriorated and can be adjusted appropriately. The temperature is preferably 15°C to 30°C.
○背面抗靜電層 前述背面抗靜電層為片狀或膜狀，含有抗靜電劑。 前述背面抗靜電層中，除前述抗靜電劑以外，亦可含有樹脂。○Antistatic layer on the back The aforementioned backside antistatic layer is in the form of a sheet or film and contains an antistatic agent. The back surface antistatic layer may contain resin in addition to the antistatic agent.
背面抗靜電層可由1層(單層)所構成，亦可由2層以上之多層所構成，於由多層所構成之情形時，這些多層相互可相同亦可不同，這些多層的組合並無特別限定。The backside antistatic layer can be composed of one layer (single layer), or it can be composed of two or more layers. When it is composed of multiple layers, these multiple layers can be the same or different from each other. The combination of these multiple layers is not particularly limited. .
背面抗靜電層的厚度較佳為200nm以下，更佳為180nm以下，例如亦可為100nm以下。厚度為200nm以下之背面抗靜電層中，能夠維持充分的抗靜電能力，並且能夠降低抗靜電劑的使用量，因此能夠降低具備此種背面抗靜電層之保護膜形成用複合片的成本。進而，於背面抗靜電層的厚度為100nm以下之情形時，除上述效果以外，亦能夠獲得如下效果：能夠將因具備背面抗靜電層所致之保護膜形成用複合片的特性的變動抑制為最小限度。作為前述特性，例如可列舉擴展性。 此處，所謂「背面抗靜電層的厚度」，意指背面抗靜電層整體的厚度，例如所謂由多層所構成之背面抗靜電層的厚度，意指構成背面抗靜電層之全部層的合計厚度。The thickness of the back antistatic layer is preferably 200 nm or less, more preferably 180 nm or less, for example, it may also be 100 nm or less. A backside antistatic layer with a thickness of 200 nm or less can maintain sufficient antistatic capability and reduce the amount of antistatic agent used. Therefore, the cost of a composite sheet for forming a protective film having such a backside antistatic layer can be reduced. Furthermore, when the thickness of the back antistatic layer is 100 nm or less, in addition to the above-mentioned effects, the following effect can be obtained: the variation in characteristics of the protective film forming composite sheet due to the provision of the back antistatic layer can be suppressed to Minimum. Examples of the aforementioned characteristics include scalability. Here, the "thickness of the back antistatic layer" means the thickness of the entire back antistatic layer. For example, the thickness of the back antistatic layer composed of multiple layers means the total thickness of all the layers constituting the back antistatic layer. .
背面抗靜電層的厚度較佳為30nm以上，更佳為40nm以上，例如亦可為65nm以上。厚度為前述下限值以上之背面抗靜電層更容易形成，且結構更穩定。The thickness of the back antistatic layer is preferably 30 nm or more, more preferably 40 nm or more, for example, it may also be 65 nm or more. A backside antistatic layer with a thickness above the aforementioned lower limit is easier to form and has a more stable structure.
背面抗靜電層的厚度可適宜調節為將上述之較佳的下限值及上限值任意組合而設定之範圍內。例如，一實施形態中，背面抗靜電層的厚度較佳為30nm至200nm，更佳為40nm至180nm，例如亦可為65nm至100nm。但這些係背面抗靜電層的厚度的一例。The thickness of the back antistatic layer can be appropriately adjusted to a range set by any combination of the above-mentioned preferred lower limit values and upper limit values. For example, in one embodiment, the thickness of the back antistatic layer is preferably 30 nm to 200 nm, more preferably 40 nm to 180 nm, for example, it may also be 65 nm to 100 nm. However, these are examples of the thickness of the backside antistatic layer.
背面抗靜電層可為透明，亦可為不透明，還可根據目的而著色。 例如，為了經由背面抗靜電層將保護膜形成用複合片中的保護膜形成用膜進行光學檢查，背面抗靜電層較佳為透明。The back antistatic layer can be transparent or opaque, and can also be colored according to the purpose. For example, in order to optically inspect the protective film-forming film in the protective film-forming composite sheet via the back antistatic layer, the back antistatic layer is preferably transparent.
[抗靜電組成物(VI-1)] 背面抗靜電層可使用含有前述抗靜電劑之抗靜電組成物(VI-1)而形成。例如，於背面抗靜電層的形成對象面塗敷抗靜電組成物(VI-1)，並視需要使之乾燥，藉此能夠於目標部位形成背面抗靜電層。抗靜電組成物(VI-1)中的常溫下不會氣化的成分彼此的含量比率通常與背面抗靜電層中的前述成分彼此的含量比率相同。 背面抗靜電層的更具體的形成方法與其他層的形成方法一起於後文詳細地進行說明。[Antistatic composition (VI-1)] The backside antistatic layer can be formed using the antistatic composition (VI-1) containing the aforementioned antistatic agent. For example, the antistatic composition (VI-1) is applied to the surface to be formed of the back antistatic layer and dried if necessary, thereby forming the back antistatic layer at the target location. The content ratio of components that do not vaporize at normal temperature in the antistatic composition (VI-1) is usually the same as the content ratio of the above-mentioned components in the back antistatic layer. A more specific method of forming the back antistatic layer will be described in detail later along with methods of forming other layers.
利用公知的方法塗敷抗靜電組成物(VI-1)即可，例如可為與上述之黏著劑組成物之情形相同的方法。The antistatic composition (VI-1) may be applied by a known method, for example, the same method as in the case of the above-mentioned adhesive composition may be used.
於基材上設置背面抗靜電層之情形時，例如於基材上塗敷抗靜電組成物(VI-1)，並視需要使之乾燥，藉此於基材上積層背面抗靜電層即可。另外，於基材上設置背面抗靜電層之情形時，例如亦可於剝離膜上塗敷抗靜電組成物(VI-1)，並視需要使之乾燥，藉此於剝離膜上預先形成背面抗靜電層，將該背面抗靜電層的露出面與基材的一表面貼合，藉此於基材上積層背面抗靜電層。該情形時的剝離膜在保護膜形成用複合片的製造過程或使用過程中的任意時間點移除即可。When providing a back antistatic layer on a base material, for example, the antistatic composition (VI-1) is applied to the base material and dried if necessary, thereby laminating the back antistatic layer on the base material. In addition, when providing a back antistatic layer on a base material, for example, the antistatic composition (VI-1) can be applied on the release film and dried if necessary, thereby forming a back antistatic layer on the release film in advance. The electrostatic layer laminates the back antistatic layer on the base material by bonding the exposed surface of the back antistatic layer to one surface of the base material. The release film in this case may be removed at any time point during the manufacturing process or use of the protective film-forming composite sheet.
抗靜電組成物(VI-1)的乾燥條件並無特別限定，於抗靜電組成物(VI-1)含有後述溶劑之情形時，較佳為進行加熱乾燥。並且，含有溶劑之抗靜電組成物(VI-1)例如較佳為於40℃至130℃且10秒至5分鐘之條件進行乾燥。The drying conditions of the antistatic composition (VI-1) are not particularly limited. When the antistatic composition (VI-1) contains the solvent described below, it is preferable to perform heat drying. Furthermore, the antistatic composition (VI-1) containing a solvent is preferably dried at 40°C to 130°C for 10 seconds to 5 minutes, for example.
抗靜電組成物(VI-1)中，除前述抗靜電劑以外，亦可含有前述樹脂。The antistatic composition (VI-1) may contain the aforementioned resin in addition to the aforementioned antistatic agent.
[抗靜電劑] 前述抗靜電劑可為導電性化合物等公知的化合物，並無特別限定。前述抗靜電劑例如可為低分子化合物及高分子化合物(換言之，低聚物或聚合物)之任一種。[antistatic agent] The antistatic agent may be a known compound such as a conductive compound, and is not particularly limited. The antistatic agent may be, for example, any of a low molecular compound and a high molecular compound (in other words, an oligomer or a polymer).
前述抗靜電劑中，作為低分子化合物，例如可列舉各種離子液體。 作為前述離子液體，例如可列舉：嘧啶鎓鹽、吡啶鎓鹽、哌啶鎓鹽、吡咯啶鎓鹽、咪唑鎓鹽、嗎啉鎓鹽、鋶鹽、鏻鹽、銨鹽等公知的化合物。Among the aforementioned antistatic agents, examples of low molecular compounds include various ionic liquids. Examples of the ionic liquid include well-known compounds such as pyrimidinium salts, pyridinium salts, piperidinium salts, pyrrolidinium salts, imidazolium salts, morpholinium salts, sulfonium salts, phosphonium salts, and ammonium salts.
前述抗靜電劑中，作為高分子化合物，例如可列舉：聚(3,4-乙二氧基噻吩)/聚苯乙烯磺酸鹽(本說明書中，有時稱為「PEDOT/PSS」)、聚吡咯、奈米碳管等。前述聚吡咯為具有多個(多數)吡咯骨架之低聚物或聚合物。Among the aforementioned antistatic agents, examples of polymer compounds include poly(3,4-ethylenedioxythiophene)/polystyrenesulfonate (herein, may be referred to as “PEDOT/PSS”), Polypyrrole, carbon nanotubes, etc. The aforementioned polypyrrole is an oligomer or polymer having multiple (majority) pyrrole skeletons.
抗靜電組成物(VI-1)所含有之抗靜電劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The antistatic composition (VI-1) may contain only one type of antistatic agent or two or more types. In the case of two or more types, the combination and ratio of these agents can be selected arbitrarily.
抗靜電組成物(VI-1)中，抗靜電劑的含量相對於溶劑以外的全部成分的總含量之比例(亦即，背面抗靜電層中的抗靜電劑的含量相對於背面抗靜電層的總質量之比例)例如可為0.1質量%至30質量%、以及0.5質量%至15質量%之任一者。藉由前述比例為前述下限值以上，保護膜形成用複合片的抗靜電效果變高，結果保護膜形成用膜與半導體晶圓之間的異物混入的抑制效果變高。藉由前述比例為前述上限值以下，背面抗靜電層的強度變得更高。In the antistatic composition (VI-1), the ratio of the content of the antistatic agent to the total content of all components except the solvent (that is, the content of the antistatic agent in the back antistatic layer relative to the content of the back antistatic layer The ratio of the total mass) may be, for example, any one of 0.1% to 30% by mass and 0.5% to 15% by mass. When the ratio is equal to or higher than the lower limit, the antistatic effect of the protective film-forming composite sheet becomes higher, and as a result, the effect of suppressing the mixing of foreign matter between the protective film-forming film and the semiconductor wafer becomes higher. When the ratio is equal to or less than the upper limit, the strength of the back antistatic layer becomes higher.
[樹脂] 抗靜電組成物(VI-1)及背面抗靜電層所含有之前述樹脂可為硬化性及非硬化性之任一種，於為硬化性之情形時，可為能量線硬化性及熱硬化性之任一種。[resin] The aforementioned resin contained in the antistatic composition (VI-1) and the back antistatic layer may be either curable or non-curable. In the case of curable, it may be energy ray curable or thermosetting. Any kind.
作為較佳的前述樹脂，例如可列舉作為黏合劑樹脂發揮功能之樹脂。Preferable examples of the resin include resins that function as binder resins.
作為前述樹脂，更具體而言，例如可列舉丙烯酸系樹脂等，較佳為能量線硬化性丙烯酸系樹脂。 作為抗靜電組成物(VI-1)及背面抗靜電層中的前述丙烯酸系樹脂，例如可列舉與前述黏著劑層中的丙烯酸系樹脂相同的樹脂。作為抗靜電組成物(VI-1)及背面抗靜電層中的前述能量線硬化性丙烯酸系樹脂，例如可列舉與前述黏著劑層中的黏著性樹脂(I-2a)相同的樹脂。More specific examples of the resin include acrylic resins, and energy ray-curable acrylic resins are preferred. Examples of the acrylic resin in the antistatic composition (VI-1) and the back surface antistatic layer include the same resin as the acrylic resin in the adhesive layer. Examples of the energy ray-curable acrylic resin in the antistatic composition (VI-1) and the back surface antistatic layer include the same resin as the adhesive resin (I-2a) in the adhesive layer.
抗靜電組成物(VI-1)及背面抗靜電層所含有之前述樹脂可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The above-mentioned resin contained in the antistatic composition (VI-1) and the back antistatic layer may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily.
抗靜電組成物(VI-1)中，前述樹脂的含量相對於溶劑以外的全部成分的總含量之比例(亦即，背面抗靜電層中的前述樹脂的含量相對於背面抗靜電層的總質量之比例)例如可為30質量%至99.9質量%、35質量%至98質量%、60質量%至98質量%、以及85質量%至98質量%之任一種。藉由前述比例為前述下限值以上，背面抗靜電層的強度變得更高。藉由前述比例為前述上限值以下，能夠使抗靜電層中的抗靜電劑的含量更多。In the antistatic composition (VI-1), the ratio of the content of the aforementioned resin to the total content of all components except the solvent (that is, the content of the aforementioned resin in the back antistatic layer to the total mass of the back antistatic layer The proportion) may be, for example, any one of 30 mass% to 99.9 mass%, 35 mass% to 98 mass%, 60 mass% to 98 mass%, and 85 mass% to 98 mass%. When the ratio is equal to or higher than the lower limit, the strength of the backside antistatic layer becomes higher. When the aforementioned ratio is equal to or less than the aforementioned upper limit, the content of the antistatic agent in the antistatic layer can be increased.
[能量線硬化性化合物、光聚合起始劑] 於抗靜電組成物(VI-1)含有能量線硬化性的前述樹脂之情形時，亦可含有能量線硬化性化合物。 另外，於抗靜電組成物(VI-1)含有能量線硬化性的前述樹脂之情形時，為了高效率地進行前述樹脂的聚合反應，亦可含有光聚合起始劑。 作為抗靜電組成物(VI-1)所含有之前述能量線硬化性化合物及光聚合起始劑，例如可列舉分別與黏著劑組成物(I-1)所含有之能量線硬化性化合物及光聚合起始劑相同的化合物。 抗靜電組成物(VI-1)所含有之能量線硬化性化合物及光聚合起始劑分別可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。 抗靜電組成物(VI-1)中的能量線硬化性化合物及光聚合起始劑的含量分別無特別限定，根據前述樹脂、能量線硬化性化合物或光聚合起始劑的種類適宜選擇即可。[Energy ray curable compound, photopolymerization initiator] When the antistatic composition (VI-1) contains the energy-ray-curable resin, it may also contain an energy-ray-curable compound. In addition, when the antistatic composition (VI-1) contains the energy-beam curable resin, a photopolymerization initiator may be included in order to efficiently carry out the polymerization reaction of the resin. Examples of the energy ray curable compound and photopolymerization initiator contained in the antistatic composition (VI-1) include the energy ray curable compound and photopolymerization initiator contained in the adhesive composition (I-1), respectively. The same compound as the polymerization initiator. The energy ray curable compound and the photopolymerization initiator contained in the antistatic composition (VI-1) may be only one type, or two or more types. In the case of two or more types, the combination of these and The ratio can be chosen arbitrarily. The contents of the energy ray curable compound and the photopolymerization initiator in the antistatic composition (VI-1) are not particularly limited, and may be appropriately selected according to the types of the aforementioned resin, energy ray curable compound, or photopolymerization initiator. .
[其他添加劑、溶劑] 抗靜電組成物(VI-1)亦可在無損本發明的效果之範圍內含有不符合上述任一種成分之其他添加劑。 另外，抗靜電組成物(VI-1)亦可以與上述之黏著劑組成物(I-1)之情形相同的目的含有溶劑。 作為抗靜電組成物(VI-1)所含有之前述其他添加劑及溶劑，可列舉分別與上述之黏著劑組成物(I-1)所含有之其他添加劑(但抗靜電劑除外)及溶劑相同的化合物。進而，作為抗靜電組成物(VI-1)所含有之前述其他添加劑，除上述化合物以外，亦可列舉乳化劑。進而，作為抗靜電組成物(VI-1)所含有之溶劑，除上述化合物以外，亦可列舉：乙醇等其他醇；2-甲氧基乙醇(乙二醇單甲醚)、2-乙氧基乙醇(乙二醇單乙醚)、1-甲氧基-2-丙醇(丙二醇單甲醚)等烷氧基醇等。 抗靜電組成物(VI-1)所含有之其他添加劑及溶劑分別可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。 抗靜電組成物(VI-1)中的其他添加劑及溶劑的含量分別無特別限定，根據該其他添加劑及溶劑的種類適宜選擇即可。[Other additives, solvents] The antistatic composition (VI-1) may also contain other additives that do not meet any of the above ingredients within a range that does not impair the effects of the present invention. In addition, the antistatic composition (VI-1) may also contain a solvent for the same purpose as the above-mentioned adhesive composition (I-1). Examples of the aforementioned other additives and solvents contained in the antistatic composition (VI-1) include the same additives (except for the antistatic agent) and solvents contained in the above-mentioned adhesive composition (I-1). compound. Furthermore, as the aforementioned other additives contained in the antistatic composition (VI-1), in addition to the above-mentioned compounds, emulsifiers can also be cited. Furthermore, as the solvent contained in the antistatic composition (VI-1), in addition to the above compounds, other alcohols such as ethanol; 2-methoxyethanol (ethylene glycol monomethyl ether), 2-ethoxy Alkoxy alcohols such as ethanol (ethylene glycol monoethyl ether) and 1-methoxy-2-propanol (propylene glycol monomethyl ether). The other additives and solvents contained in the antistatic composition (VI-1) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily. The contents of other additives and solvents in the antistatic composition (VI-1) are not particularly limited, and may be appropriately selected according to the types of the other additives and solvents.
[抗靜電組成物(VI-1)之製造方法] 抗靜電組成物(VI-1)可藉由調配前述抗靜電劑、及視需要前述抗靜電劑以外的成分等用以構成抗靜電組成物(VI-1)之各成分而獲得。 抗靜電組成物(VI-1)除調配成分不同之方面以外，可利用與上述之黏著劑組成物之情形相同的方法製造。[Production method of antistatic composition (VI-1)] The antistatic composition (VI-1) can be obtained by blending each component constituting the antistatic composition (VI-1) such as the aforementioned antistatic agent and, if necessary, components other than the aforementioned antistatic agent. The antistatic composition (VI-1) can be produced by the same method as the above-mentioned adhesive composition except that the ingredients are different.
○抗靜電性基材 前述抗靜電性基材為片狀或膜狀，具有抗靜電性，進而具有與前述基材相同的功能。 前述保護膜形成用複合片中，抗靜電性基材具有與上文說明之基材及背面抗靜電層之積層物相同的功能，可代替該積層物而配置。 抗靜電性基材含有抗靜電劑及樹脂，例如除進而含有抗靜電劑之方面以外，可與上文說明之基材相同。○Antistatic base material The antistatic base material is in the form of a sheet or film, has antistatic properties, and has the same function as the base material. In the composite sheet for forming a protective film, the antistatic base material has the same function as the laminate of the base material and the back antistatic layer described above, and may be disposed in place of the laminate. The antistatic base material contains an antistatic agent and a resin, and may be the same as the base material described above except that it further contains an antistatic agent.
抗靜電性基材可由1層(單層)所構成，亦可由2層以上之多層所構成，於由多層所構成之情形時，這些多層相互可相同亦可不同，這些多層的組合並無特別限定。The antistatic base material can be composed of one layer (single layer), or it can be composed of two or more layers. When it is composed of multiple layers, these multiple layers can be the same or different from each other. There is no particular combination of these multiple layers. limited.
抗靜電性基材的厚度例如可與上文說明之基材的厚度相同。藉由抗靜電性基材的厚度為此種範圍，前述保護膜形成用複合片的可撓性、及朝半導體晶圓或半導體晶片之貼附性進一步提高。 此處，所謂「抗靜電性基材的厚度」，意指抗靜電性基材整體的厚度，例如所謂由多層所構成之抗靜電性基材的厚度，意指構成抗靜電性基材之全部層的合計厚度。The thickness of the antistatic base material may be, for example, the same as the thickness of the base material described above. When the thickness of the antistatic base material is within this range, the flexibility of the protective film forming composite sheet and the adhesion to the semiconductor wafer or the semiconductor wafer are further improved. Here, the "thickness of the antistatic base material" means the thickness of the entire antistatic base material. For example, the thickness of the antistatic base material composed of multiple layers means the entire thickness of the antistatic base material. The total thickness of the layers.
抗靜電性基材可為透明，亦可為不透明，還可根據目的而著色。 例如，為了經由抗靜電性基材將保護膜形成用複合片中的保護膜形成用膜進行光學檢查，抗靜電性基材較佳為透明。The antistatic base material may be transparent or opaque, and may be colored according to the purpose. For example, in order to optically inspect the protective film-forming film in the protective film-forming composite sheet via the antistatic base material, the antistatic base material is preferably transparent.
為了提高抗靜電性基材與設置於該抗靜電性基材上之層(例如黏著劑層、中間層或保護膜形成用膜)之接著性，亦可對抗靜電性基材表面實施利用噴砂處理、溶劑處理等之凹凸化處理；電暈放電處理、電子束照射處理、電漿處理、臭氧／紫外線照射處理、火焰處理、鉻酸處理、熱風處理等氧化處理等。另外，亦可對抗靜電性基材表面進行底塗處理。In order to improve the adhesion between the antistatic base material and the layer provided on the antistatic base material (such as an adhesive layer, an intermediate layer or a film for forming a protective film), the surface of the antistatic base material may also be sandblasted. , solvent treatment and other concave and convex treatments; corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments, etc. In addition, the antistatic substrate surface can also be primed.
[抗靜電組成物(VI-2)] 抗靜電性基材例如可藉由將含有前述抗靜電劑及樹脂之抗靜電組成物(VI-2)成形而製造。抗靜電組成物(VI-2)中的常溫下不會氣化的成分彼此的含量比率通常與抗靜電性基材中的前述成分彼此的含量比率相同。[Antistatic composition (VI-2)] The antistatic base material can be produced, for example, by molding the antistatic composition (VI-2) containing the aforementioned antistatic agent and resin. The content ratio of components that do not vaporize at normal temperature in the antistatic composition (VI-2) is generally the same as the content ratio of the above-mentioned components in the antistatic base material.
利用公知的方法將抗靜電組成物(VI-2)成形即可，例如可利用與製造前述基材時，將前述樹脂組成物成形之情形相同的方法進行。The antistatic composition (VI-2) may be molded by a known method. For example, the same method as that used for molding the resin composition when manufacturing the base material may be used.
[抗靜電劑] 作為抗靜電組成物(VI-2)所含有之抗靜電劑，可列舉與前述背面抗靜電層所含有之抗靜電劑相同的化合物。 抗靜電組成物(VI-2)所含有之抗靜電劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。[antistatic agent] Examples of the antistatic agent contained in the antistatic composition (VI-2) include the same compounds as the antistatic agents contained in the back surface antistatic layer. The antistatic agent contained in the antistatic composition (VI-2) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these agents may be selected arbitrarily.
抗靜電組成物(VI-2)及抗靜電性基材中，前述抗靜電劑的含量相對於前述抗靜電劑及樹脂的合計含量之比例較佳為7.5質量%以上，更佳為8.5質量%以上。藉由前述比例為前述下限值以上，保護膜形成用複合片的抗靜電效果變高，結果保護膜形成用膜與半導體晶圓之間的異物混入的抑制效果變高。In the antistatic composition (VI-2) and the antistatic base material, the content of the antistatic agent relative to the total content of the antistatic agent and resin is preferably 7.5% by mass or more, more preferably 8.5% by mass. above. When the ratio is equal to or higher than the lower limit, the antistatic effect of the protective film-forming composite sheet becomes higher, and as a result, the effect of suppressing the mixing of foreign matter between the protective film-forming film and the semiconductor wafer becomes higher.
抗靜電組成物(VI-2)及抗靜電性基材中，前述抗靜電劑的含量相對於前述抗靜電劑及樹脂的合計含量之比例的上限值並無特別限定。例如，就抗靜電劑的相容性更良好之方面而言，前述比例較佳為20質量%以下。In the antistatic composition (VI-2) and the antistatic base material, the upper limit of the ratio of the content of the antistatic agent to the total content of the antistatic agent and resin is not particularly limited. For example, in order to achieve better compatibility with the antistatic agent, the proportion is preferably 20% by mass or less.
前述抗靜電劑的含量之比例可適宜調節為將上述之較佳的下限值及上限值任意組合而設定之範圍內。例如，一實施形態中，前述比例較佳為7.5質量%至20質量%，更佳為8.5質量%至20質量%。但這些係前述比例的一例。The content ratio of the aforementioned antistatic agent can be appropriately adjusted to be within a range set by any combination of the above-mentioned preferred lower limit values and upper limit values. For example, in one embodiment, the aforementioned proportion is preferably 7.5 mass% to 20 mass%, more preferably 8.5 mass% to 20 mass%. But these are examples of the aforementioned proportions.
[樹脂] 作為抗靜電組成物(VI-2)及抗靜電性基材所含有之樹脂，可列舉與前述基材所含有之樹脂相同的樹脂。 抗靜電組成物(VI-2)及抗靜電性基材所含有之前述樹脂可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。[resin] Examples of the resin contained in the antistatic composition (VI-2) and the antistatic base material include the same resins as those contained in the base material. The above-mentioned resins contained in the antistatic composition (VI-2) and the antistatic base material may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily. .
抗靜電組成物(VI-2)中，前述樹脂的含量相對於溶劑以外的全部成分的總含量之比例(亦即，抗靜電性基材中的前述樹脂的含量相對於抗靜電性基材的總質量之比例)較佳為30質量%至99.9質量%，更佳為35質量%至98質量%，進而較佳為60質量%至98質量%，尤佳為85質量%至98質量%。藉由前述比例為前述下限值以上，抗靜電性基材的強度變得更高。藉由前述比例為前述上限值以下，能夠使抗靜電性基材的抗靜電劑的含量更多。In the antistatic composition (VI-2), the ratio of the content of the resin to the total content of all components except the solvent (that is, the content of the resin in the antistatic base material to the amount of the resin in the antistatic base material) The ratio of the total mass) is preferably 30 mass% to 99.9 mass%, more preferably 35 mass% to 98 mass%, further preferably 60 mass% to 98 mass%, particularly preferably 85 mass% to 98 mass%. When the ratio is equal to or higher than the lower limit, the strength of the antistatic base material becomes higher. When the ratio is equal to or less than the upper limit, the content of the antistatic agent in the antistatic base material can be increased.
[光聚合起始劑] 於抗靜電組成物(VI-2)含有能量線硬化性的前述樹脂之情形時，為了高效率地進行前述樹脂的聚合反應，亦可含有光聚合起始劑。 作為抗靜電組成物(VI-2)所含有之前述光聚合起始劑，例如可列舉與黏著劑組成物(I-1)所含有之光聚合起始劑相同的化合物。 抗靜電組成物(VI-2)所含有之光聚合起始劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。 抗靜電組成物(VI-2)中的光聚合起始劑的含量並無特別限定，根據前述樹脂或光聚合起始劑的種類適宜選擇即可。[Photopolymerization initiator] When the antistatic composition (VI-2) contains the energy-beam curable resin, a photopolymerization initiator may be included in order to efficiently carry out the polymerization reaction of the resin. Examples of the photopolymerization initiator contained in the antistatic composition (VI-2) include the same compounds as the photopolymerization initiator contained in the adhesive composition (I-1). The photopolymerization initiator contained in the antistatic composition (VI-2) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily. The content of the photopolymerization initiator in the antistatic composition (VI-2) is not particularly limited and may be appropriately selected depending on the type of the resin or photopolymerization initiator.
[添加劑、溶劑] 抗靜電組成物(VI-2)中，除前述抗靜電劑、樹脂及光聚合起始劑以外，亦可含有不符合這些任一種成分之填充材料、著色劑、抗氧化劑、有機潤滑劑、觸媒、軟化劑(塑化劑)等公知的各種添加劑。 作為抗靜電組成物(VI-2)所含有之前述添加劑，可列舉與上述之黏著劑組成物(I-1)所含有之其他添加劑(但抗靜電劑除外)相同的化合物。 另外，為了提高抗靜電組成物(VI-2)的流動性，亦可含有溶劑。 作為抗靜電組成物(VI-2)所含有之前述溶劑，可列舉與上述之黏著劑組成物(I-1)所含有之溶劑相同的化合物。 抗靜電組成物(VI-2)所含有之抗靜電劑及樹脂分別可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。 抗靜電組成物(VI-2)中的添加劑及溶劑的含量分別無特別限定，根據該添加劑及溶劑的種類適宜選擇即可。[Additives, solvents] In addition to the aforementioned antistatic agent, resin and photopolymerization initiator, the antistatic composition (VI-2) may also contain fillers, colorants, antioxidants, organic lubricants, contacts that do not meet any of these ingredients. Various well-known additives such as media, softeners (plasticizers), etc. Examples of the aforementioned additives contained in the antistatic composition (VI-2) include the same compounds as the other additives contained in the above-mentioned adhesive composition (I-1) (excluding the antistatic agent). In addition, in order to improve the fluidity of the antistatic composition (VI-2), a solvent may be contained. Examples of the solvent contained in the antistatic composition (VI-2) include the same compounds as the solvent contained in the above-mentioned adhesive composition (I-1). The antistatic agent and resin contained in the antistatic composition (VI-2) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily. The contents of the additives and the solvent in the antistatic composition (VI-2) are not particularly limited, and may be appropriately selected according to the types of the additives and solvents.
[抗靜電組成物(VI-2)之製造方法] 抗靜電組成物(VI-2)藉由調配前述抗靜電劑、前述樹脂、及視需要這些以外的成分等用以構成抗靜電組成物(VI-2)之各成分而獲得。 抗靜電組成物(VI-2)除調配成分不同之方面以外，可利用與上述之黏著劑組成物之情形相同的方法製造。[Production method of antistatic composition (VI-2)] The antistatic composition (VI-2) is obtained by blending the above-mentioned antistatic agent, the above-mentioned resin, and optionally other components other than these to form each component of the antistatic composition (VI-2). The antistatic composition (VI-2) can be produced by the same method as the above-mentioned adhesive composition except that the ingredients are different.
○表面抗靜電層 保護膜形成用複合片中的前述表面抗靜電層的配置位置與前述背面抗靜電層不同，但前述表面抗靜電層的構成本身與前述背面抗靜電層相同。例如，表面抗靜電層可使用抗靜電組成物(VI-1)，利用與上文說明之背面抗靜電層之形成方法相同的方法形成。因此，表面抗靜電層的詳細說明省略。 於保護膜形成用複合片一併具備表面抗靜電層及背面抗靜電層之情形時，這些表面抗靜電層及背面抗靜電層相互可相同亦可不同。○Surface antistatic layer The arrangement position of the surface antistatic layer in the protective film-forming composite sheet is different from that of the back surface antistatic layer, but the structure of the surface antistatic layer itself is the same as that of the back surface antistatic layer. For example, the surface antistatic layer can be formed using the antistatic composition (VI-1) by the same method as the formation method of the backside antistatic layer described above. Therefore, detailed description of the surface antistatic layer is omitted. When the composite sheet for forming a protective film is provided with both a surface antistatic layer and a back antistatic layer, these surface antistatic layers and back antistatic layers may be the same as or different from each other.
◎中間層 前述中間層為片狀或膜狀。 如上文所說明，作為較佳的中間層，可列舉一面經剝離處理之剝離性改善層。作為前述剝離性改善層，例如可列舉具備樹脂層、及形成於前述樹脂層上之剝離處理層而構成之由多層所構成之層。保護膜形成用複合片中，剝離性改善層係使該剝離性改善層的剝離處理層朝向保護膜形成用膜側而配置。◎Middle layer The aforementioned intermediate layer is in the form of a sheet or film. As described above, a preferable intermediate layer may include a peelability-improving layer having one side subjected to peeling treatment. Examples of the peelability improving layer include a multi-layered layer including a resin layer and a peeling treatment layer formed on the resin layer. In the composite sheet for protective film formation, the peelability improving layer is arranged so that the peeling treatment layer of the peelability improving layer faces the film side for protective film formation.
剝離性改善層中的前述樹脂層可藉由將含有樹脂之樹脂組成物成形而製作。 並且，剝離性改善層可藉由將前述樹脂層的一面進行剝離處理而製造。The resin layer in the peelability improving layer can be produced by molding a resin composition containing resin. Furthermore, the peelability improving layer can be produced by subjecting one side of the resin layer to a peeling process.
前述樹脂層的剝離處理例如可藉由以下之公知的各種剝離劑進行：醇酸系、聚矽氧系、氟系、不飽和聚酯系、聚烯烴系或蠟系等。 就具有耐熱性之方面而言，前述剝離劑較佳為醇酸系、聚矽氧系或氟系之剝離劑。The peeling treatment of the resin layer can be performed, for example, by using various known peeling agents: alkyd-based, polysiloxane-based, fluorine-based, unsaturated polyester-based, polyolefin-based or wax-based release agents. In terms of heat resistance, the release agent is preferably an alkyd-based, polysiloxane-based or fluorine-based release agent.
作為前述樹脂層的構成材料之樹脂根據目的適宜選擇即可，並無特別限定。 作為較佳的前述樹脂，例如可列舉：聚對苯二甲酸乙二酯(PET；polyethylene terephthalate)、聚萘二甲酸乙二酯(PEN；polyethylene naphthalate)、聚對苯二甲酸丁二酯(PBT；polybutylene terephthalate)、聚乙烯(PE；polyethylene)、聚丙烯(PP；polypropylene)等。The resin that is a constituent material of the resin layer is not particularly limited as long as it is appropriately selected depending on the purpose. Examples of preferred resins include polyethylene terephthalate (PET; polyethylene terephthalate), polyethylene naphthalate (PEN; polyethylene naphthalate), and polybutylene terephthalate (PBT). ; polybutylene terephthalate), polyethylene (PE; polyethylene), polypropylene (PP; polypropylene), etc.
前述中間層無論是否為剝離性改善層，均可由1層(單層)所構成，亦可由2層以上之多層所構成，於由多層所構成之情形時，這些多層相互可相同亦可不同，這些多層的組合並無特別限定。例如，於中間層為剝離性改善層之情形時，前述樹脂層與前述剝離處理層均可由1層(單層)所構成，亦可由2層以上之多層所構成。The aforementioned intermediate layer, regardless of whether it is a peelability-improving layer or not, may be composed of one layer (single layer), or may be composed of two or more multiple layers. When it is composed of multiple layers, these multiple layers may be the same or different from each other. The combination of these multiple layers is not particularly limited. For example, when the intermediate layer is a peelability improving layer, both the resin layer and the peeling treatment layer may be composed of one layer (single layer) or may be composed of two or more layers.
中間層的厚度根據該中間層的種類適宜調節即可，並無特別限定。 例如，剝離性改善層的厚度(樹脂層及剝離處理層的合計厚度)較佳為10nm至2000nm，更佳為25nm至1500nm，尤佳為50nm至1200nm。藉由剝離性改善層的厚度為前述下限值以上，剝離性改善層的作用變得更顯著，進而抑制剝離性改善層之切斷等破損之效果變得更高。藉由剝離性改善層的厚度為前述上限值以下，於後述拾取附保護膜之半導體晶片或附保護膜形成用膜之半導體晶片時，頂起這些晶片之力容易傳遞至這些晶片，從而能夠更容易地進行拾取。The thickness of the intermediate layer can be appropriately adjusted according to the type of the intermediate layer and is not particularly limited. For example, the thickness of the peelability improving layer (the total thickness of the resin layer and the peeling treatment layer) is preferably 10 nm to 2000 nm, more preferably 25 nm to 1500 nm, and particularly preferably 50 nm to 1200 nm. When the thickness of the releasability-improving layer is equal to or greater than the aforementioned lower limit, the effect of the releasability-improving layer becomes more significant, and the effect of suppressing damage such as cutting of the releasability-improving layer becomes even higher. By having the thickness of the releasability improving layer below the above-mentioned upper limit, when a semiconductor wafer with a protective film or a semiconductor wafer with a film for forming a protective film is picked up as will be described later, the force that lifts up the wafers can be easily transmitted to the wafers, so that it is possible to Make picking up easier.
中間層可為透明，亦可為不透明，還可根據目的而著色。 例如，為了經由中間層將保護膜形成用複合片中的保護膜形成用膜進行光學檢查，中間層較佳為透明。The middle layer can be transparent or opaque, and can also be colored according to the purpose. For example, in order to optically inspect the protective film-forming film in the protective film-forming composite sheet via the intermediate layer, the intermediate layer is preferably transparent.
◎保護膜形成用膜 前述保護膜形成用膜藉由熱硬化而成為保護膜。該保護膜係用以保護半導體晶圓或半導體晶片的內面(換言之，與電極形成面為相反側的面)。保護膜形成用膜為軟質，能夠容易地貼附於貼附對象物。◎Film for protective film formation The film for protective film formation becomes a protective film by thermal curing. This protective film is used to protect the semiconductor wafer or the inner surface of the semiconductor wafer (in other words, the surface opposite to the electrode formation surface). The film for forming a protective film is soft and can be easily attached to an object to be attached.
本說明書中，所謂「保護膜形成用膜」，意指熱硬化前的膜，所謂「保護膜」，意指使保護膜形成用膜熱硬化而成之膜。 另外，本說明書中，即便為保護膜形成用膜熱硬化後，只要維持支撐片及保護膜形成用膜之硬化物(換言之，支撐片及保護膜)之積層結構，則亦將該積層結構體稱為「保護膜形成用複合片」。In this specification, the "film for protective film formation" means a film before thermosetting, and the term "protective film" means a film obtained by thermosetting the film for protective film formation. In addition, in this specification, even after the film for protective film formation is thermally cured, as long as the laminated structure of the cured product of the support sheet and the film for protective film formation (in other words, the support sheet and the protective film) is maintained, the laminated structure is also referred to as the laminated structure. It is called "composite sheet for protective film formation".
保護膜形成用膜可由1層(單層)所構成，亦可由2層以上之多層所構成。於保護膜形成用膜由多層所構成之情形時，這些多層相互可相同亦可不同，這些多層的組合並無特別限定。The film for forming a protective film may be composed of one layer (single layer) or may be composed of two or more layers. When the film for forming a protective 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.
保護膜形成用膜的厚度較佳為1μm至100μm，更佳為3μm至80μm，尤佳為5μm至60μm。藉由保護膜形成用膜的厚度為前述下限值以上，能夠形成保護能力更高之保護膜。另外，藉由保護膜形成用膜的厚度為前述上限值以下，能夠避免厚度過厚。 此處，所謂「保護膜形成用膜的厚度」，意指保護膜形成用膜整體的厚度，例如所謂由多層所構成之保護膜形成用膜的厚度，意指構成保護膜形成用膜之全部層的合計厚度。The thickness of the film for forming a protective film is preferably 1 μm to 100 μm, more preferably 3 μm to 80 μm, and particularly preferably 5 μm to 60 μm. When the thickness of the protective film-forming film is not less than the aforementioned lower limit, a protective film with higher protective capability can be formed. In addition, when the thickness of the protective film-forming film is equal to or less than the aforementioned upper limit, excessive thickness can be avoided. Here, the "thickness of the protective film-forming film" means the thickness of the entire protective film-forming film. For example, the thickness of the protective film-forming film composed of multiple layers means the entire thickness of the protective film-forming film. The total thickness of the layers.
[保護膜形成用組成物] 保護膜形成用膜可使用含有該保護膜形成用膜的構成材料之保護膜形成用組成物而形成。例如，保護膜形成用膜可藉由於該保護膜形成用膜的形成對象面塗敷保護膜形成用組成物，並視需要使之乾燥而形成。保護膜形成用組成物中的常溫下不會氣化的成分彼此的含量比率通常與保護膜形成用膜中的前述成分彼此的含量比率相同。[Composition for protective film formation] The protective film-forming film can be formed using a protective film-forming composition containing a constituent material of the protective film-forming film. For example, the protective film-forming film can be formed by applying the protective film-forming composition to a surface to be formed of the protective film-forming film and drying it if necessary. The content ratio of components that do not vaporize at normal temperature in the protective film-forming composition is generally the same as the content ratio of the aforementioned components in the protective film-forming film.
例如可利用與上述塗敷黏著劑組成物之情形相同的方法塗敷保護膜形成用組成物。For example, the protective film forming composition can be applied by the same method as the above-mentioned application of the adhesive composition.
保護膜形成用組成物的乾燥條件並無特別限定。但於保護膜形成用組成物含有後述溶劑之情形時，較佳為進行加熱乾燥。並且，含有溶劑之保護膜形成用組成物例如較佳為於70℃至130℃且10秒至5分鐘之條件進行加熱乾燥，較佳為以該組成物本身及由該組成物所形成之保護膜形成用膜不熱硬化之方式進行加熱乾燥。The drying conditions of the protective film forming composition are not particularly limited. However, when the composition for forming a protective film contains a solvent described below, it is preferred to perform heating and drying. Furthermore, the composition for forming a protective film containing a solvent is preferably heated and dried at 70°C to 130°C for 10 seconds to 5 minutes, and it is preferred that the composition itself and the protection formed by the composition The film is formed by heating and drying without thermal hardening of the film.
關於將保護膜形成用膜貼附於半導體晶圓的內面並使之熱硬化而形成保護膜時的硬化條件，只要保護膜成為充分地發揮該保護膜的功能之程度的硬化度，則並無特別限定，根據保護膜形成用膜的種類適宜選擇即可。 例如，保護膜形成用膜之熱硬化時的加熱溫度較佳為100℃至200℃，更佳為110℃至180℃，尤佳為120℃至170℃。並且，前述熱硬化時的加熱時間較佳為0.5小時至5小時，更佳為0.5小時至3小時，尤佳為1小時至2小時。Regarding the curing conditions when a protective film-forming film is attached to the inner surface of a semiconductor wafer and thermally cured to form a protective film, as long as the protective film has a degree of curing that sufficiently exerts the function of the protective film, It is not particularly limited and may be appropriately selected according to the type of film for forming a protective film. For example, the heating temperature during thermosetting of the film for forming a protective film is preferably 100°C to 200°C, more preferably 110°C to 180°C, and particularly preferably 120°C to 170°C. Moreover, the heating time during the thermal hardening is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours, and even more preferably 1 to 2 hours.
作為較佳的保護膜形成用膜，例如可列舉含有聚合物成分(A)及熱硬化性成分(B)之膜。聚合物成分(A)係被視為聚合性化合物進行聚合反應而形成之成分。另外，熱硬化性成分(B)係可將熱作為反應之觸發而進行硬化(聚合)反應之成分。此外，本說明書中，聚合反應亦包括縮聚反應。As a preferable film for protective film formation, a film containing a polymer component (A) and a thermosetting component (B) can be mentioned, for example. The polymer component (A) is a component formed by polymerization reaction as a polymerizable compound. In addition, the thermosetting component (B) is a component that can perform a curing (polymerization) reaction using heat as a trigger for the reaction. In addition, in this specification, polymerization reaction also includes polycondensation reaction.
[熱硬化性保護膜形成用組成物(III-1)] 作為較佳的熱硬化性保護膜形成用組成物，例如可列舉含有前述聚合物成分(A)及熱硬化性成分(B)之熱硬化性保護膜形成用組成物(III-1)(本說明書中，有時僅簡稱為「組成物(III-1)」)等。[Thermosetting protective film forming composition (III-1)] As a preferred composition for forming a thermosetting protective film, for example, the composition for forming a thermosetting protective film (III-1) containing the aforementioned polymer component (A) and the thermosetting component (B) can be cited. In the specification, it may be simply referred to as "composition (III-1)"), etc.
[聚合物成分(A)] 聚合物成分(A)係用以對保護膜形成用膜賦予造膜性以及／或者可撓性等之成分。 組成物(III-1)及保護膜形成用膜所含有之聚合物成分(A)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。[Polymer component (A)] The polymer component (A) is a component for imparting film-forming properties and/or flexibility to the protective film-forming film. The polymer component (A) contained in the composition (III-1) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be Take your pick.
作為聚合物成分(A)，例如可列舉：丙烯酸系樹脂、聚酯、胺基甲酸酯系樹脂、丙烯酸胺基甲酸酯樹脂、聚矽氧系樹脂、橡膠系樹脂、苯氧基樹脂、熱硬化性聚醯亞胺等，較佳為丙烯酸系樹脂。Examples of the polymer component (A) include acrylic resin, polyester, urethane resin, acrylic urethane resin, silicone resin, rubber resin, and phenoxy resin. Thermosetting polyimide, etc., preferably acrylic resin.
作為聚合物成分(A)中的前述丙烯酸系樹脂，可列舉公知的丙烯酸聚合物。 丙烯酸系樹脂的重量平均分子量(Mw)較佳為10000至2000000，更佳為100000至1500000。藉由丙烯酸系樹脂的重量平均分子量為前述下限值以上，保護膜形成用膜的形狀穩定性(保管時的經時穩定性)提高。另外，藉由丙烯酸系樹脂的重量平均分子量為前述上限值以下，保護膜形成用膜變得易於追隨於被接著體的凹凸面，能夠進一步抑制於被接著體與保護膜形成用膜之間產生空隙(void)等。 此外，本說明書中，所謂重量平均分子量，只要無特別說明，則係指藉由凝膠滲透層析(GPC；Gel Permeation Chromatography)法所測定之聚苯乙烯換算值。Examples of the acrylic resin in the polymer component (A) include known acrylic polymers. The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is equal to or higher than the aforementioned lower limit, the shape stability of the film for protective film formation (stability over time during storage) is improved. In addition, when the weight average molecular weight of the acrylic resin is equal to or less than the aforementioned upper limit, the protective film-forming film becomes easy to follow the uneven surface of the adherend, and can further suppress interference between the adherend and the protective film-forming film. Produce voids, etc. In addition, in this specification, the weight average molecular weight refers to the polystyrene-converted value measured by gel permeation chromatography (GPC; Gel Permeation Chromatography) unless otherwise specified.
丙烯酸系樹脂的玻璃轉移溫度(Tg)較佳為-60℃至70℃，更佳為-30℃至50℃。藉由丙烯酸系樹脂的Tg為前述下限值以上，例如保護膜形成用膜之硬化物與支撐片之接著力受到抑制，支撐片的剝離性適度提高。另外，藉由丙烯酸系樹脂的Tg為前述上限值以下，保護膜形成用膜及其硬化物與被接著體之接著力提高。 此外，並不限定於丙烯酸系樹脂，本說明書中的樹脂的Tg例如藉由下述方式求出，亦即，使用示差掃描熱量計(DSC；Differential Scanning Calorimeter)，將升溫速度或降溫速度設為10℃/min，於-70℃至150℃之間使測定對象物的溫度變化，確認反曲點。The glass transition temperature (Tg) of the acrylic resin is preferably -60°C to 70°C, more preferably -30°C to 50°C. When the Tg of the acrylic resin is equal to or higher than the aforementioned lower limit, for example, the adhesive force between the cured product of the protective film-forming film and the support sheet is suppressed, and the peelability of the support sheet is moderately improved. In addition, when the Tg of the acrylic resin is equal to or less than the aforementioned upper limit, the adhesive force between the protective film-forming film and its cured product and the adherend is improved. In addition, it is not limited to acrylic resin. The Tg of the resin in this specification is determined by, for example, using a differential scanning calorimeter (DSC; Differential Scanning Calorimeter) and setting the temperature increase rate or temperature decrease rate to 10°C/min, change the temperature of the object to be measured between -70°C and 150°C, and confirm the inflection point.
作為丙烯酸系樹脂，例如可列舉：1種或2種以上之(甲基)丙烯酸酯之聚合物；選自(甲基)丙烯酸、衣康酸、乙酸乙烯酯、丙烯腈、苯乙烯及N-羥甲基丙烯醯胺等中的2種以上之單體之共聚物等。Examples of the acrylic resin include polymers of one or more (meth)acrylic acid esters selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N- Copolymers of two or more monomers such as hydroxymethylacrylamide, etc.
此外，本說明書中，「(甲基)丙烯酸」的概念包括「丙烯酸」及「甲基丙烯酸」兩者。關於與(甲基)丙烯酸類似之用語亦相同，例如「(甲基)丙烯醯基」的概念包括「丙烯醯基」及「甲基丙烯醯基」兩者，「(甲基)丙烯酸酯」的概念包括「丙烯酸酯」及「甲基丙烯酸酯」兩者。In addition, in this specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid. For example, the concept of "(meth)acrylyl" includes both "acrylyl" and "methacrylyl", and "(meth)acrylate" The concept includes both "acrylate" and "methacrylate".
作為構成丙烯酸系樹脂之前述(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯((甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯((甲基)丙烯酸肉豆蔻酯)、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯((甲基)丙烯酸棕櫚酯)、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯((甲基)丙烯酸硬脂酯)等構成烷基酯之烷基為碳數為1至18之鏈狀結構之(甲基)丙烯酸烷基酯；(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊酯等(甲基)丙烯酸環烷基酯；(甲基)丙烯酸苄酯等(甲基)丙烯酸芳烷基酯；(甲基)丙烯酸二環戊烯酯等(甲基)丙烯酸環烯酯；(甲基)丙烯酸二環戊烯氧基乙酯等(甲基)丙烯酸環烯氧基烷基酯；(甲基)丙烯醯亞胺；(甲基)丙烯酸縮水甘油酯等含縮水甘油基之(甲基)丙烯酸酯；(甲基)丙烯酸羥基甲酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等含羥基之(甲基)丙烯酸酯；(甲基)丙烯酸N-甲基胺基乙酯等含取代胺基之(甲基)丙烯酸酯等。此處，所謂「取代胺基」，意指胺基的1個或2個氫原子被氫原子以外的基取代而成之基。Examples of the (meth)acrylate constituting the acrylic resin include: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid isopropyl acrylate Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate Hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-octyl (meth)acrylate Nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate) , Tridecyl (meth)acrylate, Myristyl (meth)acrylate (Myristyl (meth)acrylate), Pentadecyl (meth)acrylate, Tendecyl (meth)acrylate Hexaalkyl ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. constitute alkyl esters The alkyl group is a (meth)acrylic acid alkyl ester with a chain structure of 1 to 18 carbon atoms; (meth)acrylic acid cycloalkanes such as (meth)acrylic acid isobornyl ester, (meth)acrylic acid dicyclopentyl ester, etc. (meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate; (meth)acrylic acid cycloalkyl esters such as (meth)dicyclopentenyl acrylate; (meth)acrylic acid dicyclopentene (meth)acrylic acid cycloalkenyloxyalkyl esters such as oxyethyl ester; (meth)acrylimide; (meth)acrylic acid glycidyl ester and other glycidyl group-containing (meth)acrylates; Hydroxymethyl acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate , 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyl-containing (meth)acrylates; N-methylaminoethyl (meth)acrylate and other substituted amines Based on (meth)acrylate, etc. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of the amino group are substituted with a group other than hydrogen atoms.
丙烯酸系樹脂例如除前述(甲基)丙烯酸酯以外，亦可為使選自(甲基)丙烯酸、衣康酸、乙酸乙烯酯、丙烯腈、苯乙烯及N-羥甲基丙烯醯胺等中的1種或2種以上之單體進行共聚而成之丙烯酸系樹脂。For example, the acrylic resin may be selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, etc., in addition to the aforementioned (meth)acrylate. Acrylic resin formed by copolymerizing one or more monomers.
構成丙烯酸系樹脂之單體可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The monomer constituting the acrylic resin may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily.
丙烯酸系樹脂亦可具有乙烯基、(甲基)丙烯醯基、胺基、羥基、羧基、異氰酸酯基等能夠與其他化合物鍵結之官能基。丙烯酸系樹脂的前述官能基可經由後述交聯劑(F)與其他化合物鍵結，亦可不經由交聯劑(F)而與其他化合物直接鍵結。藉由丙烯酸系樹脂經由前述官能基與其他化合物鍵結，有使用保護膜形成用複合片所獲得之封裝體的可靠性提高之傾向。Acrylic resins may also have functional groups capable of bonding with other compounds, such as vinyl groups, (meth)acrylyl groups, amine groups, hydroxyl groups, carboxyl groups, and isocyanate groups. The aforementioned functional group of the acrylic resin may be bonded to other compounds via the cross-linking agent (F) described below, or may be directly bonded to other compounds without the cross-linking agent (F). Since the acrylic resin is bonded to other compounds via the functional groups, the reliability of the package obtained using the protective film-forming composite sheet tends to be improved.
本實施形態中，作為聚合物成分(A)，可不使用丙烯酸系樹脂而單獨使用丙烯酸系樹脂以外的熱塑性樹脂(以下，有時僅簡稱為「熱塑性樹脂」)，亦可與丙烯酸系樹脂併用。藉由使用前述熱塑性樹脂，有時樹脂膜自支撐片之剝離性提高，或保護膜形成用膜變得易於追隨於被接著體的凹凸面，能夠進一步抑制於被接著體與保護膜形成用膜之間產生空隙等。In this embodiment, as the polymer component (A), a thermoplastic resin other than the acrylic resin may be used alone instead of the acrylic resin (hereinafter, sometimes simply referred to as "thermoplastic resin"), or may be used in combination with the acrylic resin. By using the aforementioned thermoplastic resin, the peelability of the resin film self-supporting sheet may be improved, or the protective film-forming film may become easier to follow the uneven surface of the adherend, which can further suppress the separation between the adherend and the protective film-forming film. Gaps are created between them.
前述熱塑性樹脂的重量平均分子量較佳為1000至100000，更佳為3000至80000。The weight average molecular weight of the aforementioned thermoplastic resin is preferably 1,000 to 100,000, more preferably 3,000 to 80,000.
前述熱塑性樹脂的玻璃轉移溫度(Tg)較佳為-30℃至150℃，更佳為-20℃至120℃。The glass transition temperature (Tg) of the thermoplastic resin is preferably -30°C to 150°C, more preferably -20°C to 120°C.
作為前述熱塑性樹脂，例如可列舉：聚酯、聚胺基甲酸酯、苯氧基樹脂、聚丁烯、聚丁二烯、聚苯乙烯等。Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, and the like.
組成物(III-1)及保護膜形成用膜所含有之前述熱塑性樹脂可僅為1種，亦可為2種以上，於為2種以上之情形時，這些熱塑性樹脂的組合及比率可任意選擇。The aforementioned thermoplastic resin contained in the composition (III-1) and the 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 thermoplastic resins may be arbitrary. select.
組成物(III-1)中，無論聚合物成分(A)的種類如何，聚合物成分(A)的含量相對於溶劑以外的全部成分的總含量之比例(亦即，保護膜形成用膜中的聚合物成分(A)的含量相對於保護膜形成用膜的總質量之比例)均較佳為5質量%至85質量%，更佳為5質量%至80質量%，例如可為5質量%至65質量%、5質量%至50質量%、以及5質量%至35質量%之任一者。In the composition (III-1), regardless of the type of the polymer component (A), the ratio of the content of the polymer component (A) to the total content of all components except the solvent (that is, in the film for protective film formation The content of the polymer component (A) relative to the total mass of the film for protective film formation) is preferably 5 mass% to 85 mass%, more preferably 5 mass% to 80 mass%, for example, it can be 5 mass% Any one of % to 65% by mass, 5% to 50% by mass, and 5% to 35% by mass.
聚合物成分(A)有時亦符合熱硬化性成分(B)。本實施形態中，於組成物(III-1)含有此種符合聚合物成分(A)及熱硬化性成分(B)兩者之成分之情形時，組成物(III-1)視為含有聚合物成分(A)及熱硬化性成分(B)。The polymer component (A) may also correspond to the thermosetting component (B). In this embodiment, when the composition (III-1) contains such a component that corresponds to both the polymer component (A) and the thermosetting component (B), the composition (III-1) is regarded as containing a polymer component. Physical 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用膜硬化之成分。 組成物(III-1)及保護膜形成用膜所含有之熱硬化性成分(B)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。[Thermosetting 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-1) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these You can choose whatever you want.
作為熱硬化性成分(B)，例如可列舉：環氧系熱硬化性樹脂、熱硬化性聚醯亞胺、聚胺基甲酸酯、不飽和聚酯、聚矽氧樹脂等，較佳為環氧系熱硬化性樹脂。Examples of the thermosetting component (B) include epoxy thermosetting resin, thermosetting polyimide, polyurethane, unsaturated polyester, polysiloxane resin, etc., and preferred ones are Epoxy thermosetting resin.
(環氧系熱硬化性樹脂) 環氧系熱硬化性樹脂由環氧樹脂(B1)及熱硬化劑(B2)所構成。 組成物(III-1)及保護膜形成用膜所含有之環氧系熱硬化性樹脂可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。(Epoxy thermosetting resin) The epoxy thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2). The epoxy-based thermosetting resin contained in the composition (III-1) and the 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 You can choose whatever you want.
・環氧樹脂(B1) 作為環氧樹脂(B1)，可列舉公知的環氧樹脂，例如可列舉：多官能系環氧樹脂、聯苯化合物、雙酚A二縮水甘油醚及其氫化物、鄰甲酚酚醛清漆環氧樹脂、二環戊二烯型環氧樹脂、聯苯型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、伸苯基骨架型環氧樹脂等2官能以上之環氧化合物。・Epoxy resin (B1) Examples of the epoxy resin (B1) include known epoxy resins. Examples include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, and o-cresol novolak epoxy. Resin, dicyclopentadiene-type epoxy resin, biphenyl-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenylene skeleton type epoxy resin and other 2-functional or higher epoxy resins compound.
作為環氧樹脂(B1)，亦可使用具有不飽和烴基之環氧樹脂。具有不飽和烴基之環氧樹脂相較於不具有不飽和烴基之環氧樹脂而言，與丙烯酸系樹脂之相容性較高。因此，藉由使用具有不飽和烴基之環氧樹脂，使用保護膜形成用複合片所獲得之附樹脂膜之半導體晶片的可靠性提高。As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can also be used. Epoxy resins with unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the resin film-attached semiconductor wafer obtained using the composite sheet for forming a protective film is improved.
作為具有不飽和烴基之環氧樹脂，例如可列舉：多官能系環氧樹脂的一部分環氧基變換為具有不飽和烴基之基而成之化合物。此種化合物例如藉由使(甲基)丙烯酸或其衍生物與環氧基進行加成反應而獲得。 另外，作為具有不飽和烴基之環氧樹脂，例如可列舉：構成環氧樹脂之芳香環等上直接鍵結有具有不飽和烴基之基之化合物等。 不飽和烴基為具有聚合性之不飽和基，作為該不飽和烴基的具體例，可列舉：次乙基(乙烯基)、2-丙烯基(烯丙基)、(甲基)丙烯醯基、(甲基)丙烯醯胺基等，較佳為丙烯醯基。Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a part of the epoxy groups of a polyfunctional epoxy resin is converted into a group having an unsaturated hydrocarbon group. Such a compound is obtained, for example, by addition reaction of (meth)acrylic acid or a derivative thereof and an epoxy group. Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring constituting the epoxy resin. The unsaturated hydrocarbon group is a polymerizable unsaturated group. Specific examples of the unsaturated hydrocarbon group include: ethylidene (vinyl), 2-propenyl (allyl), (meth)acrylyl, (Meth)acrylamide group and the like, preferably acrylyl group.
環氧樹脂(B1)的數量平均分子量並無特別限定，就保護膜形成用膜的硬化性、以及硬化後的樹脂膜的強度及耐熱性之方面而言，較佳為300至30000，更佳為300至10000，尤佳為300至3000。 本說明書中，所謂數量平均分子量，只要無特別說明，則係指藉由凝膠滲透層析(GPC)法所測定之聚苯乙烯換算值。 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。 本說明書中，所謂「環氧當量」，意指包含1克當量之環氧基之環氧化合物的克數(g/eq)，可依據JIS K 7236：2001之方法進行測定。The number average molecular weight of the epoxy resin (B1) is not particularly limited, but in terms of the curability of the protective film-forming film and the strength and heat resistance of the cured resin film, it is preferably 300 to 30,000, more preferably The range is 300 to 10,000, preferably 300 to 3,000. In this specification, the number average molecular weight refers to the polystyrene-converted value measured by gel permeation chromatography (GPC) unless otherwise specified. The epoxy equivalent of the epoxy resin (B1) is preferably 100g/eq to 1000g/eq, more preferably 150g/eq to 950g/eq. In this specification, "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured according to the method of JIS K 7236:2001.
環氧樹脂(B1)可單獨使用1種，亦可併用2種以上，於併用2種以上之情形時，這些的組合及比率可任意選擇。One type of epoxy resin (B1) may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the combination and ratio of these may be selected arbitrarily.
・熱硬化劑(B2) 熱硬化劑(B2)發揮針對環氧樹脂(B1)之硬化劑的功能。 作為熱硬化劑(B2)，例如可列舉：1分子中具有2個以上之可與環氧基反應之官能基之化合物。作為前述官能基，例如可列舉：酚性羥基、醇性羥基、胺基、羧基、酸基經酐化而成之基等，較佳為酚性羥基、胺基、或酸基經酐化而成之基，更佳為酚性羥基或胺基。・Thermal hardener (B2) The thermal hardener (B2) functions as a hardener for the epoxy resin (B1). Examples of the thermosetting agent (B2) include compounds having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, an acidic group and the like, and preferably a phenolic hydroxyl group, an alcoholic hydroxyl group, an acidic group and an anhydride group. The group is preferably a phenolic hydroxyl group or an amine group.
熱硬化劑(B2)中，作為具有酚性羥基之酚系硬化劑，例如可列舉：多官能酚樹脂、聯苯酚、酚醛清漆型酚樹脂、二環戊二烯系酚樹脂、芳烷基型酚樹脂等。 熱硬化劑(B2)中，作為具有胺基之胺系硬化劑，例如可列舉：二氰二胺等。Among the thermal curing agents (B2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-based phenol resins, and aralkyl-type phenol resins. Phenol resin, etc. Among the thermal curing agents (B2), examples of the amine-based curing agent having an amino group include dicyandiamide and the like.
熱硬化劑(B2)亦可具有不飽和烴基。 作為具有不飽和烴基之熱硬化劑(B2)，例如可列舉：酚樹脂的一部分羥基被具有不飽和烴基之基取代而成之化合物、酚樹脂的芳香環上直接鍵結具有不飽和烴基之基而成之化合物等。 熱硬化劑(B2)中的前述不飽和烴基與上述之具有不飽和烴基之環氧樹脂中的不飽和烴基相同。The thermal hardener (B2) may have an unsaturated hydrocarbon group. Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include a compound in which a part of the hydroxyl groups of a phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a group having an unsaturated hydrocarbon group directly bonded to the aromatic ring of the phenol resin. Compounds formed, etc. The aforementioned unsaturated hydrocarbon group in the thermal hardener (B2) is the same as the aforementioned unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group.
於使用酚系硬化劑作為熱硬化劑(B2)之情形時，就保護膜自支撐片之剝離性提高之方面而言，熱硬化劑(B2)較佳為軟化點或玻璃轉移溫度高的酚系硬化劑。When a phenolic hardener is used as the thermal hardener (B2), in order to improve the peelability of the protective film self-supporting sheet, the thermal hardener (B2) is preferably a phenol with a high softening point or glass transition temperature. Hardener.
熱硬化劑(B2)中，例如多官能酚樹脂、酚醛清漆型酚樹脂、二環戊二烯型酚樹脂、芳烷基型酚樹脂等樹脂成分的數量平均分子量較佳為300至30000，更佳為400至10000，尤佳為500至3000。 熱硬化劑(B2)中，例如聯苯酚、雙氰胺等非樹脂成分的分子量並無特別限定，例如較佳為60至500。In the thermal hardener (B2), the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, aralkyl type phenol resin, etc. is preferably 300 to 30,000, more preferably 300 to 30,000. The best value is 400 to 10,000, especially the best value is 500 to 3,000. In the thermosetting agent (B2), the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.
熱硬化劑(B2)可單獨使用1種，亦可併用2種以上，於併用2種以上之情形時，這些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 can be selected arbitrarily.
組成物(III-1)及保護膜形成用膜中，熱硬化劑(B2)的含量相對於環氧樹脂(B1)的含量100質量份，較佳為0.1質量份至500質量份，更佳為1質量份至200質量份，例如可為1質量份至100質量份、1質量份至50質量份、1質量份至25質量份、以及1質量份至10質量份之任一者。 藉由熱硬化劑(B2)的前述含量為前述下限值以上，保護膜形成用膜變得更容易進行硬化。藉由熱硬化劑(B2)的前述含量為前述上限值以下，保護膜形成用膜的吸濕率降低，使用保護膜形成用複合片所獲得之封裝體的可靠性進一步提高。In the composition (III-1) and the film for forming a protective film, the content of the thermosetting agent (B2) is preferably 0.1 to 500 parts by mass relative to 100 parts by mass of the epoxy resin (B1), and more preferably It is 1 to 200 parts by mass, for example, any one of 1 to 100 parts by mass, 1 to 50 parts by mass, 1 to 25 parts by mass, and 1 to 10 parts by mass. When the aforementioned content of the thermosetting agent (B2) is equal to or more than the aforementioned lower limit, the film for protective film formation becomes easier to cure. When the content of the thermosetting agent (B2) is equal to or less than the upper limit, the moisture absorption rate of the film for protective film formation is reduced, and the reliability of the package obtained using the composite sheet for protective film formation is further improved.
組成物(III-1)及保護膜形成用膜中，熱硬化性成分(B)的含量(例如環氧樹脂(B1)及熱硬化劑(B2)的總含量)相對於聚合物成分(A)的含量100質量份，較佳為20質量份至500質量份，更佳為25質量份至300質量份，進而較佳為30質量份至150質量份，例如可為35質量份至100質量份、以及40質量份至80質量份之任一者。藉由熱硬化性成分(B)的前述含量為此種範圍，例如保護膜形成用膜之硬化物與支撐片之接著力受到抑制，支撐片的剝離性提高。In the composition (III-1) and the protective film-forming film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) relative to the polymer component (A ) content is 100 parts by mass, preferably 20 parts by mass to 500 parts by mass, more preferably 25 parts by mass to 300 parts by mass, further preferably 30 parts by mass to 150 parts by mass, for example, 35 parts by mass to 100 parts by mass parts, and any one from 40 parts by mass to 80 parts by mass. When the aforementioned content of the thermosetting component (B) is in such a range, for example, the adhesive force between the cured product of the protective film-forming film and the support sheet is suppressed, and the peelability of the support sheet is improved.
[硬化促進劑(C)] 組成物(III-1)及保護膜形成用膜亦可含有硬化促進劑(C)。硬化促進劑(C)係用以調整組成物(III-1)的硬化速度之成分。 作為較佳的硬化促進劑(C)，例如可列舉：三乙二胺、苄基二甲胺、三乙醇胺、二甲胺基乙醇、三(二甲胺基甲基)苯酚等三級胺；2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑等咪唑類(1個以上之氫原子被氫原子以外的基取代而成之咪唑)；三丁基膦、二苯基膦、三苯基膦等有機膦類(1個以上之氫原子被有機基取代而成之膦)；四苯基硼酸四苯基鏻、四苯基硼酸三苯基膦等四苯基硼鹽等。[Harding accelerator (C)] The composition (III-1) and the film for protective film formation may contain a hardening accelerator (C). The hardening accelerator (C) is a component for adjusting the hardening speed of the composition (III-1). Preferred hardening accelerators (C) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethylimidazole (imidazole in which more than one hydrogen atom is replaced by a group other than a hydrogen atom); organic phosphines such as tributylphosphine, diphenylphosphine and triphenylphosphine (one or more hydrogen atoms substituted with a group other than hydrogen atom) Phosphines in which hydrogen atoms are substituted by organic groups); tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate.
組成物(III-1)及保護膜形成用膜所含有之硬化促進劑(C)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The hardening accelerator (C) contained in the composition (III-1) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be Take your pick.
於使用硬化促進劑(C)之情形時，組成物(III-1)及保護膜形成用膜中，硬化促進劑(C)的含量相對於熱硬化性成分(B)的含量100質量份，較佳為0.01質量份至10質量份，更佳為0.1質量份至7質量份。藉由硬化促進劑(C)的前述含量為前述下限值以上，能夠獲得更顯著的由使用硬化促進劑(C)所帶來之效果。藉由硬化促進劑(C)的含量為前述上限值以下，例如抑制高極性的硬化促進劑(C)於高溫、高濕度條件下在保護膜形成用膜中朝與被接著體之接著界面側移動而偏析之效果變高。結果為，使用保護膜形成用複合片所獲得之附保護膜之半導體晶片的可靠性進一步提高。When a hardening accelerator (C) is used, the content of the hardening accelerator (C) in the composition (III-1) and the protective film-forming film is 100 parts by mass relative to the content of the thermosetting component (B). Preferably, it is 0.01 to 10 parts by mass, and more preferably, it is 0.1 to 7 parts by mass. When the aforementioned content of the hardening accelerator (C) is equal to or higher than the aforementioned lower limit, more significant effects brought about by the use of the hardening accelerator (C) can be obtained. By keeping the content of the hardening accelerator (C) below the aforementioned upper limit, for example, the highly polar hardening accelerator (C) is suppressed from moving toward the bonding interface with the adherend in the protective film-forming film under high temperature and high humidity conditions. The effect of segregation becomes higher as it moves sideways. As a result, the reliability of the protective film-attached semiconductor wafer obtained using the protective film forming composite sheet is further improved.
[填充材料(D)] 組成物(III-1)及保護膜形成用膜亦可含有填充材料(D)。藉由保護膜形成用膜含有填充材料(D)，使保護膜形成用膜硬化而獲得之保護膜容易調整熱膨脹係數，使該熱膨脹係數最適於保護膜之形成對象物，藉此使用保護膜形成用複合片所獲得之附保護膜之半導體晶片的可靠性進一步提高。另外，藉由保護膜形成用膜含有填充材料(D)，亦能夠降低保護膜的吸濕率，或提高散熱性。[Filling material (D)] The composition (III-1) and the film for protective film formation may contain a filler (D). Since the film for protective film formation contains the filler (D), the protective film obtained by hardening the film for protective film formation can easily adjust the thermal expansion coefficient so that the thermal expansion coefficient is optimal for the object to be formed of the protective film, thereby forming the protective film The reliability of the semiconductor wafer with protective film obtained by using the composite sheet is further improved. In addition, when the film for protective film formation contains the filler (D), the moisture absorption rate of the protective film can also be reduced or the heat dissipation property can be improved.
填充材料(D)可為有機填充材料及無機填充材料之任一者，較佳為無機填充材料。 作為較佳的無機填充材料，例如可列舉：二氧化矽、氧化鋁、滑石、碳酸鈣、鈦白、鐵丹、碳化矽、氮化硼等的粉末；將這些無機填充材料球形化而成之珠粒；這些無機填充材料的表面改質品；這些無機填充材料的單晶纖維；玻璃纖維等。 這些之中，無機填充材料較佳為二氧化矽或氧化鋁，更佳為二氧化矽。The filler (D) may be either an organic filler or an inorganic filler, and an inorganic filler is preferred. Preferable inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium dioxide, titanium dioxide, silicon carbide, boron nitride, etc.; these inorganic fillers are formed into spherical shapes. Beads; surface modifications of these inorganic filler materials; single crystal fibers of these inorganic filler materials; glass fibers, etc. Among these, the inorganic filler material is preferably silica or alumina, and more preferably silica.
組成物(III-1)及保護膜形成用膜所含有之填充材料(D)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The filler material (D) contained in the composition (III-1) and the film for forming a protective film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be arbitrary. select.
組成物(III-1)中，填充材料(D)的含量相對於溶劑以外的全部成分的總含量之比例(亦即，保護膜形成用膜中的填充材料(D)的含量相對於保護膜形成用膜的總質量之比例)較佳為5質量%至80質量%，更佳為10質量%至70質量%，例如可為20質量%至65質量%、30質量%至65質量%、以及40質量%至65質量%之任一者。藉由前述比例為此種範圍，上述之保護膜的熱膨脹係數之調整變得更容易。In the composition (III-1), the ratio of the content of the filler (D) to the total content of all components except the solvent (that is, the content of the filler (D) in the protective film-forming film relative to the total content of the protective film) The ratio of the total mass of the film to be formed) is preferably 5% to 80% by mass, more preferably 10% to 70% by mass, for example, 20% to 65% by mass, 30% to 65% by mass, and any one from 40 mass% to 65 mass%. By keeping the aforementioned ratio within this range, it becomes easier to adjust the thermal expansion coefficient of the protective film.
[偶合劑(E)] 組成物(III-1)及保護膜形成用膜亦可含有偶合劑(E)。藉由使用具有能夠與無機化合物或有機化合物反應之官能基之化合物作為偶合劑(E)，能夠提高保護膜形成用膜對被接著體之接著性及密接性。另外，藉由使用偶合劑(E)，保護膜形成用膜之硬化物不損害耐熱性而耐水性提高。[Coupling agent (E)] The composition (III-1) and the film for forming a protective film may contain a coupling agent (E). By using a compound having a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (E), the adhesiveness and adhesiveness of the protective film-forming film to the adherend can be improved. In addition, by using the coupling agent (E), the cured product of the protective film forming film has improved water resistance without impairing the heat resistance.
偶合劑(E)較佳為具有能夠與聚合物成分(A)、熱硬化性成分(B)等所具有之官能基反應之官能基之化合物，更佳為矽烷偶合劑。 作為較佳的前述矽烷偶合劑，例如可列舉：3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基甲基二乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基甲基二乙氧基矽烷、3-(苯基胺基)丙基三甲氧基矽烷、3-苯胺基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、雙(3-三乙氧基矽烷基丙基)四硫化物、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、咪唑矽烷等。The coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional group possessed by the polymer component (A), the thermosetting component (B), etc., and is more preferably a silane coupling agent. Preferred silane coupling agents include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyl Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethyl Oxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl Diethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethyl Oxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, ethylene Trimethoxysilane, vinyltriethyloxysilane, imidazolesilane, etc.
組成物(III-1)及保護膜形成用膜所含有之偶合劑(E)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The coupling agent (E) contained in the composition (III-1) and the 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 may be arbitrary. select.
於使用偶合劑(E)之情形時，組成物(III-1)及保護膜形成用膜中，偶合劑(E)的含量相對於聚合物成分(A)及熱硬化性成分(B)的總含量100質量份，較佳為0.03質量份至20質量份，更佳為0.05質量份至10質量份，尤佳為0.1質量份至5質量份。藉由偶合劑(E)的前述含量為前述下限值以上，填充材料(D)於樹脂中之分散性提高，以及／或者保護膜形成用膜與被接著體之接著性提高等，能夠獲得更顯著的由使用偶合劑(E)所帶來之效果。另外，藉由偶合劑(E)的前述含量為前述上限值以下，能夠進一步抑制產生逸氣。When a coupling agent (E) is used, the content of the coupling agent (E) in the composition (III-1) and the film for forming a protective film is determined relative to the polymer component (A) and the thermosetting component (B). The total content is 100 parts by mass, preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass. When the content of the coupling agent (E) is equal to or higher than the lower limit, the dispersibility of the filler (D) in the resin is improved, and/or the adhesion between the protective film-forming film and the adherend is improved, etc., it is possible to obtain The effect brought about by the use of coupling agent (E) is more significant. In addition, when the aforementioned content of the coupling agent (E) is equal to or less than the aforementioned upper limit, the generation of outgassing can be further suppressed.
[交聯劑(F)] 作為聚合物成分(A)若使用上述丙烯酸系樹脂等具有能夠與其他化合物鍵結之官能基，例如乙烯基、(甲基)丙烯醯基、胺基、羥基、羧基、異氰酸酯基等之情形時，組成物(III-1)及保護膜形成用膜亦可含有交聯劑(F)。交聯劑(F)係用以使聚合物成分(A)中的前述官能基與其他化合物鍵結而進行交聯之成分，藉由如此進行交聯，能夠調節保護膜形成用膜的初始接著力及凝聚力。[Crosslinking agent (F)] When using the above-mentioned acrylic resin as the polymer component (A) and having functional groups capable of bonding to other compounds, such as vinyl groups, (meth)acrylyl groups, amine groups, hydroxyl groups, carboxyl groups, isocyanate groups, etc. , the composition (III-1) and the protective film-forming film may also contain a cross-linking agent (F). The cross-linking agent (F) is a component for cross-linking the aforementioned functional group in the polymer component (A) by bonding it to other compounds. By cross-linking in this way, the initial adhesion of the protective film-forming film can be adjusted. strength and cohesion.
作為交聯劑(F)，例如可列舉：有機多元異氰酸酯化合物、有機多元亞胺化合物、金屬螯合物系交聯劑(具有金屬螯合物結構之交聯劑)、氮丙啶系交聯劑(具有氮丙啶基之交聯劑)等。Examples of the cross-linking agent (F) include organic polyisocyanate compounds, organic polyimine compounds, metal chelate-based cross-linking agents (cross-linking agents having a metal chelate structure), and aziridine-based cross-linking agents. Agent (cross-linking agent with aziridine group), etc.
作為前述有機多元異氰酸酯化合物，例如可列舉：芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物及脂環族多元異氰酸酯化合物(以下，有時將這些化合物統一簡稱為「芳香族多元異氰酸酯化合物等」)；前述芳香族多元異氰酸酯化合物等的三聚物、異氰脲酸酯體及加合物；使前述芳香族多元異氰酸酯化合物等與多元醇化合物反應而獲得之末端異氰酸酯胺基甲酸酯預聚物等。前述「加合物」意指前述芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物或脂環族多元異氰酸酯化合物，與乙二醇、丙二醇、新戊二醇、三羥甲基丙烷或蓖麻油等含低分子活性氫化合物之反應物。作為前述加合物的示例，可列舉如後述之三羥甲基丙烷之苯二甲基二異氰酸酯加成物等。另外，所謂「末端異氰酸酯胺基甲酸酯預聚物」，意指具有胺基甲酸酯鍵、並且於分子的末端部具有異氰酸酯基之預聚物。Examples of the organic polyisocyanate compound include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyisocyanate compounds, etc."); Trimers, isocyanurates and adducts of the aforementioned aromatic polyisocyanate compounds, etc.; terminal isocyanate urethane prepolymers, etc. obtained by reacting the aforementioned aromatic polyisocyanate compounds, etc. with polyol compounds. . The aforementioned "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, etc. Reactant of low molecular weight active hydrogen compounds. Examples of the adduct include a xylylene diisocyanate adduct of trimethylolpropane, which will be described later. In addition, the "terminated isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the terminal portion of the molecule.
作為前述有機多元異氰酸酯化合物，更具體而言，例如可列舉：2,4-甲苯二異氰酸酯；2,6-甲苯二異氰酸酯；1,3-苯二甲基二異氰酸酯；1,4-二甲苯二異氰酸酯；二苯基甲烷-4,4'-二異氰酸酯；二苯基甲烷-2,4'-二異氰酸酯；3-甲基二苯基甲烷二異氰酸酯；六亞甲基二異氰酸酯；異佛爾酮二異氰酸酯；二環己基甲烷-4,4'-二異氰酸酯；二環己基甲烷-2,4'-二異氰酸酯；於三羥甲基丙烷等多元醇的全部或一部分羥基加成了甲苯二異氰酸酯、六亞甲基二異氰酸酯及苯二甲基二異氰酸酯中的任1種或2種以上而成之化合物；離胺酸二異氰酸酯等。More specific examples of the organic polyisocyanate compound include: 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylylenedimethyldiisocyanate; 1,4-xylylenediisocyanate Isocyanates; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone Diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; toluene diisocyanate added to all or part of the hydroxyl groups of polyols such as trimethylolpropane, Any one or two or more compounds of hexamethylene diisocyanate and xylylene diisocyanate; lysine diisocyanate, etc.
作為前述有機多元亞胺化合物，例如可列舉：N,N'-二苯基甲烷-4,4'-雙(1-氮丙啶甲醯胺)、三羥甲基丙烷-三-β-氮丙啶基丙酸酯、四羥甲基甲烷-三-β-氮丙啶基丙酸酯、N,N'-甲苯-2,4-雙(1-氮丙啶甲醯胺)三伸乙基三聚氰胺等。Examples of the organic polyimine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinemethane), trimethylolpropane-tris-β-nitrogen Propiridylpropionate, tetramethylolmethane-tris-β-aziridinylpropionate, N,N'-toluene-2,4-bis(1-aziridinylcarboxamide)triethylene Based on melamine, etc.
於使用有機多元異氰酸酯化合物作為交聯劑(F)之情形時，作為聚合物成分(A)，較佳為使用含羥基之聚合物。於交聯劑(F)具有異氰酸酯基，聚合物成分(A)具有羥基之情形時，藉由交聯劑(F)與聚合物成分(A)之反應，能夠簡便地將交聯結構導入至保護膜形成用膜中。When an organic polyvalent isocyanate compound is used as the cross-linking agent (F), it is preferred to use a hydroxyl-containing polymer as the polymer component (A). When the cross-linking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the cross-linked structure can be easily introduced through the reaction between the cross-linking agent (F) and the polymer component (A). In the film for forming protective film.
組成物(III-1)及保護膜形成用膜所含有之交聯劑(F)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The cross-linking agent (F) contained in the composition (III-1) and the film for forming a protective 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 may be Take your pick.
於使用交聯劑(F)之情形時，組成物(III-1)中，交聯劑(F)的含量相對於聚合物成分(A)的含量100質量份，較佳為0.01質量份至20質量份，更佳為0.1質量份至10質量份，尤佳為0.5質量份至5質量份。藉由交聯劑(F)的前述含量為前述下限值以上，能夠獲得更顯著的由使用交聯劑(F)所帶來之效果。另外，藉由交聯劑(F)的前述含量為前述上限值以下，能夠抑制使用過量的交聯劑(F)。When a cross-linking agent (F) is used, the content of the cross-linking agent (F) in the composition (III-1) is preferably 0.01 to 0.01 parts by mass relative to 100 parts by mass of the polymer component (A). 20 parts by mass, more preferably 0.1 to 10 parts by mass, particularly preferably 0.5 to 5 parts by mass. When the aforementioned content of the cross-linking agent (F) is equal to or higher than the aforementioned lower limit, more significant effects brought about by the use of the cross-linking agent (F) can be obtained. In addition, when the content of the cross-linking agent (F) is equal to or less than the upper limit, use of an excessive amount of the cross-linking agent (F) can be suppressed.
[著色劑(I)] 組成物(III-1)及保護膜形成用膜亦可含有著色劑(I)。 作為著色劑(I)，例如可列舉無機系顏料、有機系顏料、有機系染料等公知的著色劑。[Color(I)] The composition (III-1) and the film for protective film formation may contain the colorant (I). Examples of the colorant (I) include known colorants such as inorganic pigments, organic pigments, and organic dyes.
作為前述有機系顏料及有機系染料，例如可列舉：銨系色素、花青系色素、部花青系色素、克酮鎓(croconium)系色素、方酸鎓(squalilium)系色素、薁鎓系色素、聚次甲基系色素、萘醌系色素、吡喃鎓系色素、酞菁系色素、萘酞菁系色素、萘內醯胺系色素、偶氮系色素、縮合偶氮系色素、靛藍系色素、紫環酮(perinone)系色素、苝系色素、二噁嗪系色素、喹吖啶酮系色素、異吲哚啉酮系色素、喹啉黃(quinophthalone)系色素、吡咯系色素、硫代靛藍系色素、金屬錯合物系色素(金屬錯鹽染料)、二硫醇金屬錯合物系色素、吲哚酚系色素、三烯丙基甲烷系色素、蒽醌系色素、萘酚系色素、次甲基偶氮系色素、苯并咪唑酮系色素、皮蒽酮系色素及士林(threne)系色素等。Examples of the organic pigments and organic dyes include ammonium pigments, cyanine pigments, merocyanine pigments, croconium pigments, squalilium pigments, and azulium pigments. Pigments, polymethine pigments, naphthoquinone pigments, pyranium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphtholactam pigments, azo pigments, condensed azo pigments, indigo Pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, Thioindigo-based pigments, metal complex-based pigments (metal complex dyes), dithiol metal complex-based pigments, indoxyl-based pigments, triallylmethane-based pigments, anthraquinone-based pigments, naphthols pigments, methine azo pigments, benzimidazolone pigments, picanthrone pigments and threne pigments, etc.
作為前述無機系顏料，例如可列舉：碳黑、鈷系色素、鐵系色素、鉻系色素、鈦系色素、釩系色素、鋯系色素、鉬系色素、釕系色素、鉑系色素、ITO(Indium Tin Oxide；氧化銦錫)系色素、ATO(Antimony Tin Oxide；氧化銻錫)系色素等。Examples of the inorganic pigment include carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, and ITO (Indium Tin Oxide; indium tin oxide) pigments, ATO (Antimony Tin Oxide; antimony tin oxide) pigments, etc.
組成物(III-1)及保護膜形成用膜所含有之著色劑(I)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The colorant (I) contained in the composition (III-1) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be arbitrary. select.
於使用著色劑(I)之情形時，保護膜形成用膜中的著色劑(I)的含量根據目的適宜調節即可。例如，藉由調節保護膜形成用膜中的著色劑(I)的含量，調節保護膜的透光性，能夠調節對保護膜進行雷射印字之情形時的印字視認性。另外，藉由調節保護膜形成用膜中的著色劑(I)的含量，亦能夠提高保護膜的設計性，或使得半導體晶圓的內面的研削痕跡不易見。若考慮這些方面，則組成物(III-1)中，著色劑(I)的含量相對於溶劑以外的全部成分的總含量之比例(亦即，保護膜形成用膜中的著色劑(I)的含量相對於保護膜形成用膜的總質量之比例)較佳為0.1質量%至10質量%，更佳為0.1質量%至7.5質量%，尤佳為0.1質量%至5質量%。藉由前述比例為前述下限值以上，能夠獲得更顯著的由使用著色劑(I)所帶來之效果。另外，藉由前述比例為前述上限值以下，能夠抑制保護膜形成用膜的透光性過度降低。When using the colorant (I), 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, it is possible to adjust the printing visibility when laser printing is performed on the protective film. In addition, by adjusting the content of the colorant (I) in the film for forming a protective film, the designability of the protective film can also be improved, or grinding marks on the inner surface of the semiconductor wafer can be made less visible. Taking these aspects into consideration, the ratio of the content of the colorant (I) in the composition (III-1) to the total content of all components except the solvent (that is, the colorant (I) in the protective film-forming film The ratio of the content to the total mass of the film for protective film formation) is preferably 0.1 mass% to 10 mass%, more preferably 0.1 mass% to 7.5 mass%, and particularly preferably 0.1 mass% to 5 mass%. When the ratio is equal to or higher than the lower limit, a more significant effect of using the colorant (I) can be obtained. In addition, when the ratio is equal to or less than the upper limit, excessive decrease in the light transmittance of the protective film forming film can be suppressed.
[通用添加劑(J)] 組成物(III-1)及保護膜形成用膜亦可在無損本發明的效果之範圍內含有通用添加劑(J)。 通用添加劑(J)可為公知的添加劑，可根據目的任意選擇，並無特別限定，作為較佳的通用添加劑(J)，例如可列舉：塑化劑、抗靜電劑、抗氧化劑、吸氣劑(gettering agent)等。[General Additive(J)] The composition (III-1) and the protective film-forming film may contain a general-purpose additive (J) within a range that does not impair the effects of the present invention. The general-purpose additive (J) can be a well-known additive, and can be selected arbitrarily according to the purpose, and is not particularly limited. Examples of preferred general-purpose additives (J) include plasticizers, antistatic agents, antioxidants, and getters. (gettering agent) etc.
組成物(III-1)及保護膜形成用膜所含有之通用添加劑(J)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。 組成物(III-1)及保護膜形成用膜中的通用添加劑(J)的含量並無特別限定，根據目的適宜選擇即可。The general additive (J) contained in the composition (III-1) and the protective film-forming film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be arbitrary. select. The content of the general-purpose additive (J) in the composition (III-1) and the protective film-forming film is not particularly limited and may be appropriately selected depending on the purpose.
[溶劑] 組成物(III-1)較佳為進而含有溶劑。含有溶劑之組成物(III-1)的操作性良好。 前述溶劑並無特別限定，作為較佳的溶劑，例如可列舉：甲苯、二甲苯等烴；甲醇、乙醇、2-丙醇、異丁醇(2-甲基丙烷-1-醇)、1-丁醇等醇；乙酸乙酯等酯；丙酮、甲基乙基酮等酮；四氫呋喃等醚；二甲基甲醯胺、N-甲基吡咯啶酮等醯胺(具有醯胺鍵之化合物)等。 組成物(III-1)所含有之溶劑可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。[Solvent] The composition (III-1) preferably further contains a solvent. The composition (III-1) containing a solvent has good operability. The solvent is not particularly limited. Examples of preferred solvents include: hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), 1- Alcohols such as butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amide such as dimethylformamide and N-methylpyrrolidone (compounds with amide bonds) wait. The solvent contained in the composition (III-1) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these solvents may be selected arbitrarily.
就能夠使組成物(III-1)中的含有成分更均勻地混合之方面而言，組成物(III-1)所含有之溶劑較佳為甲基乙基酮等。From the viewpoint that the components contained in the composition (III-1) can be mixed more uniformly, the solvent contained in the composition (III-1) is preferably methyl ethyl ketone or the like.
組成物(III-1)的溶劑的含量並無特別限定，例如根據溶劑以外的成分的種類適宜選擇即可。The content of the solvent in the composition (III-1) is not particularly limited, and may be appropriately selected depending on the types of components other than the solvent, for example.
[熱硬化性保護膜形成用組成物之製造方法] 組成物(III-1)等熱硬化性保護膜形成用組成物藉由調配用以構成該組成物之各成分而獲得。 熱硬化性保護膜形成用組成物例如除調配成分的種類不同之方面以外，可利用與上文說明之黏著劑組成物之情形相同的方法製造。[Method for manufacturing composition for forming thermosetting protective film] A composition for forming a thermosetting protective film such as composition (III-1) is obtained by blending each component constituting the composition. The composition for forming a thermosetting protective film can be produced by the same method as the adhesive composition described above, except that the types of ingredients are different.
◎剝離膜 前述剝離膜可作為於前述保護膜形成用複合片中之保護膜形成用膜側的最表層所具備之任意的構成要素。成為於保護膜形成用膜上具備剝離膜之狀態之保護膜形成用複合片中，將該剝離膜自保護膜形成用膜移除時，保護膜形成用複合片的剝離帶電得到抑制。◎Peel-off film The release film may be an arbitrary component included in the outermost layer on the protective film forming film side of the protective film forming composite sheet. In the composite sheet for protective film formation in which the release film is provided on the film for protective film formation, peeling charging of the composite sheet for protective film formation is suppressed when the release film is removed from the film for protective film formation.
前述剝離膜可為公知的膜，例如可列舉聚對苯二甲酸乙二酯製膜等樹脂製膜的單面經實施聚矽氧處理等剝離處理而成之膜。 前述剝離膜亦可與上述之作為中間層之剝離性改善層具有相同的構成。The release film may be a known film, and examples thereof include a film made of a resin film such as a polyethylene terephthalate film and one surface thereof subjected to a release treatment such as polysiloxane treatment. The said peeling film may have the same structure as the said peelability improving layer as an intermediate layer.
前述剝離膜的厚度並無特別限定，例如可為10μm至1000μm等。The thickness of the release film is not particularly limited, and may be, for example, 10 μm to 1000 μm.
作為前述保護膜形成用複合片的一實施形態，例如可列舉以下之保護膜形成用複合片：具備支撐片、及形成於前述支撐片的一面上之熱硬化性保護膜形成用膜，並且前述支撐片具備基材、及形成於前述基材的單面或雙面上之抗靜電層，或者前述支撐片具備具有抗靜電性之基材作為抗靜電層，前述熱硬化性保護膜形成用膜之加熱硬化前，前述保護膜形成用複合片中之前述支撐片側的最表層的表面電阻率為1.0×1011 Ω/□以下，前述熱硬化性保護膜形成用膜之加熱硬化後，前述保護膜形成用複合片中之前述支撐片側的最表層的表面電阻率為1.0×1011 Ω/□以下，前述抗靜電層含有選自由嘧啶鎓鹽、吡啶鎓鹽、哌啶鎓鹽、吡咯啶鎓鹽、咪唑鎓鹽、嗎啉鎓鹽、鋶鹽、鏻鹽、銨鹽、聚(3,4-乙二氧基噻吩)/聚苯乙烯磺酸鹽、聚吡咯及奈米碳管所組成之群組中的1種或2種以上。An example of an embodiment of the protective film-forming composite sheet includes a protective film-forming composite sheet including a support sheet and a thermosetting protective film-forming film formed on one side of the support sheet, and the above-mentioned The support sheet is provided with a base material and an antistatic layer formed on one or both sides of the base material, or the support sheet is provided with a base material having antistatic properties as an antistatic layer, and the film for forming a thermosetting protective film Before heating and curing, the surface resistivity of the outermost layer on the side of the supporting sheet in the composite sheet for protective film formation is 1.0×10 11 Ω/□ or less. After heating and curing of the film for forming a thermosetting protective film, the protection In the film-forming composite sheet, the surface resistivity of the outermost layer on the support sheet side is 1.0×10 11 Ω/□ or less, and the antistatic layer contains a material selected from the group consisting of pyrimidinium salt, pyridinium salt, piperidinium salt, and pyrrolidinium salt. Salt, imidazolium salt, morpholinium salt, sulfonium salt, phosphonium salt, ammonium salt, poly(3,4-ethylenedioxythiophene)/polystyrene sulfonate, polypyrrole and carbon nanotubes 1 or 2 or more types in the group.
作為前述保護膜形成用複合片的一實施形態，例如可列舉以下之保護膜形成用複合片：具備支撐片、及形成於前述支撐片的一面上之熱硬化性保護膜形成用膜，並且前述支撐片具備基材、及形成於前述基材的單面或雙面上之抗靜電層，前述熱硬化性保護膜形成用膜之加熱硬化前，前述保護膜形成用複合片中之前述支撐片側的最表層的表面電阻率為1.0×1011 Ω/□以下，前述熱硬化性保護膜形成用膜之加熱硬化後，前述保護膜形成用複合片中之前述支撐片側的最表層的表面電阻率為1.0×1011 Ω/□以下，前述抗靜電層含有選自由聚(3,4-乙二氧基噻吩)/聚苯乙烯磺酸鹽、及聚吡咯所組成之群組中的1種以上。An example of an embodiment of the protective film-forming composite sheet includes a protective film-forming composite sheet including a support sheet and a thermosetting protective film-forming film formed on one side of the support sheet, and the above-mentioned The support sheet includes a base material and an antistatic layer formed on one or both sides of the base material. Before the thermosetting protective film forming film is heated and cured, the supporting sheet side of the protective film forming composite sheet is The surface resistivity of the outermost layer is 1.0×10 11 Ω/□ or less. After the thermosetting protective film-forming film is heated and cured, the surface resistivity of the outermost layer on the support sheet side of the protective film-forming composite sheet is 1.0×10 11 Ω/□ or less. is 1.0×10 11 Ω/□ or less, and the antistatic layer contains at least one selected from the group consisting of poly(3,4-ethylenedioxythiophene)/polystyrenesulfonate and polypyrrole. .
作為前述保護膜形成用複合片的一實施形態，例如可列舉以下之保護膜形成用複合片：具備支撐片、及形成於前述支撐片的一面上之熱硬化性保護膜形成用膜，並且前述支撐片具備具有抗靜電性之基材作為抗靜電層，前述熱硬化性保護膜形成用膜之加熱硬化前，前述保護膜形成用複合片中之前述支撐片側的最表層的表面電阻率為1.0×1011 Ω/□以下，前述熱硬化性保護膜形成用膜之加熱硬化後，前述保護膜形成用複合片中之前述支撐片側的最表層的表面電阻率為1.0×1011 Ω/□以下，前述抗靜電層含有鏻鹽。An example of an embodiment of the protective film-forming composite sheet includes a protective film-forming composite sheet including a support sheet and a thermosetting protective film-forming film formed on one side of the support sheet, and the above-mentioned The support sheet has an antistatic base material as an antistatic layer, and before the thermosetting protective film-forming film is heated and cured, the surface resistivity of the outermost layer on the support sheet side of the protective film-forming composite sheet is 1.0. ×10 11 Ω/□ or less. After the thermosetting protective film-forming film is heated and cured, the surface resistivity of the outermost layer on the support sheet side of the protective film-forming composite sheet is 1.0 × 10 11 Ω/□ or less. , the aforementioned antistatic layer contains phosphonium salt.
◇保護膜形成用複合片之製造方法 前述保護膜形成用複合片可藉由將上述各層以成為對應的位置關係之方式進行積層而製造。各層之形成方法如上文所說明。◇Production method of composite sheet for protective film formation The composite sheet for forming a protective film can be produced by laminating each of the above layers so as to have a corresponding positional relationship. Each layer is formed as described above.
例如，於製造支撐片時，於基材上或抗靜電性基材上積層黏著劑層之情形時，於基材上或抗靜電性基材上塗敷上述黏著劑組成物，並視需要使之乾燥即可。該方法可應用於在基材或抗靜電性基材的前述凹凸面上積層黏著劑層之情形、及在基材或抗靜電性基材的前述平滑面上積層黏著劑層之情形之任一情形。並且，該方法尤其適於在前述凹凸面上積層黏著劑層之情形。原因在於，於應用該方法之情形時，能夠獲得抑制於基材或抗靜電性基材的前述凹凸面與黏著劑層之間產生空隙部之高效果。For example, when an adhesive layer is laminated on a base material or an antistatic base material when manufacturing a support sheet, the above-mentioned adhesive composition is applied on the base material or the antistatic base material, and if necessary, Just dry. This method can be applied to both the case where an adhesive layer is laminated on the uneven surface of the base material or the antistatic base material, and the case where the adhesive layer is laminated on the aforementioned smooth surface of the base material or the antistatic base material. situation. Furthermore, this method is particularly suitable for laminating an adhesive layer on the uneven surface. The reason is that when this method is applied, a high effect of suppressing the generation of voids between the uneven surface of the base material or the antistatic base material and the adhesive layer can be obtained.
於製造支撐片時，於基材上或抗靜電性基材上積層背面抗靜電層或表面抗靜電層之情形亦相同。 該情形時，除使用抗靜電組成物(VI-1)代替黏著劑組成物之方面以外，可利用與上述之積層黏著劑層之方法相同的方法，於基材上或抗靜電性基材上積層背面抗靜電層或表面抗靜電層。The same is true for laminating a back antistatic layer or a surface antistatic layer on a base material or an antistatic base material when manufacturing the support sheet. In this case, except for using the antistatic composition (VI-1) instead of the adhesive composition, the same method as the above-mentioned method of laminating the adhesive layer can be used, on the base material or on the antistatic base material. Laminate a back antistatic layer or a surface antistatic layer.
另一方面，於基材上或抗靜電性基材上積層黏著劑層之情形時，亦可應用以下之方法代替如上所述般於基材上或抗靜電性基材上塗敷黏著劑組成物之方法。 亦即，亦可利用以下之方法於基材上或抗靜電性基材上積層黏著劑層：於剝離膜上塗敷黏著劑組成物，並視需要使之乾燥，藉此於剝離膜上預先形成黏著劑層，使該黏著劑層的露出面與基材或抗靜電性基材的一表面貼合。並且，該方法尤其適於在前述平滑面上積層黏著劑層之情形。原因在於，於應用該方法之情形時，能夠獲得抑制於基材或抗靜電性基材的前述平滑面與黏著劑層之間產生空隙部之高效果。On the other hand, when an adhesive layer is laminated on a base material or an antistatic base material, the following method can be used instead of coating the adhesive composition on the base material or the antistatic base material as described above. method. That is, the adhesive layer can also be laminated on the base material or the antistatic base material by the following method: applying the adhesive composition on the release film and drying it if necessary, thereby preforming the adhesive layer on the release film The adhesive layer is used to bond the exposed surface of the adhesive layer to a surface of the base material or the antistatic base material. Furthermore, this method is particularly suitable for laminating an adhesive layer on the smooth surface. The reason is that when this method is applied, a high effect of suppressing the generation of gaps between the base material or the smooth surface of the antistatic base material and the adhesive layer can be obtained.
於製造支撐片時，使用剝離膜，於基材上或抗靜電性基材上積層背面抗靜電層或表面抗靜電層之情形亦相同。 該情形時，除使用抗靜電組成物(VI-1)代替黏著劑組成物之方面以外，可利用與上述之使用剝離膜積層黏著劑層之方法相同的方法，於基材上或抗靜電性基材上積層背面抗靜電層或表面抗靜電層。The same applies to the case where a release film is used to laminate a back antistatic layer or a surface antistatic layer on a base material or an antistatic base material when manufacturing a support sheet. In this case, except that the antistatic composition (VI-1) is used instead of the adhesive composition, the same method as the above-mentioned method of laminating an adhesive layer using a release film can be used to form antistatic properties on the base material or the adhesive layer. A back antistatic layer or surface antistatic layer is laminated on the base material.
前文列舉了於基材上或抗靜電性基材上積層黏著劑層、背面抗靜電層或表面抗靜電層之情形作為示例，但上述方法例如亦可應用於在基材上或抗靜電性基材上積層中間層之情形等積層其他層之情形。The above mentioned lamination of an adhesive layer, a back antistatic layer, or a surface antistatic layer on a base material or an antistatic base material is cited as an example. However, the above method can also be applied to a base material or an antistatic base material. The situation in which a middle layer is laminated on the material is the same as the situation in which other layers are laminated.
另一方面，例如於已積層於基材上或抗靜電性基材上之黏著劑層上，進而積層保護膜形成用膜之情形時，可於黏著劑層上塗敷保護膜形成用組成物，而直接形成保護膜形成用膜。保護膜形成用膜以外的層亦可使用用以形成該層之組成物，利用相同的方法，於黏著劑層上積層該層。如此，於已積層於基材上之任一層(以下，簡稱為「第1層」)上，形成新的層(以下，簡稱為「第2層」)，而形成連續的2層之積層結構(換言之，第1層及第2層之積層結構)之情形時，可應用於前述第1層上塗敷用以形成前述第2層之組成物，並視需要使之乾燥之方法。 但是，較佳為藉由下述方式形成連續的2層之積層結構：使用用以形成第2層之組成物，於剝離膜上預先形成第2層，將該已形成之第2層中之與和前述剝離膜接觸之側為相反側的露出面來與第1層的露出面貼合。此時，前述組成物較佳為塗敷於剝離膜的剝離處理面。剝離膜於形成積層結構後視需要移除即可。 此處列舉了於黏著劑層上積層保護膜形成用膜之情形作為示例，但例如於黏著劑層上積層中間層之情形、於中間層上積層保護膜形成用膜之情形、於表面抗靜電層上積層黏著劑層之情形等，成為對象之積層結構可任意選擇。On the other hand, for example, when a film for forming a protective film is laminated on an adhesive layer that has been laminated on a base material or an antistatic base material, the composition for forming a protective film can be applied on the adhesive layer. Instead, the protective film forming film is directly formed. The composition used to form this layer can also be used as a layer other than the film for forming a protective film, and this layer is laminated on the adhesive layer by the same method. In this way, a new layer (hereinafter, referred to as the "second layer") is formed on any layer already laminated on the base material (hereinafter, referred to as the "first layer"), thereby forming a continuous 2-layer laminated structure. (In other words, a laminated structure of the first layer and the second layer), the method of applying a composition for forming the second layer on the first layer and drying it if necessary can be applied. However, it is preferable to form a continuous two-layer laminated structure by forming the second layer in advance on the release film using a composition for forming the second layer, and then removing the formed second layer. The exposed surface opposite to the side in contact with the release film is bonded to the exposed surface of the first layer. At this time, the composition is preferably applied to the release-treated surface of the release film. The peeling film can be removed if necessary after forming the laminated structure. Here, the case where a protective film-forming film is laminated on the adhesive layer is given as an example. However, for example, the case where an intermediate layer is laminated on the adhesive layer, the case where a protective film-forming film is laminated on the intermediate layer, and the surface antistatic The target laminate structure can be selected arbitrarily, such as when an adhesive layer is laminated on top of each other.
如此，構成保護膜形成用複合片之基材以外的層均可利用預先形成於剝離膜上，再貼合於目標層的表面之方法進行積層，因此視需要適宜選擇採用此種步驟之層來製造保護膜形成用複合片即可。In this way, the layers other than the base material constituting the composite sheet for forming a protective film can be laminated by a method of being formed in advance on the release film and then bonded to the surface of the target layer. Therefore, it is appropriate to select the layer using this step as needed. A composite sheet for forming a protective film may be produced.
此外，保護膜形成用複合片通常係以於該保護膜形成用複合片中之與支撐片為相反側的最表層(例如保護膜形成用膜)的表面貼合有剝離膜之狀態保管。因此，可藉由下述方式獲得附剝離膜之保護膜形成用複合片：於該剝離膜(較佳為該剝離膜的剝離處理面)上，塗敷保護膜形成用組成物等用以形成構成最表層之層之組成物，並視需要使之乾燥，藉此於剝離膜上預先形成構成最表層之層，利用上述任一種方法於該層中之與剝離膜接觸之側為相反側的露出面上積層剩餘各層，不移除剝離膜而保持貼合狀態不變。In addition, the composite sheet for protective film formation is usually stored in a state in which a release film is bonded to the surface of the outermost layer (for example, the film for protective film formation) on the opposite side to the support sheet. Therefore, a protective film-forming composite sheet with a release film can be obtained by coating a protective film-forming composition or the like on the release film (preferably, the release-treated surface of the release film) to form The composition constituting the layer constituting the outermost layer is dried if necessary, whereby the layer constituting the outermost layer is preliminarily formed on the release film, and the side in contact with the release film is opposite to the side of the layer that is in contact with the release film using any of the above methods. Layer the remaining layers on the exposed surface without removing the peel-off film and keep the bonded state intact.
◇半導體晶片之製造方法 前述保護膜形成用複合片可用於製造半導體晶片。 作為此時的半導體晶片之製造方法，例如可列舉具有以下步驟之方法：使前述保護膜形成用膜熱硬化而形成保護膜之步驟(以下，有時簡稱為「保護膜形成步驟」)；分割前述半導體晶圓，切斷前述保護膜或保護膜形成用膜，獲得具備切斷後的保護膜或保護膜形成用膜之多個半導體晶片之步驟(以下，有時簡稱為「分割步驟」)；以及將具備前述切斷後的保護膜或保護膜形成用膜之半導體晶片自前述支撐片扯離而進行拾取之步驟(以下，有時簡稱為「拾取步驟」)。 前述製造方法中，於前述貼附步驟後，進行前述保護膜形成步驟、分割步驟及拾取步驟。並且，於分割步驟後進行拾取步驟，但除該方面以外，進行保護膜形成步驟、分割步驟及拾取步驟之順序可根據目的任意設定。◇Semiconductor chip manufacturing method The composite sheet for forming a protective film can be used to manufacture semiconductor wafers. Examples of the manufacturing method of the semiconductor wafer at this time include a method having the following steps: a step of thermally curing the film for forming a protective film to form a protective film (hereinafter, sometimes simply referred to as a "protective film forming step"); dividing The step of cutting the aforementioned protective film or protective film-forming film from the aforementioned semiconductor wafer to obtain a plurality of semiconductor wafers having the cut protective film or protective film-forming film (hereinafter, sometimes referred to as the “dividing step”); and a step of picking up the semiconductor wafer provided with the cut protective film or protective film-forming film from the supporting sheet (hereinafter, sometimes simply referred to as "picking up step"). In the above manufacturing method, after the above attaching step, the above protective film forming step, the dividing step and the picking up step are performed. Moreover, the pickup step is performed after the dividing step. However, other than this aspect, the order in which the protective film forming step, the dividing step, and the pickup step are performed can be arbitrarily set according to the purpose.
作為前述保護膜形成用複合片的使用對象之半導體晶圓的厚度並無特別限定，就後述更容易分割為半導體晶片之方面而言，較佳為30μm至1000μm，更佳為100μm至400μm。The thickness of the semiconductor wafer to which the protective film forming composite sheet is to be used is not particularly limited, but in order to make it easier to divide into semiconductor wafers described later, it is preferably 30 μm to 1000 μm, and more preferably 100 μm to 400 μm.
以下，一邊參照圖式，一邊對上述製造方法進行說明。圖14係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。此處，列舉保護膜形成用複合片為圖1所示之保護膜形成用複合片之情形時的製造方法作為示例而進行說明。Hereinafter, the above-mentioned manufacturing method will be described with reference to the drawings. FIG. 14 is a cross-sectional view schematically illustrating a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. Here, a manufacturing method when the composite sheet for protective film formation is the composite sheet for protective film formation shown in FIG. 1 will be described as an example.
本實施形態的製造方法(本說明書中，有時稱為「製造方法(1)」)具有以下之步驟：將保護膜形成用膜貼附於半導體晶圓之步驟(貼附步驟)；使貼附於前述半導體晶圓後的前述保護膜形成用膜熱硬化而形成保護膜之步驟(保護膜形成步驟)；分割前述半導體晶圓，切斷前述保護膜，獲得具備切斷後的保護膜之多個半導體晶片之步驟(分割步驟)；以及將前述具備切斷後的保護膜之半導體晶片自前述支撐片扯離而進行拾取之步驟(拾取步驟)。The manufacturing method of this embodiment (sometimes referred to as "manufacturing method (1)" in this specification) has the following steps: a step of attaching a protective film forming film to a semiconductor wafer (attachment step); The step of thermally curing the film for forming a protective film after being attached to the semiconductor wafer to form a protective film (protective film forming step); dividing the semiconductor wafer and cutting the protective film to obtain a protective film after cutting The step of separating the semiconductor wafer (dividing step); and the step of pulling off the semiconductor wafer with the cut protective film from the aforementioned support sheet and picking it up (picking up step).
製造方法(1)中，於使用圖1所示之保護膜形成用複合片101之情形時，如圖14中的(a)所示，自保護膜形成用膜101移除剝離膜15。
此外，此處為方便起見而對移除剝離膜15後的保護膜形成用複合片亦標附符號101而表示。In the manufacturing method (1), when the
製造方法(1)的前述貼附步驟中，如圖14中的(b)所示，於半導體晶圓9的內面9b，貼附保護膜形成用複合片101中的保護膜形成用膜13。
貼附步驟中，亦可藉由加熱保護膜形成用膜13而使之軟化，貼附於半導體晶圓9。該情形時，例如亦可將保護膜形成用膜13於70℃加熱1分鐘後，立即貼附於半導體晶圓9。
此外，此處省略圖示半導體晶圓9中電路面上的凸塊等。In the aforementioned attaching step of the manufacturing method (1), as shown in FIG. 14(b) , the protective
製造方法(1)的貼附步驟後，於前述保護膜形成步驟中，使貼附於半導體晶圓9後的保護膜形成用膜13熱硬化，如圖14中的(c)所示，形成保護膜13'。
此外，此處以符號101'表示保護膜形成用膜13成為保護膜13'後的保護膜形成用複合片。該情況於以後的圖中亦相同。After the attachment step of the manufacturing method (1), in the aforementioned protective film forming step, the protective
保護膜形成步驟中，保護膜形成用膜13的熱硬化條件、亦即熱硬化時的加熱溫度及加熱時間如上文所說明。In the protective film forming step, the thermal curing conditions of the protective
製造方法(1)的保護膜形成步驟後，於前述分割步驟中，將保護膜形成用複合片101'載置於切割台上，分割半導體晶圓9，切斷保護膜13'，如圖14中的(d)所示，獲得具備切斷後的保護膜130'之多個半導體晶片9'。保護膜13'係於沿著半導體晶片9'的周緣部之位置被切斷(分割)。此時，由於保護膜形成用複合片101'包含具有背面抗靜電層17之支撐片10，保護膜形成用複合片101'的表面電阻率為1.0×1011
Ω/□以下，故而能夠防止因靜電等的影響而於保護膜形成用複合片101'與切割台之間混入異物。結果，能夠防止於分割半導體晶圓9，切斷保護膜13'時產生碎屑。After the protective film forming step of the manufacturing method (1), in the aforementioned dividing step, the protective film forming composite sheet 101' is placed on a cutting table, the semiconductor wafer 9 is divided, and the protective film 13' is cut, as shown in Figure 14 As shown in (d), a plurality of semiconductor wafers 9' having cut protective films 130' are obtained. The protective film 13' is cut (divided) at a position along the peripheral edge of the semiconductor wafer 9'. At this time, since the composite sheet 101' for forming a protective film includes the
前述分割步驟中，分割半導體晶圓9，切斷保護膜13'之方法可為公知的方法。 作為此種方法，例如可列舉使用切割刀片將半導體晶圓9連同保護膜13'一起進行分割(切斷)之方法等。In the aforementioned dividing step, the method of dividing the semiconductor wafer 9 and cutting the protective film 13' can be a known method. An example of such a method is a method of dividing (cutting) the semiconductor wafer 9 together with the protective film 13' using a dicing blade.
製造方法(1)的分割步驟後，於前述拾取步驟中，如圖14中的(e)所示，將具備切斷後的保護膜130'之半導體晶片9'自支撐片10扯離而進行拾取。此處，以箭頭I表示拾取方向，該情況於以後的圖中亦相同。作為用以將半導體晶片9'連同保護膜130'一起自支撐片10扯離之扯離機構8，可列舉真空吸嘴等。
藉由以上步驟，獲得目標半導體晶片9'作為附保護膜之半導體晶片。After the dividing step of the manufacturing method (1), in the aforementioned picking up step, as shown in (e) in FIG. 14 , the semiconductor wafer 9 ′ with the cut protective film 130 ′ is pulled away from the supporting
製造方法(1)中，於保護膜形成步驟後進行分割步驟，但於本實施形態的半導體晶片之製造方法中，亦可不進行保護膜形成步驟而進行分割步驟，於分割步驟後進行保護膜形成步驟(有時將本實施形態稱為「製造方法(2)」)。 亦即，本實施形態的製造方法(製造方法(2))具有：將前述保護膜形成用複合片中的保護膜形成用膜貼附於半導體晶圓之步驟(貼附步驟)；分割前述半導體晶圓，切斷前述保護膜形成用膜，獲得具備切斷後的保護膜形成用膜之多個半導體晶片之步驟(分割步驟)；使貼附於前述半導體晶圓後的前述保護膜形成用膜(切斷後的保護膜形成用膜)熱硬化而形成保護膜之步驟(保護膜形成步驟)；以及將具備前述切斷後(已切斷)的保護膜之半導體晶片自前述支撐片扯離而進行拾取之步驟(拾取步驟)。 圖15係用於以示意方式說明此種半導體晶片之製造方法的一實施形態之剖視圖。In the manufacturing method (1), the dividing step is performed after the protective film forming step. However, in the manufacturing method of the semiconductor wafer of this embodiment, the dividing step may be performed without performing the protective film forming step, and the protective film may be formed after the dividing step. Steps (this embodiment may be referred to as "manufacturing method (2)"). That is, the manufacturing method (manufacturing method (2)) of this embodiment includes: a step of attaching the protective film-forming film in the protective film-forming composite sheet to a semiconductor wafer (attachment step); and dividing the semiconductor wafer. wafer, the step of cutting the protective film forming film to obtain a plurality of semiconductor wafers having the cut protective film forming film (dividing step); and attaching the protective film forming film to the semiconductor wafer (Protective film forming film after cutting) is thermally cured to form a protective film (protective film forming step); and the semiconductor wafer having the protective film after cutting (cut) is separated from the supporting sheet. Pick-up steps (pick-up steps). FIG. 15 is a cross-sectional view schematically illustrating an embodiment of a manufacturing method of such a semiconductor wafer.
製造方法(2)的前述剝離步驟及貼附步驟分別如圖15中的(a)至圖15中的(b)所示，可利用與製造方法(1)的剝離步驟及貼附步驟相同的方法(如圖14中的(a)至圖14中的(b)所示)進行。The aforementioned peeling step and attaching step of the manufacturing method (2) are shown in (a) to (b) of Figure 15 respectively. The same steps as the peeling step and the attaching step of the manufacturing method (1) can be used. The method (shown in (a) to (b) in FIG. 14 ) is performed.
製造方法(2)的前述分割步驟中，分割半導體晶圓9，切斷保護膜形成用膜13，如圖15中的(c)所示，獲得具備切斷後的保護膜形成用膜130之多個半導體晶片9'。保護膜形成用膜13係於沿著半導體晶片9'的周緣部之位置被切斷(分割)。以符號130表示該切斷後的保護膜形成用膜13。此時，由於保護膜形成用複合片101包含具有背面抗靜電層17之支撐片10，保護膜形成用複合片101的表面電阻率為1.0×1011
Ω/□以下，故而能夠防止因靜電等的影響而於保護膜形成用複合片101與切割台之間混入異物。結果，能夠防止於分割半導體晶圓9，切斷保護膜13時產生碎屑。In the aforementioned dividing step of the manufacturing method (2), the semiconductor wafer 9 is divided, and the protective
製造方法(2)的前述保護膜形成步驟中，使保護膜形成用膜130熱硬化，如圖15中的(d)所示，於半導體晶片9'形成保護膜130'。 製造方法(2)中的保護膜形成步驟可利用與製造方法(1)中的保護膜形成步驟相同的方法進行。 藉由進行本步驟，可獲得與製造方法(1)的分割步驟結束後、亦即圖14中的(d)相同的狀態的附保護膜之半導體晶片。In the protective film forming step of the manufacturing method (2), the protective film forming film 130 is thermally cured, and as shown in (d) of FIG. 15 , a protective film 130' is formed on the semiconductor wafer 9'. The protective film forming step in the manufacturing method (2) can be performed by the same method as the protective film forming step in the manufacturing method (1). By performing this step, it is possible to obtain a semiconductor wafer with a protective film in the same state as that after the dividing step of the manufacturing method (1) is completed, that is, in (d) of FIG. 14 .
製造方法(2)的前述拾取步驟中，如圖15中的(e)所示，將具備切斷後的保護膜130'之半導體晶片9'自支撐片10扯離而進行拾取。
製造方法(2)中的拾取步驟可利用與製造方法(1)中的拾取步驟相同的方法(如圖14中的(e)所示)進行。
藉由以上步驟，獲得目標半導體晶片9'作為附保護膜之半導體晶片。In the aforementioned pick-up step of the manufacturing method (2), as shown in (e) of FIG. 15 , the semiconductor wafer 9 ′ having the cut protective film 130 ′ is pulled away from the supporting
如製造方法(1)及(2)所說明，保護膜形成用複合片中之支撐片側的最表層的表面電阻率於保護膜形成用膜之加熱硬化前後均為1.0×1011
Ω/□以下，因此無論是如製造方法(1)般將保護膜形成用膜13進行加熱硬化並切斷保護膜13'之情形、亦或是如製造方法(2)般切斷保護膜形成用膜13之情形，均能夠防止因靜電等的影響而於保護膜形成用複合片101或保護膜形成用複合片101'與切割台之間混入異物。結果，能夠防止產生碎屑。As described in the manufacturing methods (1) and (2), the surface resistivity of the outermost layer on the support sheet side of the protective film-forming composite sheet is 1.0×10 11 Ω/□ or less before and after the protective film-forming film is heated and hardened. Therefore, whether it is the case of heating and curing the protective
製造方法(1)及(2)中，於保護膜形成步驟後進行拾取步驟，但本實施形態的半導體晶片之製造方法中，亦可不進行保護膜形成步驟而進行至拾取步驟，於拾取步驟後進行保護膜形成步驟(有時將本實施形態稱為「製造方法(3)」)。 亦即，本實施形態的製造方法(製造方法(3))具有：將前述保護膜形成用複合片中的保護膜形成用膜貼附於半導體晶圓之步驟(貼附步驟)；分割前述半導體晶圓，切斷前述保護膜形成用膜，獲得具備切斷後的保護膜形成用膜之多個半導體晶片之步驟(分割步驟)；將具備前述切斷後的保護膜形成用膜之半導體晶片自前述支撐片扯離而進行拾取之步驟(拾取步驟)；以及使貼附於前述半導體晶圓後的前述保護膜形成用膜(切斷及拾取後的保護膜形成用膜)熱硬化而形成保護膜之步驟(保護膜形成步驟)。 圖16係用於以示意方式說明此種半導體晶片之製造方法的一實施形態之剖視圖。In the manufacturing methods (1) and (2), the pickup step is performed after the protective film forming step. However, in the manufacturing method of the semiconductor wafer of this embodiment, the protective film forming step may not be performed and the pickup step may be performed. After the pickup step A protective film forming step is performed (this embodiment may be referred to as "manufacturing method (3)"). That is, the manufacturing method (manufacturing method (3)) of this embodiment includes: a step of attaching the protective film-forming film in the protective film-forming composite sheet to a semiconductor wafer (attachment step); and dividing the semiconductor wafer. wafer, a step (dividing step) of cutting the aforementioned protective film-forming film to obtain a plurality of semiconductor wafers having the cut protective film-forming film; and separating the semiconductor wafers having the aforementioned cut protective film-forming film from the aforementioned The step of peeling off the support sheet and picking it up (picking step); and thermally curing the film for forming a protective film after being attached to the semiconductor wafer (the film for forming a protective film after cutting and picking up) to form a protective film. step (protective film forming step). FIG. 16 is a cross-sectional view schematically illustrating an embodiment of a manufacturing method of such a semiconductor wafer.
製造方法(3)中，於使用圖1所示之保護膜形成用複合片101之情形時，如圖16中的(a)所示，亦與製造方法(1)之情形同樣地，自保護膜形成用膜101移除剝離膜15。In the manufacturing method (3), when the protective film forming
製造方法(3)的前述貼附步驟及分割步驟分別如圖16中的(b)、圖16中的(c)所示，可利用與製造方法(2)的貼附步驟及分割步驟相同的方法(如圖15中的(b)、圖15中的(c)所示)進行。前述分割步驟中，由於保護膜形成用複合片101包含具有背面抗靜電層17之支撐片10，故而能夠防止因靜電等的影響而於保護膜形成用複合片101與切割台之間混入異物。結果，能夠防止於分割半導體晶圓9，切斷保護膜13時產生碎屑。The aforementioned attaching step and dividing step of the manufacturing method (3) are shown in (b) and (c) of FIG. 16 respectively. The same methods as the attaching step and the dividing step of the manufacturing method (2) can be used. The method (shown in (b) in Figure 15 and (c) in Figure 15) is performed. In the aforementioned dividing step, since the protective film-forming
製造方法(3)的前述拾取步驟中，如圖16中的(d)所示，將具備切斷後的保護膜形成用膜130之半導體晶片9'自支撐片10扯離而進行拾取。
製造方法(3)中的拾取步驟可利用與製造方法(1)及(2)中的拾取步驟相同的方法(如圖14中的(e)及圖15中的(e)所示)進行。In the aforementioned pickup step of the manufacturing method (3), as shown in (d) of FIG. 16 , the semiconductor wafer 9 ′ provided with the cut protective film forming film 130 is pulled away from the supporting
製造方法(3)的前述保護膜形成步驟中，使拾取後的保護膜形成用膜130熱硬化，如圖16中的(e)所示，於半導體晶片9'形成保護膜130'。 製造方法(3)中的保護膜形成步驟可利用與製造方法(1)及(2)中的保護膜形成步驟相同的方法進行。 藉由以上步驟，獲得目標半導體晶片9'作為附保護膜之半導體晶片。In the aforementioned protective film forming step of the manufacturing method (3), the picked up protective film forming film 130 is thermally cured, and as shown in (e) of FIG. 16 , a protective film 130' is formed on the semiconductor wafer 9'. The protective film forming step in the manufacturing method (3) can be performed by the same method as the protective film forming step in the manufacturing methods (1) and (2). Through the above steps, the target semiconductor wafer 9' is obtained as a semiconductor wafer with a protective film.
前文對使用圖1所示之保護膜形成用複合片101之情形的半導體晶片之製造方法進行了說明，但本實施形態的半導體晶片之製造方法並不限定於此。
例如，本實施形態的半導體晶片之製造方法即便使用圖2至圖5所示之保護膜形成用複合片102至保護膜形成用複合片105、圖6至圖10所示之保護膜形成用複合片201至保護膜形成用複合片205、圖11至圖13所示之保護膜形成用複合片301、保護膜形成用複合片401及保護膜形成用複合片501等圖1所示之保護膜形成用複合片101以外的保護膜形成用複合片，亦能夠同樣地製造半導體晶片。
如此，於使用另一實施形態的保護膜形成用複合片之情形時，只要基於這些片的結構的差異，於上述製造方法中，適宜地進行步驟之追加、變更、刪除等來製造半導體晶片即可。The manufacturing method of the semiconductor wafer in the case of using the protective film forming
◇半導體裝置之製造方法 藉由上述製造方法獲得附保護膜之半導體晶片後，藉由公知的方法將該半導體晶片倒裝晶片連接於基板的電路面，然後製成半導體封裝體，藉由使用該半導體封裝體，能夠製造目標半導體裝置(省略圖示)。 [實施例]◇Manufacturing method of semiconductor device After obtaining a semiconductor wafer with a protective film through the above-mentioned manufacturing method, the semiconductor wafer is flip-chip connected to the circuit surface of the substrate by a known method, and then a semiconductor package is produced. By using the semiconductor package, it is possible to manufacture Target semiconductor device (illustration omitted). [Example]
以下，藉由具體的實施例，對本發明更詳細地進行說明。但本發明完全不受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 at all by the Examples shown below.
[抗靜電組成物] 以下表示實施例或比較例中所使用之抗靜電組成物。 抗靜電組成物(VI-1)-1：藉由反應性乳化劑將聚吡咯進行乳化，並溶解於有機溶劑而獲得之聚吡咯溶液。 抗靜電組成物(VI-1)-2：出光興產公司製造的「UVH515」 抗靜電組成物(VI-1)-3：COLCOAT公司製造的「PC-303E」 抗靜電組成物(VI-1)-4：COLCOAT公司製造的「PC-309」[Antistatic composition] The following shows antistatic compositions used in Examples or Comparative Examples. Antistatic composition (VI-1)-1: a polypyrrole solution obtained by emulsifying polypyrrole with a reactive emulsifier and dissolving it in an organic solvent. Antistatic composition (VI-1)-2: "UVH515" manufactured by Idemitsu Kosan Co., Ltd. Antistatic composition (VI-1)-3: "PC-303E" manufactured by COLCOAT Antistatic composition (VI-1)-4: "PC-309" manufactured by COLCOAT
[保護膜形成用組成物的製造原料] 以下表示用於製造保護膜形成用組成物之原料。 [聚合物成分(A)] (A)-1：使丙烯酸正丁酯(10質量份)、丙烯酸甲酯(70質量份)、甲基丙烯酸縮水甘油酯(5質量份)及丙烯酸2-羥基乙酯(15質量份)共聚而成之丙烯酸系樹脂(重量平均分子量400000、玻璃轉移溫度-1℃) [熱硬化性成分(B)] ・環氧樹脂(B1) (B1)-1：雙酚A型環氧樹脂(三菱化學公司製造的「jER1055」，環氧當量800g/eq至900g/eq) (B1)-2：雙酚A型環氧樹脂(日本觸媒公司製造的「BPA328」，環氧當量235g/eq) (B1)-3：二環戊二烯型環氧樹脂(DIC公司製造的「Epiclon HP-7200HH」，環氧當量274g/eq至286g/eq) ・熱硬化劑(B2) (B2)-1：雙氰胺(熱活性潛伏性環氧樹脂硬化劑，三菱化學公司製造的「DICY7」，活性氫量21g/eq) [硬化促進劑(C)] (C)-1：2-苯基-4,5-二羥基甲基咪唑(四國化成工業公司製造的「Curezol 2PHZ-PW」) [填充材料(D)] (D)-1：二氧化矽填料(Admatechs公司製造的「SC2050MA」，利用環氧系化合物進行了表面修飾之二氧化矽填料，平均粒徑500nm) [著色劑(I)] (I)-1：碳黑(三菱化學公司製造的「MA600B」)[Raw materials for manufacturing compositions for forming protective films] The raw materials used for manufacturing the protective film forming composition are shown below. [Polymer component (A)] (A)-1: Copolymerize n-butyl acrylate (10 parts by mass), methyl acrylate (70 parts by mass), glycidyl methacrylate (5 parts by mass), and 2-hydroxyethyl acrylate (15 parts by mass) Acrylic resin made from (weight average molecular weight 400000, glass transition temperature -1℃) [Thermosetting ingredient (B)] ・Epoxy resin (B1) (B1)-1: Bisphenol A type epoxy resin ("jER1055" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 800g/eq to 900g/eq) (B1)-2: Bisphenol A type epoxy resin ("BPA328" manufactured by Nippon Shokubai Co., Ltd., epoxy equivalent 235g/eq) (B1)-3: Dicyclopentadiene-type epoxy resin ("Epiclon HP-7200HH" manufactured by DIC Corporation, epoxy equivalent 274g/eq to 286g/eq) ・Thermal hardener (B2) (B2)-1: Dicyandiamide (heat-active latent epoxy resin hardener, "DICY7" manufactured by Mitsubishi Chemical Corporation, active hydrogen content 21g/eq) [Harding accelerator (C)] (C)-1: 2-phenyl-4,5-dihydroxymethylimidazole ("Curezol 2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd.) [Filling material (D)] (D)-1: Silica filler ("SC2050MA" manufactured by Admatechs, a silica filler surface-modified with an epoxy compound, average particle size 500nm) [Color(I)] (I)-1: Carbon black ("MA600B" manufactured by Mitsubishi Chemical Corporation)
[實施例1] [保護膜形成用複合片之製造] [熱硬化性保護膜形成用組成物(III-1)之製造] 將聚合物成分(A)-1(150質量份)、環氧樹脂(B1)-1(10質量份)、環氧樹脂(B1)-2(60質量份)、環氧樹脂(B1)-3(30質量份)、熱硬化劑(B2)-1(2.4質量份)、硬化促進劑(C)-1(2.4質量份)、填充材料(D)-1(320質量份)、及著色劑(I)-1(1.16質量份)進行混合，進而以這些成分的合計濃度成為55質量%之方式，利用甲基乙基酮進行稀釋，製備熱硬化性保護膜形成用組成物(III-1)。[Example 1] [Manufacture of composite sheet for protective film formation] [Production of thermosetting protective film forming composition (III-1)] Polymer component (A)-1 (150 parts by mass), epoxy resin (B1)-1 (10 parts by mass), epoxy resin (B1)-2 (60 parts by mass), epoxy resin (B1)- 3 (30 parts by mass), thermal hardener (B2)-1 (2.4 parts by mass), hardening accelerator (C)-1 (2.4 parts by mass), filler (D)-1 (320 parts by mass), and coloring Agent (I)-1 (1.16 parts by mass) was mixed, and further diluted with methyl ethyl ketone so that the total concentration of these components became 55 mass %, to prepare a thermosetting protective film forming composition (III- 1).
[保護膜形成用膜之製造] 使用聚對苯二甲酸乙二酯製膜的單面藉由聚矽氧處理進行了剝離處理之剝離膜(琳得科公司製造的「SP-PET381031」，厚度38μm)，於該剝離膜的前述剝離處理面，塗敷上述所獲得之熱硬化性保護膜形成用組成物(III-1)，於100℃乾燥2分鐘，藉此製造厚度40μm之熱硬化性的保護膜形成用膜。[Manufacture of film for protective film formation] A release film ("SP-PET381031" manufactured by Lintec Co., Ltd., thickness 38 μm) made of polyethylene terephthalate and subjected to release treatment by polysiloxane treatment on one side. The thermosetting protective film-forming composition (III-1) obtained above was applied to the peeling-treated surface and dried at 100° C. for 2 minutes to produce a thermosetting protective film-forming film with a thickness of 40 μm.
[抗靜電層之形成] 作為基材，準備以下之聚丙烯製基材(厚度80μm)，其中一面的表面粗糙度Ra為0.2μm，另一面的表面粗糙度Ra小於該值，如此一面為凹凸面，另一面為平滑面。 於該聚丙烯製基材的前述凹凸面，使用棒式塗佈機，塗佈前述抗靜電組成物(VI-1)-1，於100℃乾燥2分鐘，藉此於前述基材上形成厚度75nm之背面抗靜電層。[Formation of antistatic layer] As the base material, prepare the following polypropylene base material (thickness 80 μm). The surface roughness Ra of one side is 0.2 μm, and the surface roughness Ra of the other side is less than this value. In this way, one side has an uneven surface and the other side has a smooth surface. . The antistatic composition (VI-1)-1 is coated on the uneven surface of the polypropylene base material using a rod coater and dried at 100° C. for 2 minutes, thereby forming a thickness on the base material. 75nm backside antistatic layer.
[黏著劑組成物(I-4)之製造] 製備非能量線硬化性的黏著劑組成物(I-4)，該黏著劑組成物(I-4)含有丙烯酸系聚合物(100質量份)、雙酚A型環氧樹脂(三菱化學公司製造的「JER828」)(以前述環氧樹脂的量計為30質量份)、及3官能苯二甲基二異氰酸酯系交聯劑(三井武田化學公司製造的「Takenate D110N」)(以前述交聯劑的量計為35質量份)，進而含有作為溶劑之甲基乙基酮，且前述丙烯酸系聚合物、環氧樹脂及交聯劑的合計濃度為35質量%。前述丙烯酸系聚合物係使丙烯酸-2-乙基己酯(60質量份)、甲基丙烯酸甲酯(30質量份)、及丙烯酸2-羥基乙酯(10質量份)共聚而成之重量平均分子量為600000之共聚物。[Production of adhesive composition (I-4)] A non-energy ray curable adhesive composition (I-4) containing an acrylic polymer (100 parts by mass) and bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation) was prepared. "JER828") (based on the amount of the above-mentioned epoxy resin as 30 parts by mass), and a trifunctional xylylene diisocyanate-based cross-linking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (based on the above-mentioned cross-linking The amount of the agent is 35 parts by mass), and further contains methyl ethyl ketone as a solvent, and the total concentration of the acrylic polymer, epoxy resin and cross-linking agent is 35 mass %. The weight average of the acrylic polymer copolymerized 2-ethylhexyl acrylate (60 parts by mass), methyl methacrylate (30 parts by mass), and 2-hydroxyethyl acrylate (10 parts by mass) A copolymer with a molecular weight of 600,000.
[支撐片之製造] 使用與上述製造保護膜形成用膜時所使用之剝離膜相同的剝離膜(琳得科公司製造的「SP-PET381031」，厚度38μm)，於該剝離膜的剝離處理面塗敷上述所獲得之黏著劑組成物(I-4)，於120℃加熱乾燥2分鐘，藉此形成厚度5μm之非能量線硬化性的黏著劑層。 繼而，將該剝離膜及黏著劑層之積層物中黏著劑層的露出面(換言之，黏著劑層中之與剝離膜側為相反側的面)、與上述所獲得之基材及背面抗靜電層之積層物中基材的露出面(換言之，基材中之與背面抗靜電層側為相反側的面)貼合。藉此，製造背面抗靜電層、基材、黏著劑層及剝離膜依序於這些層的厚度方向上積層而構成之附剝離膜之支撐片。[Manufacture of support sheet] The same release film ("SP-PET381031" manufactured by Lintec Co., Ltd., thickness 38 μm) as the release film used in the above-mentioned production of the protective film-forming film was used, and the resultant obtained above was applied to the release-treated surface of the release film. The adhesive composition (I-4) was heated and dried at 120° C. for 2 minutes to form a non-energy ray curable adhesive layer with a thickness of 5 μm. Next, the exposed surface of the adhesive layer in the laminate of the release film and the adhesive layer (in other words, the surface of the adhesive layer opposite to the release film side), the base material and the back surface obtained above are antistatic. The exposed surface of the base material in the laminate of the layers (in other words, the surface of the base material that is opposite to the back antistatic layer side) is bonded together. Thereby, a support sheet with a release film is produced, in which the back antistatic layer, the base material, the adhesive layer and the release film are sequentially laminated in the thickness direction of these layers.
[保護膜形成用複合片之製造]
於上述所獲得之支撐片中，移除剝離膜。然後，將該支撐片中新產生之黏著劑層的露出面(換言之，黏著劑層中之與基材側為相反側的面)、與上述所獲得之剝離膜及保護膜形成用膜之積層物中保護膜形成用膜的露出面(換言之，保護膜形成用膜中之與剝離膜側為相反側的面)貼合。藉此，獲得背面抗靜電層(厚度75nm)、基材(厚度80μm)、黏著劑層(厚度5μm)、保護膜形成用膜(厚度40μm)及剝離膜(厚度38μm)依序於這些層的厚度方向上積層而構成之保護膜形成用複合片。該保護膜形成用複合片中，將背面抗靜電層、基材及黏著劑層之積層體(換言之，支撐片)的平面形狀設為直徑為270mm之圓形，將保護膜形成用膜及剝離膜之積層體的平面形狀設為直徑為210mm之圓形，使這些2個圓成為同心。
繼而，移除剝離膜，於保護膜形成用膜的露出面(換言之，保護膜形成用膜中之與黏著劑層側為相反側的面、或第1面)中之保護膜形成用膜的周緣部附近的區域，設置治具用接著劑層。
繼而，於保護膜形成用膜的第1面及治具用接著劑層的第1面，貼合與之前移除之剝離膜相同的剝離膜(琳得科公司製造的「SP-PET381031」，厚度38μm)。
藉由以上步驟，製造附剝離膜之保護膜形成用複合片，該複合片為圖1所示之構成且保護膜形成用膜的大小較支撐片的大小略小。
表1中表示構成保護膜形成用複合片之各層。層一欄記載為「-」時，表示保護膜形成用複合片不具備該層。[Manufacture of composite sheet for protective film formation]
From the support sheet obtained above, remove the release film. Then, the exposed surface of the newly generated adhesive layer in the support sheet (in other words, the surface of the adhesive layer opposite to the base material side) is laminated with the release film and protective film forming film obtained above. The exposed surface of the protective film forming film in the object (in other words, the surface of the protective film forming film opposite to the peeling film side) is bonded together. In this way, the back antistatic layer (thickness 75 nm), the base material (thickness 80 μm), the adhesive layer (thickness 5 μm), the protective film forming film (
[實施例2]
使用前述抗靜電組成物(VI-1)-2代替前述抗靜電組成物(VI-1)-1，變更前述抗靜電組成物(VI-1)-2的塗佈量，於50℃乾燥1分鐘，藉此於基材上形成厚度170nm之背面抗靜電層，除這些方面以外，利用與實施例1之情形相同的方法，製造及評價保護膜形成用複合片。本實施例中所製造之附剝離膜之保護膜形成用複合片係背面抗靜電層(厚度170nm)、基材(厚度80μm)、黏著劑層(厚度5μm)、保護膜形成用膜(厚度40μm)及剝離膜(厚度38μm)依序於這些層的厚度方向上積層而構成，並且為圖1所示之構成且保護膜形成用膜的大小較支撐片的大小略小。[Example 2]
Use the aforementioned antistatic composition (VI-1)-2 instead of the aforementioned antistatic composition (VI-1)-1, change the coating amount of the aforementioned antistatic composition (VI-1)-2, and dry at 50°C for 1 minutes, thereby forming a backside antistatic layer with a thickness of 170 nm on the base material. Except for these points, a composite sheet for forming a protective film was produced and evaluated in the same manner as in Example 1. The composite sheet for forming a protective film with a release film produced in this example consists of a back antistatic layer (thickness 170 nm), a base material (thickness 80 μm), an adhesive layer (thickness 5 μm), and a film for forming a protective film (
[實施例3]
變更前述抗靜電組成物(VI-1)-2的塗佈量，將背面抗靜電層的厚度設為50nm代替170nm，除這些方面以外，利用與實施例2之情形相同的方法，製造及評價保護膜形成用複合片。本實施例中所製造之附剝離膜之保護膜形成用複合片係背面抗靜電層(厚度50nm)、基材(厚度80μm)、黏著劑層(厚度5μm)、保護膜形成用膜(厚度40μm)及剝離膜(厚度38μm)依序於這些層的厚度方向上積層而構成，並且為圖1所示之構成且保護膜形成用膜的大小較支撐片的大小略小。[Example 3]
The coating amount of the antistatic composition (VI-1)-2 was changed, and the thickness of the back antistatic layer was set to 50 nm instead of 170 nm. Except for these points, the same method as in Example 2 was used for production and evaluation. Composite sheet for protective film formation. The composite sheet for forming a protective film with a release film produced in this example consists of a back antistatic layer (
[實施例4] [保護膜形成用複合片之製造] [抗靜電性基材之製造] 對含有丙烯酸胺基甲酸酯樹脂及光聚合起始劑，且光聚合起始劑的含量相對於丙烯酸胺基甲酸酯樹脂的含量之比例為3.0質量%之組成物，調配作為抗靜電劑之鏻系離子液體(由鏻鹽所構成之離子液體)，並進行攪拌，藉此獲得能量線硬化性的抗靜電組成物(VI-2)。此時，抗靜電組成物(VI-2)中，抗靜電劑的含量相對於抗靜電劑及丙烯酸胺基甲酸酯樹脂的合計含量之比例係設為9.0質量%。[Example 4] [Manufacture of composite sheet for protective film formation] [Manufacture of antistatic substrate] A composition containing an acrylic urethane resin and a photopolymerization initiator, and the content of the photopolymerization initiator relative to the content of the acrylic urethane resin is 3.0% by mass, is prepared as an antistatic agent The phosphonium-based ionic liquid (an ionic liquid composed of a phosphonium salt) is stirred to obtain an energy ray-curable antistatic composition (VI-2). At this time, the ratio of the content of the antistatic agent to the total content of the antistatic agent and acrylic urethane resin in the antistatic composition (VI-2) was 9.0 mass %.
繼而，藉由噴注式模具(fountain die)方式，將上述所獲得之抗靜電組成物(VI-2)塗佈於聚對苯二甲酸乙二酯製之製程膜(東麗公司製造之「Lumirror T60 PET 50 T-60 Toray」，厚度50μm製品)上，形成厚度80μm之塗膜。然後，使用紫外線照射裝置(EYEGRAPHICS公司製造的「ECS-401GX」)，使用高壓水銀燈(EYEGRAPHICS公司製造的「H04-L41」)，將燈的高度設為150mm、燈輸出設為3kw(換算輸出120mW/cm)、波長365nm之光線的照度設為271mW/cm2 、光量設為175mJ/cm2 ，對該塗膜照射紫外線。 繼而，使用剝離膜(琳得科公司製造的「SP-PET3801」，厚度38μm)，將該剝離膜的剝離處理面貼合於該紫外線照射後的塗膜。 繼而，使用與上述相同的紫外線照射裝置及高壓水銀燈，將燈的高度設為150mm、波長365nm之光線的照度設為271mW/cm2 、光量設為600mJ/cm2 ，經由前述剝離膜，對前述塗膜照射紫外線2次，藉此使前述塗膜(更具體而言，前述丙烯酸胺基甲酸酯樹脂)進行紫外線硬化。 繼而，自該紫外線硬化後的塗膜，移除前述製程膜及剝離膜，獲得含有聚丙烯酸胺基甲酸酯及鏻系離子液體，且厚度為80μm之抗靜電性基材。所獲得之抗靜電性基材中，抗靜電劑的含量相對於抗靜電劑及聚丙烯酸胺基甲酸酯的合計含量之比例為9.0質量%。表1中的「抗靜電劑(含量之比例(質量%))」一欄中表示該數值。Then, the antistatic composition (VI-2) obtained above was coated on a process film made of polyethylene terephthalate (manufactured by Toray Corporation) using an injection mold (fountain die). Lumirror T60 PET 50 T-60 Toray", 50μm thick product), forming a coating film with a thickness of 80μm. Then, an ultraviolet irradiation device ("ECS-401GX" manufactured by EYEGRAPHICS) was used, a high-pressure mercury lamp ("H04-L41" manufactured by EYEGRAPHICS) was used, the height of the lamp was set to 150mm, and the lamp output was set to 3kw (converted output: 120mW /cm), the illuminance of light with a wavelength of 365 nm was set to 271 mW/cm 2 , and the light amount was set to 175 mJ/cm 2 , and the coating film was irradiated with ultraviolet rays. Next, a release film ("SP-PET3801" manufactured by Lindec Corporation, thickness 38 μm) was used, and the release-treated surface of the release film was bonded to the ultraviolet irradiated coating film. Then, the same ultraviolet irradiation device and high-pressure mercury lamp as above were used, the height of the lamp was set to 150mm, the illumination intensity of the light with a wavelength of 365nm was set to 271mW/cm 2 , and the light amount was set to 600mJ/cm 2 , and the above-mentioned film was removed through the aforementioned peeling film. The coating film (more specifically, the acrylic urethane resin) is cured by ultraviolet rays by irradiating the coating film twice with ultraviolet rays. Then, from the ultraviolet cured coating film, the aforementioned process film and peeling film were removed to obtain an antistatic substrate containing polyacrylic urethane and phosphonium-based ionic liquid and having a thickness of 80 μm. In the obtained antistatic base material, the content of the antistatic agent was 9.0% by mass relative to the total content of the antistatic agent and polyacrylic urethane. This value is shown in the column "Antistatic agent (content ratio (mass %))" in Table 1.
[支撐片之製造] 利用與實施例1之情形相同的方法，於剝離膜(琳得科公司製造的「SP-PET381031」，厚度38μm)的剝離處理面，形成厚度5μm之非能量線硬化性的黏著劑層。 繼而，將該剝離膜及黏著劑層之積層物中黏著劑層的露出面(換言之，黏著劑層中之與剝離膜側為相反側的面)、與上述所獲得之抗靜電性基材的一面貼合。藉此，製造抗靜電性基材、黏著劑層及剝離膜依序於這些層的厚度方向上積層而構成的附剝離膜之支撐片。[Manufacture of support sheet] Using the same method as in Example 1, a non-energy ray curable adhesive layer with a thickness of 5 μm was formed on the release-treated surface of the release film ("SP-PET381031" manufactured by Lintec Corporation, thickness 38 μm). Next, the exposed surface of the adhesive layer in the laminate of the release film and the adhesive layer (in other words, the surface of the adhesive layer opposite to the release film side) was compared with the surface of the antistatic base material obtained above. One side fits. Thereby, a support sheet with a release film is produced, in which an antistatic base material, an adhesive layer, and a release film are sequentially laminated in the thickness direction of these layers.
[保護膜形成用複合片之製造]
使用上述所獲得之具備抗靜電性基材之支撐片代替具備背面抗靜電層及基材之前述支撐片，除該方面以外，利用與實施例1之情形相同的方法，製造附剝離膜之保護膜形成用複合片，該附剝離膜之保護膜形成用複合片係抗靜電性基材(厚度80μm)、黏著劑層(厚度5μm)、保護膜形成用膜(厚度40μm)及剝離膜(厚度38μm)依序於這些層的厚度方向上積層而構成，且進而具備治具用接著劑層。於該附剝離膜之保護膜形成用複合片中，抗靜電性基材及黏著劑層之積層體(換言之，支撐片)的平面形狀係直徑為270mm之圓形，保護膜形成用膜及剝離膜之積層體的平面形狀係直徑為210mm之圓形，這些2個圓為同心。該附剝離膜之保護膜形成用複合片為圖6所示之構成且保護膜形成用膜的大小較支撐片的大小略小。[Manufacture of composite sheet for protective film formation]
The support sheet having the antistatic base material obtained above was used instead of the aforementioned support sheet having the back antistatic layer and the base material. Except for this point, the same method as in Example 1 was used to produce a protective film with a release film. Composite sheet for film formation. The composite sheet for protective film formation with a release film is composed of an antistatic base material (thickness 80 μm), an adhesive layer (thickness 5 μm), a film for protective film formation (
[比較例1]
使用前述抗靜電組成物(VI-1)-3代替前述抗靜電組成物(VI-1)-1，變更前述抗靜電組成物(VI-1)-3的塗佈量，於基材上形成厚度110nm之背面抗靜電層，以及將前述抗靜電組成物(VI-1)-3的乾燥條件設為乾燥溫度125℃、乾燥時間1分鐘，除這些方面以外，利用與實施例1之情形相同的方法，製造及評價保護膜形成用複合片。本比較例中所製造之附剝離膜之保護膜形成用複合片係背面抗靜電層(厚度110nm)、基材(厚度80μm)、黏著劑層(厚度5μm)、保護膜形成用膜(厚度40μm)及剝離膜(厚度38μm)依序於這些層的厚度方向上積層而構成，並且為圖1所示之構成且保護膜形成用膜的大小較支撐片的大小略小。[Comparative example 1]
Use the aforementioned antistatic composition (VI-1)-3 instead of the aforementioned antistatic composition (VI-1)-1, change the coating amount of the aforementioned antistatic composition (VI-1)-3, and form a The back antistatic layer with a thickness of 110 nm and the drying conditions of the antistatic composition (VI-1)-3 were set to a drying temperature of 125°C and a drying time of 1 minute. The same conditions were used as in Example 1 except for these aspects. A method for manufacturing and evaluating a composite sheet for forming a protective film. The composite sheet for forming a protective film with a release film produced in this comparative example consists of a back antistatic layer (thickness 110 nm), a base material (thickness 80 μm), an adhesive layer (thickness 5 μm), and a film for forming a protective film (
[比較例2]
使用前述抗靜電組成物(VI-1)-4代替前述抗靜電組成物(VI-1)-1，變更前述抗靜電組成物(VI-1)-4的塗佈量，於基材上形成厚度110nm之背面抗靜電層，以及將前述抗靜電組成物(VI-1)-4的乾燥條件設為乾燥溫度125℃、乾燥時間1分鐘，除此以外，利用與實施例1之情形相同的方法，製造及評價保護膜形成用複合片。本實施例中所製造之附剝離膜之保護膜形成用複合片係背面抗靜電層(厚度110nm)、基材(厚度80μm)、黏著劑層(厚度5μm)、保護膜形成用膜(厚度40μm)及剝離膜(厚度38μm)依序於這些層的厚度方向上積層而構成，並且為圖1所示之構成且保護膜形成用膜的大小較支撐片的大小略小。[Comparative example 2]
Use the aforementioned antistatic composition (VI-1)-4 instead of the aforementioned antistatic composition (VI-1)-1, change the coating amount of the aforementioned antistatic composition (VI-1)-4, and form a The same conditions as in Example 1 were used except that the back antistatic layer had a thickness of 110 nm and the drying conditions of the antistatic composition (VI-1)-4 were set to a drying temperature of 125°C and a drying time of 1 minute. Method, production and evaluation of composite sheet for protective film formation. The composite sheet for forming a protective film with a release film produced in this example consists of a back antistatic layer (thickness 110 nm), a base material (thickness 80 μm), an adhesive layer (thickness 5 μm), and a film for forming a protective film (
[比較例3]
不形成背面抗靜電層，除該方面以外，利用與實施例1之情形相同的方法，製造及評價保護膜形成用複合片。本比較例中所製造之附剝離膜之保護膜形成用複合片係基材(厚度80μm)、黏著劑層(厚度5μm)、保護膜形成用膜(厚度40μm)及剝離膜(厚度38μm)依序於這些層的厚度方向上積層而構成，且進而具備治具用接著劑層之保護膜形成用複合片，並且於圖1中不具備背面抗靜電層，且保護膜形成用膜的大小較支撐片的大小略小。[Comparative example 3]
A composite sheet for forming a protective film was produced and evaluated in the same manner as in Example 1 except that the back antistatic layer was not formed. The composite sheet for forming a protective film with a peeling film produced in this comparative example is composed of a base material (thickness 80 μm), an adhesive layer (thickness 5 μm), a film for forming a protective film (
[表1]
[保護膜形成用複合片之評價] [保護膜形成用膜熱硬化前的保護膜形成用複合片的表面電阻率之測定] 使用表面電阻率計(Advantest公司製造的「R12704 Resistivity chamber」)，不使上述所獲得之保護膜形成用複合片中的保護膜形成用膜熱硬化，而將施加電壓設為100V，測定該片中的背面抗靜電層的表面電阻率。結果示於表2中的「表面電阻率(Ω/□)/加熱前」一欄。[Evaluation of composite sheet for protective film formation] [Measurement of the surface resistivity of the protective film-forming composite sheet before thermal curing of the protective film-forming film] Using a surface resistivity meter ("R12704 Resistivity chamber" manufactured by Advantest Corporation), the protective film-forming film in the protective film-forming composite sheet obtained above was measured by setting the applied voltage to 100V without thermally curing the sheet. The surface resistivity of the backside antistatic layer in . The results are shown in the column "Surface resistivity (Ω/□)/before heating" in Table 2.
[保護膜形成用膜熱硬化後的保護膜形成用複合片的表面電阻率之測定] 使用測定上述之熱硬化前的表面電阻率之保護膜形成用複合片，將該保護膜形成用複合片中的保護膜形成用膜於130℃熱硬化2小時。繼而，利用與上述相同的方法，測定該熱硬化後的保護膜形成用複合片中的背面抗靜電層的表面電阻率。結果示於表2中的「表面電阻率(Ω/□)/加熱後」一欄。[Measurement of the surface resistivity of the protective film-forming composite sheet after the protective film-forming film was thermally cured] Using the composite sheet for protective film formation whose surface resistivity before thermal curing was measured, the film for protective film formation in the composite sheet for protective film formation was thermally cured at 130° C. for 2 hours. Next, the surface resistivity of the back surface antistatic layer in the thermally cured composite sheet for forming a protective film was measured using the same method as described above. The results are shown in the column "Surface resistivity (Ω/□)/after heating" in Table 2.
[支撐片的全光線透過率之測定] 針對上述所獲得之支撐片，依據JIS K 7375：2008，使用分光光度計(島津製作所股份有限公司製造，製品名「UV-VIS-NIR SPECTROPHOTOMETER UV-3600」)，測定全光線透過率(%)。結果示於表2中的「支撐片的全光線透過率(%)」一欄。[Measurement of total light transmittance of support sheet] For the support sheet obtained above, the total light transmittance (%) was measured using a spectrophotometer (manufactured by Shimadzu Corporation, product name "UV-VIS-NIR SPECTROPHOTOMETER UV-3600") in accordance with JIS K 7375:2008. . The results are shown in the column "Total light transmittance (%) of the support sheet" in Table 2.
[抗靜電層的耐擦傷性之評價] 針對上述所獲得之支撐片中的背面抗靜電層，利用下述方法評價耐擦傷性。 亦即，使用大榮科學精器製作所製造的平面磨耗試驗機「PA-2A」，於該試驗機中的頭部的按壓面被覆法蘭絨布。前述按壓面為平面狀，且前述按壓面的面積為2cm×2cm。作為法蘭絨布，使用厚度處於上文所說明之範圍內之法蘭絨布。將被覆有該法蘭絨布之頭部的按壓面壓抵於背面抗靜電層的表面，以該狀態，一邊藉由頭部對背面抗靜電層施加125g/cm2 之荷重而進行按壓，一邊使頭部以10cm之直線距離往返運動10次，藉此一邊經由法蘭絨布而施加125g/cm2 之荷重，一邊摩擦背面抗靜電層。然後，目視觀察背面抗靜電層的該摩擦面中面積為2cm×2cm之區域，將未確認到傷痕之情形判定為「A」，將確認到傷痕之情形判定為「B」，而評價抗靜電層的耐擦傷性。 結果示於表2中的「抗靜電層或基材的耐擦傷性」一欄。[Evaluation of Scratch Resistance of Antistatic Layer] The scratch resistance of the backside antistatic layer in the support sheet obtained above was evaluated by the following method. That is, a flat abrasion testing machine "PA-2A" manufactured by Daiei Scientific Seiki Manufacturing Co., Ltd. was used, and the pressing surface of the head of the testing machine was covered with flannel cloth. The pressing surface is flat, and the area of the pressing surface is 2cm×2cm. As the flannel cloth, use a flannel cloth with a thickness within the range explained above. The pressing surface of the head covered with the flannel cloth is pressed against the surface of the back antistatic layer. In this state, a load of 125g/ cm2 is applied to the back antistatic layer by the head while pressing. The head is moved back and forth 10 times in a straight line distance of 10cm, thereby applying a load of 125g/ cm2 through the flannel cloth while rubbing the antistatic layer on the back. Then, an area of 2 cm × 2 cm on the friction surface of the back antistatic layer was visually observed, and the case where no scratches were confirmed was judged as "A", and the case where scratches were confirmed was judged as "B", and the antistatic layer was evaluated. scratch resistance. The results are shown in the column "Scuff resistance of antistatic layer or substrate" in Table 2.
[具備保護膜之半導體晶片之評價] [具備保護膜之半導體晶片之製造] 使用上述所獲得之保護膜形成用複合片，採用製造方法(1)，製造附保護膜之半導體晶片。此時，藉由依序進行前述貼附步驟、保護膜形成步驟、分割步驟、及拾取步驟，而製造附保護膜之半導體晶片。各步驟的更詳細的條件如以下所示。[Evaluation of semiconductor wafers with protective films] [Manufacturing of semiconductor wafers with protective films] Using the composite sheet for forming a protective film obtained above, a semiconductor wafer with a protective film is produced using the manufacturing method (1). At this time, a semiconductor wafer with a protective film is manufactured by sequentially performing the aforementioned attaching step, protective film forming step, dividing step, and picking up step. More detailed conditions for each step are shown below.
亦即，前述貼附步驟中，作為半導體晶圓，使用8吋矽鏡面晶圓(厚度350μm)，對該晶圓的內面(鏡面之面)貼附保護膜形成用複合片，製作分割前積層體。貼附溫度係設為70℃。That is, in the above attaching step, an 8-inch silicon mirror wafer (thickness 350 μm) is used as the semiconductor wafer, a composite sheet for forming a protective film is attached to the inner surface (mirror surface) of the wafer, and a composite sheet is attached before dividing. Laminated body. The attachment temperature system was set to 70°C.
前述保護膜形成步驟中，使保護膜形成用膜於130℃熱硬化2小時，製作已硬化的積層體。In the protective film forming step, the protective film forming film is thermally cured at 130° C. for 2 hours to prepare a cured laminated body.
前述分割步驟中，使用切割裝置(Disco公司製造的「DFD6362」)，將已硬化的積層體載置於切割台，進行切割，藉此分割已硬化的積層體，獲得大小為5mm×5mm之硬化及已分割的積層體。此時的切割係將切割刀片的移動速度設為50mm/sec，將切割刀片的轉速設為30000rpm而進行。In the aforementioned dividing step, a cutting device ("DFD6362" manufactured by Disco) is used to place the hardened laminated body on a cutting table and cut, thereby dividing the hardened laminated body into hardened pieces with a size of 5 mm × 5 mm. and divided laminates. The cutting at this time was performed by setting the moving speed of the cutting blade to 50 mm/sec and the rotation speed of the cutting blade to 30,000 rpm.
前述拾取步驟中，使用拾取-黏晶裝置(Canon Machinery公司製造的「BESTEM D-02」)，於常溫下將硬化及已分割的積層體予以固定後，於該硬化及已分割的積層體與固定該積層體之環狀框架之間新產生3mm之高低差。然後，以該狀態，自硬化及已分割的積層體之背面抗靜電層側施加力而頂起硬化及已分割的積層體，藉此將硬化及已分割的積層體自前述支撐片扯離而進行拾取。此時，作為頂起部，使用1個突起(頂銷)，將該頂起部的頂起高度設為0.6mm、頂起速度設為20mm/s、頂起保持時間設為30毫秒，頂起硬化及已分割的積層體。 藉由以上步驟，獲得大小為5mm×5mm、厚度為350μm之矽晶片作為半導體晶片。該半導體晶片的內面所具備之保護膜的大小與該半導體晶片的大小同等。In the aforementioned pick-up step, a pick-up and die-bonding device ("BESTEM D-02" manufactured by Canon Machinery Co., Ltd.) is used to fix the hardened and divided laminated body at normal temperature, and then the hardened and divided laminated body and A new height difference of 3 mm is created between the annular frames that fix the laminated body. Then, in this state, force is applied from the antistatic layer side on the back of the hardened and divided laminated body to push up the hardened and divided laminated body, thereby pulling the hardened and divided laminated body away from the aforementioned support piece. Make a pickup. At this time, a protrusion (ejector pin) is used as the jacking part, and the jacking height of the jacking part is set to 0.6mm, the jacking speed is set to 20mm/s, and the jacking holding time is set to 30 milliseconds. From hardened and divided laminates. Through the above steps, a silicon wafer with a size of 5mm×5mm and a thickness of 350μm is obtained as a semiconductor wafer. The size of the protective film provided on the inner surface of the semiconductor wafer is equal to the size of the semiconductor wafer.
[碎屑評價] 利用以下所示之方法評價上述具備保護膜之半導體晶片之製造中的前述分割步驟中所產生之碎屑的數量。 亦即，利用數位顯微鏡(KEYENCE公司製造，VE-9800)計數前述分割步驟後的10μm以上之碎屑。根據碎屑的個數，按照以下的基準進行評價。結果示於表2。 A：0個 B：1個至2個 C：3個以上[crumb evaluation] The method shown below was used to evaluate the amount of debris generated in the dividing step in the production of the semiconductor wafer provided with the protective film. That is, a digital microscope (VE-9800, manufactured by KEYENCE Corporation) was used to count the debris of 10 μm or more after the aforementioned dividing step. Based on the number of chips, evaluation is based on the following criteria. The results are shown in Table 2. A: 0 B: 1 to 2 C: 3 or more
[表2]
由上述結果可明確，實施例1至實施例4的保護膜形成用複合片中，支撐片側的最表層的表面電阻率於使保護膜形成用膜熱硬化前為2.1×105 Ω/□至3.5×1010 Ω/□，於使保護膜形成用膜熱硬化後為1.3×106 Ω/□至9.2×1010 Ω/□，這些保護膜形成用複合片的抗靜電性優異。因此，能夠防止因靜電等的影響而於前述附保護膜之半導體晶圓與切割台之間混入異物，結果於實施例1至實施例4的保護膜形成用複合片中未產生碎屑。From the above results, it is clear that in the protective film-forming composite sheets of Examples 1 to 4, the surface resistivity of the outermost layer on the support sheet side before the protective film-forming film is thermally cured is 2.1×10 5 Ω/□ to 3.5×10 10 Ω/□, and 1.3×10 6 Ω/□ to 9.2×10 10 Ω/□ after thermosetting the film for protective film formation. These composite sheets for protective film formation have excellent antistatic properties. Therefore, it is possible to prevent foreign matters from being mixed between the semiconductor wafer with a protective film and the cutting table due to the influence of static electricity, etc. As a result, no debris is generated in the protective film forming composite sheets of Examples 1 to 4.
實施例1至實施例4的保護膜形成用複合片中的支撐片的全光線透過率為80%以上(80%至91%)，這些複合片具有較佳的光學特性。The total light transmittance of the support sheet in the protective film forming composite sheets of Examples 1 to 4 is above 80% (80% to 91%), and these composite sheets have better optical properties.
實施例1至實施例3的保護膜形成用複合片中的背面抗靜電層、及實施例4的保護膜形成用複合片中的抗靜電性基材的耐擦傷性均高，這些複合片的保護膜形成用膜的檢查性良好。The backside antistatic layer in the protective film-forming composite sheet of Examples 1 to 3 and the antistatic base material in the protective film-forming composite sheet of Example 4 all have high scratch resistance. These composite sheets have The film for protective film formation has good inspection properties.
相對於此，比較例1的保護膜形成用複合片中，支撐片側的最表層的表面電阻率於使保護膜形成用膜熱硬化前為2.6×1010 Ω/□，於使保護膜形成用膜熱硬化後為1.1×1015 Ω/□，比較例1的保護膜形成用複合片的抗靜電能力不充分。因此，因靜電等的影響而於附保護膜之半導體晶圓與切割台之間混入異物，結果於比較例1的保護膜形成用複合片中產生了碎屑。In contrast, in the protective film-forming composite sheet of Comparative Example 1, the surface resistivity of the outermost layer on the support sheet side was 2.6×10 10 Ω/□ before the protective film-forming film was thermally cured. The value of the film after thermal curing was 1.1×10 15 Ω/□, indicating that the antistatic ability of the composite sheet for forming a protective film of Comparative Example 1 was insufficient. Therefore, foreign matter was mixed between the semiconductor wafer with the protective film and the dicing table due to the influence of static electricity, etc. As a result, debris was generated in the composite sheet for forming a protective film in Comparative Example 1.
比較例2的保護膜形成用複合片中，支撐片側的最表層的表面電阻率於使保護膜形成用膜熱硬化前為2.1×1011 Ω/□，於使保護膜形成用膜熱硬化後為1.5×1015 Ω/□，比較例2的保護膜形成用複合片的抗靜電能力不充分。因此，因靜電等的影響而於附保護膜之半導體晶圓與切割台之間混入異物，結果於比較例2的保護膜形成用複合片中產生了碎屑。In the protective film-forming composite sheet of Comparative Example 2, the surface resistivity of the outermost layer on the support sheet side was 2.1 × 10 11 Ω/□ before the protective film-forming film was thermally cured, and after the protective film-forming film was thermally cured. It is 1.5×10 15 Ω/□, and the antistatic ability of the protective film forming composite sheet of Comparative Example 2 is insufficient. Therefore, foreign matter was mixed between the semiconductor wafer with the protective film and the dicing table due to the influence of static electricity, etc. As a result, debris was generated in the composite sheet for forming a protective film in Comparative Example 2.
比較例3的保護膜形成用複合片不具備背面抗靜電層及抗靜電性基材兩者，因此支撐片側的最表層的表面電阻率於使保護膜形成用膜熱硬化前為5.0×1015 Ω/□，於使保護膜形成用膜熱硬化後為5.6×1015 Ω/□，比較例3的保護膜形成用複合片的抗靜電能力明顯不充分。因此，因靜電等的影響而於附保護膜之半導體晶圓與切割台之間混入異物，結果於比較例3的保護膜形成用複合片中產生了大量碎屑。The composite sheet for protective film formation in Comparative Example 3 does not include both the back antistatic layer and the antistatic base material. Therefore, the surface resistivity of the outermost layer on the support sheet side before the film for protective film formation is thermally cured is 5.0×10 15 Ω/□ was 5.6×10 15 Ω/□ after thermally curing the protective film-forming film. The antistatic ability of the protective film-forming composite sheet of Comparative Example 3 was obviously insufficient. Therefore, foreign matter was mixed between the semiconductor wafer with the protective film and the dicing table due to the influence of static electricity, etc. As a result, a large amount of debris was generated in the composite sheet for forming a protective film in Comparative Example 3.
比較例3的保護膜形成用複合片中的基材的耐擦傷性低，該複合片的保護膜形成用膜的檢查性差。The scratch resistance of the substrate in the protective film-forming composite sheet of Comparative Example 3 was low, and the protective film-forming film of this composite sheet had poor inspection properties.
以上，對本發明的較佳的實施例進行了說明，但本發明並不限定於這些實施例。可在不脫離本發明的主旨之範圍內，進行構成之附加、省略、置換、及其他變更。本發明不受前述說明的限定，而僅受隨附的申請專利範圍的限定。 [產業可利用性]The preferred embodiments of the present invention have been described above, but the present invention is not limited to these embodiments. Additions, omissions, substitutions, and other changes in the structure can be made without departing from the gist of the present invention. The present invention is not limited by the foregoing description, but only by the scope of the appended patent applications. [Industrial Availability]
本發明可用於製造半導體裝置。The present invention can be used to manufacture semiconductor devices.
8:扯離機構 9:半導體晶圓 9b:半導體晶圓的內面 9':半導體晶片 10,20,30,40,50,60,70:支撐片 10a,20a,30a,40a,50a,60a,70a:支撐片的第1面 11:基材 11a:基材的第1面 11b:基材的第2面 11':抗靜電性基材 11a':抗靜電性基材的第1面 11b':抗靜電性基材的第2面 12:黏著劑層 12a:黏著劑層的第1面 13,23:保護膜形成用膜 13a,23a:保護膜形成用膜的第1面 13':保護膜 15:剝離膜 16:治具用接著劑層 16a:治具用接著劑層的第1面 16c:治具用接著劑層的側面 17:背面抗靜電層 17a:背面抗靜電層的第1面 18:中間層 18a:中間層的第1面 18b:中間層的第2面 18c:中間層的側面 19:表面抗靜電層 19a:表面抗靜電層的第1面 23b:保護膜形成用膜的第2面 23c:保護膜形成用膜的側面 101,101',102,103,104,105,201,202,203,204,205,301,401,501:保護膜形成用複合片 130:切斷後的保護膜形成用膜 130':切斷後的保護膜 I:拾取方向8: Break away from the organization 9:Semiconductor wafer 9b: Inner surface of semiconductor wafer 9':Semiconductor wafer 10,20,30,40,50,60,70: Support piece 10a, 20a, 30a, 40a, 50a, 60a, 70a: The first side of the support piece 11:Substrate 11a:Side 1 of the substrate 11b:Side 2 of the substrate 11': Antistatic base material 11a': The first side of the antistatic substrate 11b': The second side of the antistatic substrate 12: Adhesive layer 12a: Side 1 of adhesive layer 13,23: Film for protective film formation 13a, 23a: The first side of the protective film forming film 13':Protective film 15: Peel off film 16: Adhesive layer for fixtures 16a: The first side of the adhesive layer for the jig 16c: Side of the adhesive layer for the jig 17: Antistatic layer on the back 17a: The first side of the back antistatic layer 18:Middle layer 18a: Side 1 of the middle layer 18b: Side 2 of the middle layer 18c: Side of middle layer 19: Surface antistatic layer 19a: The first side of the surface antistatic layer 23b: The second side of the protective film forming film 23c: Side surface of protective film forming film 101,101',102,103,104,105,201,202,203,204,205,301,401,501: Composite sheet for protective film formation 130: Film for forming protective film after cutting 130':Protective film after cutting I: Picking direction
[圖1]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖2]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖3]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖4]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖5]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖6]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖7]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖8]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖9]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖10]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖11]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖12]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖13]係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖視圖。 [圖14]係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。 [圖15]係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。 [圖16]係用於以示意方式說明本發明的一實施形態的半導體晶片之製造方法之剖視圖。[Fig. 1] is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. [Fig. 2] Fig. 2 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. [Fig. 3] Fig. 3 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. [Fig. 4] is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. [Fig. 5] is a cross-sectional view schematically showing the composite sheet for forming a protective film according to one embodiment of the present invention. [Fig. 6] Fig. 6 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. [Fig. 7] Fig. 7 is a cross-sectional view schematically showing the composite sheet for forming a protective film according to one embodiment of the present invention. [Fig. 8] Fig. 8 is a cross-sectional view schematically showing the composite sheet for forming a protective film according to one embodiment of the present invention. [Fig. 9] Fig. 9 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. [Fig. 10] Fig. 10 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. [Fig. 11] Fig. 11 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. [Fig. 12] Fig. 12 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. [Fig. 13] Fig. 13 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. [Fig. 14] Fig. 14 is a cross-sectional view schematically illustrating a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [Fig. 15] Fig. 15 is a cross-sectional view schematically illustrating a method of manufacturing a semiconductor wafer according to an embodiment of the present invention. [Fig. 16] Fig. 16 is a cross-sectional view schematically illustrating a method of manufacturing a semiconductor wafer according to an embodiment of the present invention.
10:支撐片 10:Support piece
10a:支撐片的第1面 10a:Side 1 of the support piece
11:基材 11:Substrate
11a:基材的第1面 11a:Side 1 of the substrate
11b:基材的第2面 11b:Side 2 of the substrate
12:黏著劑層 12: Adhesive layer
12a:黏著劑層的第1面 12a: Side 1 of adhesive layer
13:保護膜形成用膜 13: Film for protective film formation
13a:保護膜形成用膜的第1面 13a: The first side of the protective film forming film
15:剝離膜 15: Peel off film
16:治具用接著劑層 16: Adhesive layer for fixtures
16a:治具用接著劑層的第1面 16a: The first side of the adhesive layer for the jig
16c:治具用接著劑層的側面 16c: Side of the adhesive layer for the jig
17:背面抗靜電層 17: Antistatic layer on the back
17a:背面抗靜電層的第1面 17a: The first side of the back antistatic layer
101:保護膜形成用複合片 101: Composite sheet for protective film formation
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| JP5865044B2 (en) * | 2011-12-07 | 2016-02-17 | リンテック株式会社 | Dicing sheet with protective film forming layer and chip manufacturing method |
| JP6297786B2 (en) | 2012-12-10 | 2018-03-20 | 日東電工株式会社 | Adhesive sheet, dicing tape integrated adhesive sheet, semiconductor device manufacturing method, and semiconductor device |
| JP2016096239A (en) * | 2014-11-14 | 2016-05-26 | 住友ベークライト株式会社 | Adhesive tape for processing wafer for semiconductor |
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| JP6506118B2 (en) * | 2015-06-25 | 2019-04-24 | リンテック株式会社 | Protective film-forming film, protective film-forming sheet, method of manufacturing work or workpiece, inspection method, workpiece judged to be non-defective, and workpiece judged to be non-defective |
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