TW202402537A - Protective sheet - Google Patents

Protective sheet Download PDF

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Publication number
TW202402537A
TW202402537A TW112122439A TW112122439A TW202402537A TW 202402537 A TW202402537 A TW 202402537A TW 112122439 A TW112122439 A TW 112122439A TW 112122439 A TW112122439 A TW 112122439A TW 202402537 A TW202402537 A TW 202402537A
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Taiwan
Prior art keywords
protective layer
release paper
release
protective
peeling force
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TW112122439A
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Chinese (zh)
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佐藤慧
宍戸雄一郎
高本尚英
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日商日東電工股份有限公司
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Publication of TW202402537A publication Critical patent/TW202402537A/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00Adhesives based on unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/40Adhesives in the form of films or foils characterised by release liners
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67Apparatus 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
    • H01L21/683Apparatus 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

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

Abstract

A protective sheet according to the present invention includes a protective layer, a first release liner arranged on one surface of the protective layer, and a second release liner arranged on the opposite surface of the protective layer, in which the protective layer includes a water-soluble polymer compound, and, when a peeling force of the first release liner relative to the protective layer is PA and the peeling force of the second release liner relative to the protective layer is PB, the peeling force PA and the peeling force PB satisfy a formula below: P A˂ P BP B≤ 2000 mN/25 mm.

Description

保護片材protective sheet

本發明係關於一種保護片材。The invention relates to a protective sheet.

一直以來,已知使用一種具有黏著性之保護片材,其係在製造半導體晶片等半導體元件或液晶表示裝置等電子零件時,用於防止異物附著於前述電子零件等(例如下述專利文獻1)。 下述專利文獻1中,作為前述保護片材,已揭露一種保護片材,其係具備藉由含有含氧化烯基之聚乙烯醇系樹脂之樹脂組成物所形成之保護層、及配置於該保護層之兩面之2片剝離片材。 Conventionally, it has been known to use an adhesive protective sheet for preventing foreign matter from adhering to the electronic components such as semiconductor elements such as semiconductor wafers or liquid crystal display devices (for example, Patent Document 1 below). ). The following Patent Document 1 discloses a protective sheet as the above-mentioned protective sheet, which has a protective layer formed of a resin composition containing an oxyalkylene group-containing polyvinyl alcohol-based resin, and is arranged on the protective layer. 2 peel-off sheets on both sides of the protective layer.

此外,上述電子零件之製造中,半導體晶片之製造,通常係藉由將一半導體晶圓分割(割斷)而實施(例如下述專利文獻2)。 例如下述專利文獻2中,已揭露一種用以下方法實施之半導體晶片之製造: (1)在矽晶圓之一表面側,形成複數個分割預定線以成為格子狀。 (2)在藉由前述複數個分割預定線劃分為格子狀之區域(以下,亦稱為格子狀劃分區域)各自形成電路圖案的同時配置電極部。藉此,製作用以獲得半導體晶片之半導體晶圓。 (3)將該半導體晶圓沿前述複數個分割預定線分割(割斷),換言之,按前述半導體晶圓之各個前述格子狀劃分區域分割(割斷),獲得複數個半導體晶片。 [先前技術文獻] [專利文獻] In addition, in the manufacturing of the above-mentioned electronic components, the manufacturing of semiconductor wafers is usually carried out by dividing (cutting) a semiconductor wafer (for example, Patent Document 2 below). For example, in the following patent document 2, a method of manufacturing a semiconductor wafer has been disclosed: (1) On one surface side of the silicon wafer, a plurality of planned division lines are formed into a grid shape. (2) The electrode portions are arranged while each circuit pattern is formed in the areas divided into a grid shape by the plurality of planned dividing lines (hereinafter also referred to as grid-like divided areas). Thereby, a semiconductor wafer for obtaining a semiconductor wafer is produced. (3) Divide (cut) the semiconductor wafer along the plurality of planned division lines, in other words, divide (cut) the semiconductor wafer according to each of the grid-shaped divided areas, thereby obtaining a plurality of semiconductor wafers. [Prior technical literature] [Patent Document]

[專利文獻1]日本國特開2021-161735號公報 [專利文獻2]日本國特開2012-119670號公報 [Patent Document 1] Japanese Patent Application Publication No. 2021-161735 [Patent document 2] Japanese Patent Application Publication No. 2012-119670

[發明所欲解決之技術問題][Technical problem to be solved by the invention]

然而,如上所述,將半導體晶圓分割(割斷)而獲得複數個半導體晶片時,有分割部(割斷部)附近之半導體晶圓之一部分粉狀化等而產生微細異物之情形。 並且,如此之微細異物附著於前述半導體晶片之一表面側(形成有電路圖案之側)時,有形成於一表面側之電路圖案所包含之電路的動作可靠性降低之疑慮,故不理想。 因此,半導體晶片之製造,經常係將前述保護片材之前述保護層貼合於前述半導體晶圓之一表面側(形成有電路圖案之側)來實施。 However, as described above, when a semiconductor wafer is divided (cut) to obtain a plurality of semiconductor wafers, a part of the semiconductor wafer near the divided portion (cut portion) may be powdered and fine foreign matter may be generated. Furthermore, when such fine foreign matter adheres to one surface side of the semiconductor wafer (the side on which the circuit pattern is formed), the operational reliability of the circuit included in the circuit pattern formed on the one surface side may be reduced, which is not preferable. Therefore, semiconductor wafers are often manufactured by bonding the protective sheet and the protective layer to one surface side of the semiconductor wafer (the side on which the circuit pattern is formed).

使用如上所述之具備含有含氧化烯基之聚乙烯醇系樹脂等水溶性高分子化合物之保護層、及配置於該保護層之兩面之2片剝離片材之保護片材,將前述保護層貼合於前述半導體晶圓之一表面側時,需要使2片剝離片材中一側的剝離片材從前述保護片材剝離,使前述保護層露出表面。Using a protective sheet including a protective layer containing a water-soluble polymer compound such as an oxyalkylene group-containing polyvinyl alcohol resin and two release sheets arranged on both sides of the protective layer, the protective layer is When bonding to one surface side of the semiconductor wafer, it is necessary to peel one of the two release sheets from the protective sheet so that the protective layer is exposed on the surface.

前述一側的剝離片材,係從該一側的剝離片材之外側(未配置有保護層之側)被施加吸引力等外力而從前述保護層被剝離,惟使前述一側的剝離片材從前述保護層剝離時,有前述保護層從2片剝離片材中另一側的剝離片材浮起之情形。 此外,使前述保護層從前述一側的剝離片材剝離時,有前述保護層沒有從前述另一邊的片材浮起,惟前述一側的剝離片材以前述保護層之一部分附著之狀態下被剝離之情形。亦即,有前述保護層非期望剝離之情形。換言之,有在前述保護層發生凝集破壞等之情形。 The release sheet on one side is peeled off from the protective layer by applying an external force such as suction force from the outside of the release sheet on that side (the side where the protective layer is not arranged). When the material is peeled off from the protective layer, the protective layer may float from the other peeling sheet among the two peeling sheets. In addition, when the protective layer is peeled off from the release sheet on the one side, the protective layer does not float from the sheet on the other side, but the release sheet on the one side adheres to a part of the protective layer. The situation of being stripped away. That is, there may be cases where the protective layer is peeled off unintentionally. In other words, aggregation failure or the like may occur in the protective layer.

然而,對於在保護層之兩面具備剝離片材之保護片材,針對充分兼顧在使一側的剝離片材剝離時抑制前述保護層從另一側的剝離片材浮起的發生、及抑制前述保護層非期望剝離方面,尚難謂已受到充分研究。However, for a protective sheet provided with release sheets on both sides of the protective layer, it is necessary to fully achieve both the suppression of the occurrence of the protective layer lifting from the release sheet on the other side when the release sheet on one side is peeled off, and the suppression of the above-mentioned The aspect of unintended peeling of protective layers has hardly been fully studied.

因此,本發明之課題在於提供一種保護片材,其係在保護層之兩面具備剝離片材,並可充分兼顧在使一側的剝離片材剝離時抑制前述保護層從另一側的剝離片材浮起的發生、及抑制前述保護層非期望剝離。 [技術手段] Therefore, an object of the present invention is to provide a protective sheet that is provided with release sheets on both sides of the protective layer and is capable of sufficiently suppressing the release sheet of the protective layer from the other side when the release sheet on one side is peeled off. It prevents the occurrence of material floating and suppresses the undesired peeling of the aforementioned protective layer. [Technical means]

本發明之保護片材,係具備: 保護層; 第1離型紙,其係配置於該保護層之一表面;及 第2離型紙,其係配置於前述保護層之另一表面;且 前述保護層,係含有水溶性高分子化合物; 前述第1離型紙對前述保護層之剝離力為P A,第2離型紙對前述保護層之剝離力為P B時, 剝離力P A及剝離力P B滿足以下關係式: P A<P BP B≦2000mN/25mm。 The protective sheet of the present invention is provided with: a protective layer; a first release paper arranged on one surface of the protective layer; and a second release paper arranged on the other surface of the protective layer; and the aforementioned protective layer The layer contains a water-soluble polymer compound; when the peeling force of the first release paper to the protective layer is P A and the peeling force of the second release paper to the protective layer is P B , the peeling force P A and the peeling force P B satisfies the following relationship: P A <P B P B ≦2000mN/25mm.

以下,針對本發明之一實施型態進行說明。Hereinafter, one embodiment of the present invention will be described.

[保護片材] 本發明之一實施型態之保護片材10,如圖1所示,係具備保護層1、配置於保護層1之一表面之第1離型紙2、及配置於保護層1之另一表面之第2離型紙3。 又,以下,將本發明之一實施型態簡稱為本實施型態。 本實施型態之保護片材10中,保護層1,係含有水溶性高分子化合物。 亦即,保護層1,係具有水溶性。 另一方面,第1離型紙2以及第2離型紙3,係非水溶性。 [Protective sheet] A protective sheet 10 according to an embodiment of the present invention, as shown in FIG. 1 , is provided with a protective layer 1 , a first release paper 2 disposed on one surface of the protective layer 1 , and a first release paper 2 disposed on the other surface of the protective layer 1 . The second release paper 3. In the following, one embodiment of the present invention will be simply referred to as this embodiment. In the protective sheet 10 of this embodiment, the protective layer 1 contains a water-soluble polymer compound. That is, the protective layer 1 is water-soluble. On the other hand, the first release paper 2 and the second release paper 3 are water-insoluble.

如圖1所示,本實施型態之保護片材10中,保護層1、第1離型紙2、以及第2離型紙3,在俯視角下具有約略相同尺寸。 詳細而言,一實施型態之保護片材10中,第1離型紙2之內表面(與保護層之一表面對向之面)與保護層1之一表面,係以對齊彼此邊緣之形式疊合約略全區域;第2離型紙3之內表面(與保護層1之另一表面對向之面)與保護層1之另一表面,係以對齊彼此邊緣之形式疊合約略全區域。 As shown in FIG. 1 , in the protective sheet 10 of this embodiment, the protective layer 1 , the first release paper 2 , and the second release paper 3 have approximately the same size when viewed from above. Specifically, in the protective sheet 10 of one embodiment, the inner surface of the first release paper 2 (the surface opposite to one surface of the protective layer) and one surface of the protective layer 1 are aligned with each other's edges. Overlay approximately the entire area; the inner surface of the second release paper 3 (the surface facing the other surface of the protective layer 1) and the other surface of the protective layer 1 overlap approximately the entire area in such a manner that their edges are aligned with each other.

本實施型態之保護片材10中,保護層1,係具有可貼著至黏附體之程度的接著性。 本實施型態之保護片材10中,保護層1,理想係具有黏性(壓敏接著性)。 本實施型態之保護片材10,係用於使保護層1貼著於黏附體(例如半導體晶圓等電子零件)而藉此在對黏附體進行各種處理期間防止異物附著於該黏附體之表面。 In the protective sheet 10 of this embodiment, the protective layer 1 has adhesiveness to the extent that it can adhere to the adherend. In the protective sheet 10 of this embodiment, the protective layer 1 ideally has adhesiveness (pressure-sensitive adhesiveness). The protective sheet 10 of this embodiment is used to adhere the protective layer 1 to an adherend (such as a semiconductor wafer and other electronic components), thereby preventing foreign matter from adhering to the adherend during various processes on the adherend. surface.

本實施型態之保護片材10中,保護層1(更具體而言,保護層1之露出面),例如係使用如圖2所示之安裝裝置200來貼著於半導體晶圓等電子零件之保護對象面。 安裝裝置200,如圖2所示,係具備腔室201、配置於腔室201底部之靜電吸盤202、配置於腔室201內且比靜電吸盤202更上方之頭部203、及用以減壓腔室201內部之泵P。 又,安裝裝置200中,於靜電吸盤202安裝有半導體晶圓等電子零件、於頭部203安裝有保護片材10。 此外,安裝裝置200中,保護片材10以及半導體晶圓等電子零件,係以與保護層1之露出面及前述保護對象面對向之形式,各自安裝於頭部203以及靜電吸盤202。 進一步地,如圖2所示,在保持台101安裝於頭部203之狀態下,保護片材10亦可安裝於保持台101。 In the protective sheet 10 of this embodiment, the protective layer 1 (more specifically, the exposed surface of the protective layer 1) is attached to electronic components such as semiconductor wafers using, for example, a mounting device 200 as shown in FIG. 2 The object of protection. The installation device 200, as shown in Figure 2, is provided with a chamber 201, an electrostatic chuck 202 arranged at the bottom of the chamber 201, a head 203 arranged in the chamber 201 and above the electrostatic chuck 202, and a pressure reducing device. Pump P inside chamber 201. Furthermore, in the mounting device 200 , electronic components such as semiconductor wafers are mounted on the electrostatic chuck 202 , and the protective sheet 10 is mounted on the head 203 . Furthermore, in the mounting device 200 , the protective sheet 10 and electronic components such as semiconductor wafers are mounted on the head 203 and the electrostatic chuck 202 respectively in such a manner that they face the exposed surface of the protective layer 1 and the surface to be protected. Furthermore, as shown in FIG. 2 , in a state where the holding base 101 is installed on the head 203 , the protective sheet 10 can also be installed on the holding base 101 .

上下方向(垂直方向)為Z軸方向、沿將靜電吸盤202以及頭部203以平行於Z軸之平面切斷時的切斷面之水平方向(沿圖2之紙面之水平方向)為X軸方向、與Z軸以及X軸雙方正交之方向(與圖2之紙面正交之方向)為Y軸方向時,使頭部203朝X軸方向以及Y軸方向中至少一者移動後,進一步朝Z軸方向移動,藉此可使安裝於頭部203之保護層1之露出面貼著於安裝於靜電吸盤202之半導體晶圓等電子零件之保護對象面。The up and down direction (vertical direction) is the Z-axis direction, and the horizontal direction along the cut surface when the electrostatic chuck 202 and the head 203 are cut on a plane parallel to the Z-axis (the horizontal direction along the paper surface of FIG. 2 ) is the X-axis. direction, the direction orthogonal to both the Z axis and the By moving in the Z-axis direction, the exposed surface of the protective layer 1 mounted on the head 203 can be brought into contact with the surface to be protected of electronic components such as semiconductor wafers mounted on the electrostatic chuck 202 .

保持台101未安裝於頭部203之情形下,使保護層1之露出面貼著於前述保護對象面時,亦可預先使靜電吸盤202為加溫狀態。 此外,保持台101安裝於頭部203之情形下,使保護層1之露出面貼著於前述保護對象面時,亦可預先使保持台101以及靜電吸盤202中至少一者為加溫狀態。 When the holding table 101 is not installed on the head 203, the electrostatic chuck 202 can also be heated in advance when the exposed surface of the protective layer 1 is in contact with the surface to be protected. In addition, when the holding table 101 is installed on the head 203 and the exposed surface of the protective layer 1 is in contact with the protected surface, at least one of the holding table 101 and the electrostatic chuck 202 can be heated in advance.

前述第1離型紙2及前述第2離型紙3,係為了防止異物附著於貼著於黏附體前之保護層1而各自貼合於保護層1。 前述第1離型紙2及前述第2離型紙3,係各自具備與前述保護層1對向之內表面、及該內表面的相反面之外表面。 The first release paper 2 and the second release paper 3 are respectively bonded to the protective layer 1 in order to prevent foreign matter from adhering to the protective layer 1 in front of the adherend. The first release paper 2 and the second release paper 3 each have an inner surface facing the protective layer 1 and an outer surface opposite to the inner surface.

本實施型態之保護片材10,係以剝離第1離型紙2使保護層1之一表面露出,並使該一表面貼著於黏附體之保護對象面之方式來使用。 本實施型態之保護片材10,係亦可以使保護層1之一表面貼著於黏附體之保護對象面後,從保護層1之另一表面剝離第2離型紙3,使保護層1之另一表面露出之方式來使用。 亦即,本實施型態之保護片材10,可在剝離第1離型紙2使保護層1之一表面露出,使該一表面貼著於黏附體之保護對象面後,以用第2離型紙3覆蓋保護層1之另一表面之狀態來使用;亦可從保護層1之另一表面剝離第2離型紙3,以使保護層1之另一表面露出之狀態來使用。 The protective sheet 10 of this embodiment is used by peeling off the first release paper 2 to expose one surface of the protective layer 1, and making this surface adhere to the protection target surface of the adherend. In the protective sheet 10 of this embodiment, one surface of the protective layer 1 can also be attached to the protective surface of the adherend, and then the second release paper 3 can be peeled off from the other surface of the protective layer 1, leaving the protective layer 1 Use it with another surface exposed. That is to say, the protective sheet 10 of this embodiment can be used with the second release paper after peeling off the first release paper 2 to expose one surface of the protective layer 1 and making the surface adhere to the protected surface of the adherend. The liner 3 is used in a state of covering the other surface of the protective layer 1; the second release paper 3 can also be peeled off from the other surface of the protective layer 1 to expose the other surface of the protective layer 1.

本實施型態之保護片材10中,使保護層1之一表面貼著於黏附體之保護對象面時,至少會對保護層1進行切割等,使其具有與黏附體之平面尺寸約略相同之尺寸。In the protective sheet 10 of this embodiment, when one surface of the protective layer 1 is attached to the protective surface of the adherend, the protective layer 1 is at least cut, etc., so that it has approximately the same plane size as the adherend. size.

本實施型態之保護片材10中,第1離型紙2對保護層1之剝離力為P A,第2離型紙3對保護層1之剝離力為P B時,重要的是剝離力P A以及剝離力P B滿足以下關係式: P A<P BP B≦2000mN/25mm。 In the protective sheet 10 of this embodiment, when the peeling force of the first release paper 2 to the protective layer 1 is P A and the peeling force of the second release paper 3 to the protective layer 1 is P B , the important thing is the peeling force P A and the peeling force P B satisfy the following relationship: P A <P B P B ≦2000mN/25mm.

藉由剝離力P B為2000mN/25mm以下,可抑制第2離型紙3被保護層1過度黏附之情形。 藉此,剝離第1離型紙2使保護層1之一表面露出,並使該一表面黏附於作為黏附體之半導體晶圓之保護對象面後,在從保護層1之另一表面剝離第2離型紙3時,可抑制第2離型紙3以保護層1之一部分附著之狀態下被剝離之情形。 亦即,剝離第2離型紙3時,可抑制保護層1非期望剝離之情形。 此外,藉由剝離力P A以及剝離力P B滿足P A<P B之關係,剝離第1離型紙2使保護層1之一表面露出時,可抑制在保護層1之另一表面側第2離型紙3浮起之情形。 又,從使第1離型紙2對保護層1之黏附力以及第2離型紙3對保護層1之黏附力適當平衡之觀點而言,作為剝離力P B對剝離力P A之比(P B/P A)之R,理想為1.1以上,更理想為1.2以上。 此外,前述R,更理想為2.0以上,更理想為3.0以上,更理想為4.0以上,更理想為5.0以上。前述R之上限,通常為100。 藉由前述R為2.0以上,可使剝離力P A之值與剝離力P B之值產生充分差異,故從保護層1剝離第1離型紙2時,可充分抑制保護層1從第2離型紙3浮起之情形。 When the peeling force P B is 2000mN/25mm or less, excessive adhesion of the second release paper 3 to the protective layer 1 can be suppressed. Thereby, the first release paper 2 is peeled off to expose one surface of the protective layer 1, and after the one surface is adhered to the protection target surface of the semiconductor wafer as an adherend, the second release paper 2 is peeled off from the other surface of the protective layer 1. When the release paper 3 is used, the second release paper 3 can be prevented from being peeled off with a part of the protective layer 1 attached. That is, when the second release paper 3 is peeled off, the protective layer 1 can be prevented from being peeled off unintentionally. In addition, since the peeling force P A and the peeling force P B satisfy the relationship P A < P B , when the first release paper 2 is peeled off to expose one surface of the protective layer 1, it can be suppressed that the other surface of the protective layer 1 is exposed. 2. The release paper 3 is floating. Furthermore, from the viewpoint of appropriately balancing the adhesion force of the first release paper 2 to the protective layer 1 and the adhesion force of the second release paper 3 to the protective layer 1, as the ratio of the peeling force P B to the peeling force P A (P B /P A ) R is preferably 1.1 or more, more preferably 1.2 or more. In addition, the aforementioned R is more preferably 2.0 or more, more preferably 3.0 or more, more preferably 4.0 or more, and more preferably 5.0 or more. The upper limit of the aforementioned R is usually 100. By the aforementioned R being 2.0 or more, a sufficient difference can be made between the value of the peeling force P A and the value of the peeling force P B. Therefore, when the first release paper 2 is peeled off from the protective layer 1, the protective layer 1 can be sufficiently prevented from peeling off from the second release paper 2. The situation where the pattern paper 3 is floating.

為了使本實施型態之保護片材10滿足上述關係式,亦即滿足P A<P B、且P B≦2000mN/25mm,需要對第1離型紙2之內表面施以表面處理,使第1離型紙2之內表面對保護層1之一表面具有適當黏附力後,對第2離型紙3之內表面施以表面處理,使第2離型紙3之內表面對保護層1之另一表面具有適當黏附力。 In order for the protective sheet 10 of this embodiment to satisfy the above relational expression, that is, to satisfy P A < P B and P B ≦2000mN/25mm, it is necessary to perform surface treatment on the inner surface of the first release paper 2 so that the 1. After the inner surface of the release paper 2 has appropriate adhesion to one surface of the protective layer 1, surface treatment is applied to the inner surface of the second release paper 3 so that the inner surface of the second release paper 3 is in contact with the other surface of the protective layer 1. The surface has adequate adhesion.

本實施型態之保護片材10中,剝離力P A,理想為5mN/25mm以上,更理想為10mN/25mm以上,更加理想為15mN以上。 此外,本實施型態之保護片材10中,剝離力P A,理想為1000mN/25mm以下,更理想為500mN/25mm以下,更加理想為300mN/25mm以下,更進一步理想為200mN/25mm以下。 In the protective sheet 10 of this embodiment, the peeling force P A is preferably 5 mN/25mm or more, more preferably 10 mN/25mm or more, and even more preferably 15 mN or more. In addition, in the protective sheet 10 of this embodiment, the peeling force PA is preferably 1000mN/25mm or less, more preferably 500mN/25mm or less, even more preferably 300mN/25mm or less, further preferably 200mN/25mm or less.

本實施型態之保護片材10中,剝離力P B,理想為70mN/25mm以上,理想為80mN/25mm以上。 此外,本實施型態之保護片材10中,剝離力P B,理想為1500mN/25mm以下,更理想為1000mN/25mm以下。 In the protective sheet 10 of this embodiment, the peeling force P B is preferably 70 mN/25mm or more, and preferably 80 mN/25mm or more. In addition, in the protective sheet 10 of this embodiment, the peeling force PB is preferably 1500mN/25mm or less, and more preferably 1000mN/25mm or less.

剝離力P A以及剝離力P B,可使用拉伸試驗機(商品名「精密萬能試驗機(Autograph)AG-IS」,島津製作所股份有限公司製)測定。 針對使用前述拉伸試驗機之剝離力P A,係從保護片材10切出大小為長度150mm、寬度100mm之樣品後,將剝離第2離型紙3之該樣品作為試樣(以下,稱為第1試樣)。 此外,針對使用前述拉伸試驗機之剝離力P B,係從保護片材10切出大小為長度150mm、寬度100mm之樣品後,將剝離第1離型紙2之該樣品作為試樣(以下,稱為第2試樣)。 又,剝離力P A以及剝離力P B之單位「mN/25mm」,係以寬度100mm測定之值換算為寬度25mm。 The peeling force P A and the peeling force PB can be measured using a tensile testing machine (trade name "Precision Universal Testing Machine (Autograph) AG-IS", manufactured by Shimadzu Corporation). Regarding the peeling force P A using the aforementioned tensile testing machine, a sample having a length of 150 mm and a width of 100 mm was cut out from the protective sheet 10 and the second release paper 3 was peeled off from the sample (hereinafter referred to as Sample 1). In addition, regarding the peeling force P B using the aforementioned tensile testing machine, a sample having a length of 150 mm and a width of 100 mm was cut out from the protective sheet 10 and the first release paper 2 was peeled off from the sample (hereinafter, Called the 2nd sample). In addition, the unit "mN/25mm" of the peeling force P A and the peeling force P B is a value measured with a width of 100 mm and converted into a width of 25 mm.

剝離力P A之測定,係可在中間夾有雙面膠帶(例如日東電工公司製之商品名「No.500」)之狀態下,使第1試樣之保護層之露出面呈貼合於裸晶圓之表面之狀態,以使用拉伸試驗機(例如島津製作所公司製之商品名「精密萬能試驗機(Autograph)AG-IS」)進行之180°剝離試驗之方式實施。 又,前述180°剝離試驗,可藉由在溫度23±2℃、相對溼度55±5%RH、以及剝離速度300mm/min之條件下,將第1離型紙2朝長度方向拉伸來實施。 此外,剝離力P B之測定,除了以第2試樣取代第1試樣,將朝長度方向拉伸的對象以第2離型紙3取代以外,可以與剝離力P A之測定同樣方式實施。 此外,剝離力P A以及剝離力P B,係以從測定開始30mm作為起點、120mm作為終點之範圍之值的平均值。 The peeling force P A can be measured by sandwiching a double-sided tape (for example, trade name "No. 500" manufactured by Nitto Denko Co., Ltd.) so that the exposed surface of the protective layer of the first sample is adhered to The surface condition of the bare wafer is measured by a 180° peel test using a tensile testing machine (for example, "Autograph AG-IS", a product of Shimadzu Corporation). In addition, the aforementioned 180° peeling test can be implemented by stretching the first release paper 2 in the length direction under the conditions of a temperature of 23±2°C, a relative humidity of 55±5%RH, and a peeling speed of 300mm/min. In addition, the peeling force P B can be measured in the same manner as the peeling force P A except that the first sample is replaced by a second sample and the object stretched in the longitudinal direction is replaced by the second release paper 3 . In addition, the peeling force P A and the peeling force PB are the average values of the range with 30 mm as the starting point and 120 mm as the end point from the measurement.

作為前述表面處理,可列舉例如使用剝離劑,對第1離型紙2之內表面以及第2離型紙3之內表面進行離型處理。 作為前述剝離劑,在不損及本發明之效果之範圍內,可使用任意之適當剝離劑。 作為如此之剝離劑,可列舉例如乙烯-乙烯醇共聚物、脂肪酸醯胺系添加劑、低分子量聚烯烴蠟、長鏈烷基系添加劑、聚甲基戊烯、氟系剝離劑、矽酮系剝離劑等。 Examples of the surface treatment include performing release treatment on the inner surface of the first release paper 2 and the inner surface of the second release paper 3 using a release agent. As the said release agent, any appropriate release agent can be used within the range which does not impair the effect of this invention. Examples of such release agents include ethylene-vinyl alcohol copolymers, fatty acid amide additives, low molecular weight polyolefin waxes, long-chain alkyl additives, polymethylpentene, fluorine-based release agents, and silicone-based release agents. Agents, etc.

作為前述乙烯-乙烯醇共聚物,可使用例如藉由將乙烯與選自乙酸乙烯酯、甲酸乙烯酯及丙酸乙烯酯所成群中至少一種之共聚物皂化所獲得之乙烯・乙烯醇共聚物等。As the ethylene-vinyl alcohol copolymer, for example, an ethylene-vinyl alcohol copolymer obtained by saponifying ethylene and at least one copolymer selected from the group consisting of vinyl acetate, vinyl formate, and vinyl propionate can be used. wait.

作為前述脂肪酸醯胺系添加劑,可列舉例如亞甲基雙硬脂醯胺、伸乙基雙硬脂醯胺、伸乙基雙油酸醯胺、N,N-二油基己二醯胺、N-硬脂基-N'-硬脂醯胺(例如N-硬脂基-N'-硬脂基脲等)等。 此等之脂肪酸醯胺系添加劑,可單獨使用一種或組合使用二種以上。 Examples of the fatty acid amide-based additive include methylene distearamide, ethylidene distearylamide, ethylidene bisoleamide, N,N-dioleyl adipamide, N-stearyl-N'-stearylamine (such as N-stearyl-N'-stearyl urea, etc.), etc. These fatty acid amide additives may be used singly or in combination of two or more.

作為前述低分子量聚烯烴蠟,可列舉例如聚乙烯蠟之低分子量產品、聚丙烯蠟之低分子量產品等。Examples of the low molecular weight polyolefin wax include low molecular weight products of polyethylene wax, low molecular weight products of polypropylene wax, and the like.

作為前述長鏈烷基系添加劑,可列舉例如含有長鏈烷基側鏈聚合物者。 作為如此之長鏈烷基系添加劑之市售品,可列舉Peeloil(註冊商標)1010(一方社油脂工業公司製)、Peeloil(註冊商標)1010S(一方社油脂工業公司製)等。 Examples of the long-chain alkyl additive include polymers containing long-chain alkyl side chains. Examples of commercially available products of such long-chain alkyl additives include Peeloil (registered trademark) 1010 (manufactured by Yifangsha Oils and Fats Industry Co., Ltd.), Peeloil (registered trademark) 1010S (manufactured by Yifangsha Oils and Fats Industry Co., Ltd.), and the like.

作為前述聚甲基戊烯,可列舉以4-甲基-1-戊烯為基礎之烯烴共聚物等。 作為如此之聚甲基戊烯之市售品,可列舉TPX(註冊商標)MX001(三井化學公司製)、TPX(註冊商標)0004(三井化學公司製)等。 Examples of the polymethylpentene include olefin copolymers based on 4-methyl-1-pentene. Examples of such commercially available polymethylpentene include TPX (registered trademark) MX001 (manufactured by Mitsui Chemicals Co., Ltd.), TPX (registered trademark) 0004 (manufactured by Mitsui Chemicals Co., Ltd.), and the like.

前述氟系剝離劑,係含有氟系樹脂。 作為前述氟系樹脂,可列舉PTFE(聚四氟乙烯)、PVDF(聚偏二氟乙烯)、PCTFE(聚三氟氯乙烯)、PVF(聚氟乙烯)、PFA(四氟乙烯與全氟烷氧基乙烯之共聚物)、FEP(四氟乙烯與六氟丙烯之共聚物)、ETFE(四氟乙烯與乙烯之共聚物)、ECTFE(三氟氯乙烯與乙烯之共聚物)、四氟乙烯及六氟丙烯及偏氟乙烯之3元共聚物、氟橡膠等。 此等各種之氟系樹脂,可單獨使用或組合使用二種以上。 The aforementioned fluorine-based release agent contains a fluorine-based resin. Examples of the fluorine-based resin include PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride), PCTFE (polychlorotrifluoroethylene), PVF (polyfluoroethylene), and PFA (tetrafluoroethylene and perfluoroalkane). Copolymer of oxyethylene), FEP (copolymer of tetrafluoroethylene and hexafluoropropylene), ETFE (copolymer of tetrafluoroethylene and ethylene), ECTFE (copolymer of chlorotrifluoroethylene and ethylene), tetrafluoroethylene And ternary copolymers of hexafluoropropylene and vinylidene fluoride, fluorine rubber, etc. These various fluorine-based resins can be used alone or in combination of two or more.

作為前述矽酮系剝離劑,可列舉例如油型、烘烤型、以及乳液型剝離劑。Examples of the silicone-based release agent include oil-type, baking-type, and emulsion-type release agents.

作為油型矽酮剝離劑,可使用聚烷基矽氧烷、改性聚烷基矽氧烷、以及用聚烷基矽氧烷改性之樹脂等液狀矽酮化合物。As oil-type silicone strippers, liquid silicone compounds such as polyalkylsiloxane, modified polyalkylsiloxane, and resin modified with polyalkylsiloxane can be used.

作為前述聚烷基矽氧烷,可列舉所有側鏈以及末端均為甲基之二甲基矽酮、側鏈之一部分為苯基之甲基苯基矽酮、側鏈之一部分為氫之甲基氫矽酮等。 又,二甲基矽酮、甲基苯基矽酮、以及甲基氫矽酮,皆為矽(Si)彼此經由氧(O)鍵結為直鏈狀之普通矽酮(straight silicone)。 Examples of the polyalkylsiloxane include dimethylsiloxane in which all side chains and terminals are methyl, methylphenylsiloxane in which part of the side chain is phenyl, and methyl in which part of the side chain is hydrogen. Hydrogen silicone, etc. In addition, dimethyl silicone, methyl phenyl silicone, and methyl hydrogen silicone are all ordinary silicones in which silicon (Si) is bonded to each other through oxygen (O) to form a straight chain.

作為前述改性聚烷基矽氧烷,可列舉在前述聚矽氧烷之側鏈之一部分導入有機基者。 作為前述有機基,可列舉單胺基、二胺基、胺基、環氧基、甲醇基、巰基、羧基、聚醚基、芳烷基、氟烷基等。 又,前述改性聚烷基矽氧烷中,含有單胺基、二胺基、胺基、環氧基、甲醇基、巰基、羧基等具反應性之有機基者,稱為反應性矽酮;前述改性聚烷基矽氧烷中,含有聚醚基、芳烷基、氟烷基等不具反應性之有機基者,稱為非反應性矽酮。 Examples of the modified polyalkylsiloxane include those in which an organic group is introduced into a part of the side chain of the polysiloxane. Examples of the organic group include a monoamine group, a diamine group, an amine group, an epoxy group, a carbinol group, a mercapto group, a carboxyl group, a polyether group, an aralkyl group, a fluoroalkyl group, and the like. In addition, the aforementioned modified polyalkylsiloxanes that contain reactive organic groups such as monoamine groups, diamine groups, amine groups, epoxy groups, carbinol groups, mercapto groups, and carboxyl groups are called reactive silicones. ; Among the aforementioned modified polyalkylsiloxanes, those containing non-reactive organic groups such as polyether groups, aralkyl groups, and fluoroalkyl groups are called non-reactive silicones.

作為烘烤型矽酮剝離劑,可列舉在上述說明之前述聚烷基矽氧烷、前述改性聚烷基矽氧烷、以及用聚烷基矽氧烷改性之樹脂等液狀矽酮化合物,配合過氧化物或含過氧化物之矽酮化合物等交聯劑者。Examples of baking-type silicone release agents include liquid silicones such as the polyalkylsiloxanes described above, the modified polyalkylsiloxanes described above, and resins modified with polyalkylsiloxanes. Compounds that are combined with cross-linking agents such as peroxide or peroxide-containing silicone compounds.

乳液型矽酮剝離劑,係將矽酮化合物分散於水系介質之矽酮化合物的水分散體。 前述乳液型矽酮剝離劑,亦稱為矽酮系水分散性樹脂。 作為前述矽酮化合物可列舉在上述說明之聚烷基矽氧烷、改性聚烷基矽氧烷、以及用聚烷基矽氧烷改性之樹脂等液狀矽酮化合物。 Emulsion-type silicone stripper is a water dispersion of silicone compound dispersed in an aqueous medium. The aforementioned emulsion-type silicone stripper is also called silicone-based water-dispersible resin. Examples of the silicone compound include liquid silicone compounds such as polyalkylsiloxane, modified polyalkylsiloxane, and resin modified with polyalkylsiloxane described above.

前述聚烷基矽氧烷等矽酮化合物,係具有熱交聯性。 並且,在如此之矽酮化合物,可藉由調整熱交聯程度,容易地調整剝離力之程度。 因此,考慮上述因素,上述之各種剝離劑中,理想係使用矽酮系剝離劑。 The aforementioned silicone compounds such as polyalkylsiloxane have thermal crosslinkability. Furthermore, in such a silicone compound, the degree of peeling force can be easily adjusted by adjusting the degree of thermal cross-linking. Therefore, taking the above factors into consideration, it is desirable to use a silicone-based release agent among the various release agents mentioned above.

又,剝離劑,通常係液狀,以塗布至欲增加剝離性之對象物之形式來使用。 作為前述剝離劑之塗布方法,可採用各種周知之塗布方法。 作為各種周知之塗布方法,可列舉例如凹版塗布法及反轉塗布法等輥塗布法、邁耶棒(Meyer Bar)塗布等棒塗布法、噴灑塗布法、氣刀塗布法等。 又,上述剝離劑,亦可在以有機溶劑(例如乙基甲基酮)等稀釋後塗布於前述對象物。 此外,前述剝離劑,理想係塗布為使乾燥後之厚度範圍為0.05μm以上1μm以下。 In addition, the release agent is usually in a liquid form and is used in the form of being applied to an object to which release properties are to be increased. As the coating method of the said release agent, various well-known coating methods can be used. Various well-known coating methods include, for example, roll coating methods such as gravure coating and reverse coating, bar coating such as Meyer Bar coating, spray coating, and air knife coating. Moreover, the said release agent may be diluted with an organic solvent (for example, ethyl methyl ketone) etc., and may be apply|coated to the said object. In addition, the aforementioned release agent is preferably applied so that the thickness range after drying is 0.05 μm or more and 1 μm or less.

使用前述剝離劑對第1離型紙2之內表面以及第2離型紙3之內表面進行離型處理時,只要使塗布於第1離型紙2之內表面之剝離劑種類、與塗布於第2離型紙3之內表面之剝離劑種類相異,即可使第1離型紙2之內表面對保護層1之剝離力P A、與第2離型紙3之內表面對保護層1之剝離力P B相異。 此外,作為塗布於第1離型紙2之內表面之剝離劑以及塗布於第2離型紙3之內表面之剝離劑,同樣使用矽酮系剝離劑時,如上述說明,只要使塗布於第1離型紙2之內表面之前述矽酮系剝離劑之熱交聯程度、與塗布於第2離型紙3之內表面之前述矽酮系剝離劑之熱交聯程度相異,即可使第1離型紙2之內表面對保護層1之剝離力P A、與第2離型紙3之內表面對保護層1之剝離力P B相異。 又,熱交聯程度,可藉由使加熱溫度相異、或使加熱時間相異來調整。 進一步地,塗布於第1離型紙2之內表面之剝離劑、以及塗布於第2離型紙3之內表面之剝離劑為同一種時,亦可使用有機溶劑等改變稀釋倍率之剝離劑,各自塗布於第1離型紙2之內表面以及第2離型紙3之內表面。以如此之形式進行塗布處理時,可使第1離型紙2之內表面對保護層1之剝離力P A、與第2離型紙3之內表面對保護層1之剝離力P B相異。 When using the aforementioned release agent to perform release treatment on the inner surface of the first release paper 2 and the inner surface of the second release paper 3, it is only necessary to use the same type of release agent coated on the inner surface of the first release paper 2 and the same type of release agent coated on the second release paper 3. The type of release agent on the inner surface of the release paper 3 is different, that is, the peeling force P A of the inner surface of the first release paper 2 to the protective layer 1 and the peeling force of the inner surface of the second release paper 3 to the protective layer 1 P B are different. In addition, when a silicone-based release agent is also used as the release agent coated on the inner surface of the first release paper 2 and the release agent coated on the inner surface of the second release paper 3, as described above, as long as the release agent is coated on the first release paper The thermal cross-linking degree of the silicone-based release agent on the inner surface of the release paper 2 is different from the thermal cross-linking degree of the silicone-based release agent coated on the inner surface of the second release paper 3, that is, the first The peeling force P A of the inner surface of the release paper 2 to the protective layer 1 is different from the peeling force P B of the inner surface of the second release paper 3 to the protective layer 1 . In addition, the degree of thermal cross-linking can be adjusted by varying the heating temperature or heating time. Furthermore, when the release agent coated on the inner surface of the first release paper 2 and the release agent coated on the inner surface of the second release paper 3 are the same, organic solvents and other release agents with different dilution ratios can also be used, respectively. Coat on the inner surface of the first release paper 2 and the inner surface of the second release paper 3 . When the coating treatment is performed in this manner, the peeling force P A of the inner surface of the first release paper 2 to the protective layer 1 can be made different from the peeling force P B of the inner surface of the second release paper 3 to the protective layer 1 .

此外,作為前述表面處理,可列舉例如藉由消光加工或壓印加工等,在第1離型紙2之內表面(配置有保護層1之面)以及第2離型紙3之內表面設置凹凸。 在第1離型紙2之內表面以及第2離型紙3之內表面設置凹凸時,第1離型紙2之內表面之算術平均粗度Ra,理想為0.1μm以上,更理想為0.5μm以上,更加理想為1.0μm以上。 此外,第1離型紙2之內表面之算術平均粗度Ra,理想為50μm以下,更理想為30μm以下,更加理想為10μm以下。 進一步地,第2離型紙3之內表面之算術平均粗度Ra,理想為0.050μm以上,更理想為0.075μm以上,更加理想為0.100μm以上。 Examples of the surface treatment include providing unevenness on the inner surface of the first release paper 2 (the surface on which the protective layer 1 is disposed) and the inner surface of the second release paper 3 by matte processing or embossing processing. When the inner surface of the first release paper 2 and the inner surface of the second release paper 3 are provided with unevenness, the arithmetic mean roughness Ra of the inner surface of the first release paper 2 is preferably 0.1 μm or more, and more preferably 0.5 μm or more. More preferably, it is 1.0 μm or more. In addition, the arithmetic mean roughness Ra of the inner surface of the first release paper 2 is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 10 μm or less. Furthermore, the arithmetic mean roughness Ra of the inner surface of the second release paper 3 is preferably 0.050 μm or more, more preferably 0.075 μm or more, and even more preferably 0.100 μm or more.

第1離型紙2之內表面之算術平均粗度Ra以及第2離型紙3之內表面之算術平均粗度Ra,可使用共軛焦雷射顯微鏡(例如商品名「OPTELICS H300」,雷泰光電(Lasertec)公司製)測定。The arithmetic mean roughness Ra of the inner surface of the first release paper 2 and the arithmetic mean roughness Ra of the inner surface of the second release paper 3 can be measured using a conjugate focal laser microscope (for example, trade name "OPTELICS H300", Leitai Optoelectronics ( Lasertec) measured.

算術平均粗度Ra之值越大,第1離型紙2之內表面以及第2離型紙3之內表面與保護層1之表面之接觸面積會越小。 因此,算術平均粗度Ra之值越大,第1離型紙2之內表面對保護層1之剝離力P A、以及第2離型紙3之內表面對保護層1之剝離力P B會越小。亦即,第1離型紙2以及第2離型紙3可從保護層1輕剝離。 因此,藉由使第1離型紙2之內表面之算術平均粗度Ra之值比第2離型紙3之內表面之算術平均粗度Ra之值更大,即可滿足剝離力P A<剝離力P B之關係。 此外,藉由第1離型紙2之內表面之算術平均粗度Ra在上述數值範圍內、第2離型紙3之內表面之算術平均粗度Ra在上述數值範圍內,容易使本實施型態之保護片材10滿足上述各關係式。 The greater the value of the arithmetic mean roughness Ra, the smaller the contact area between the inner surface of the first release paper 2 and the inner surface of the second release paper 3 and the surface of the protective layer 1 will be. Therefore, the greater the value of the arithmetic mean roughness Ra, the greater the peeling force P A of the inner surface of the first release paper 2 to the protective layer 1, and the greater the peeling force P B of the inner surface of the second release paper 3 to the protective layer 1. Small. That is, the first release paper 2 and the second release paper 3 can be easily peeled off from the protective layer 1 . Therefore, by making the value of the arithmetic mean roughness Ra of the inner surface of the first release paper 2 larger than the value of the arithmetic mean roughness Ra of the inner surface of the second release paper 3, the peeling force P A < peeling can be satisfied The relationship between force P and B. In addition, since the arithmetic mean roughness Ra of the inner surface of the first release paper 2 is within the above numerical range, and the arithmetic mean roughness Ra of the inner surface of the second release paper 3 is within the above numerical range, it is easy to make this embodiment The protective sheet 10 satisfies each of the above relational expressions.

保護層1,如上述說明,係貼合於黏附體之保護對象面來使用。 作為前述黏附體,可列舉電子零件;作為前述電子零件,可列舉例如半導體晶圓等。 作為前述半導體晶圓,可列舉一種半導體晶圓,其係在一表面側形成有劃分為格子狀之區域(以下,亦稱為格子狀劃分區域),且前述格子狀劃分區域各自在形成有電路圖案的同時配置有電極部。 前述電子零件為如上所述之半導體晶圓時,保護層1,係貼合於前述半導體晶圓之一表面來使用。 如此一來,藉由保護層1貼合於前述半導體晶圓之一表面,將前述半導體晶圓分割(割斷)而獲得複數個半導體晶片時,可抑制分割部(割斷部)附近之前述半導體晶圓之一部分粉狀化等而產生之微細異物附著於形成於前述一表面之各電路圖案(形成於各個前述格子狀劃分區域之電路圖案)、以及配置於前述一表面之各電極部(配置於各個前述格子狀劃分區域之電極部)。 The protective layer 1, as described above, is used in conjunction with the protective surface of the adherend. Examples of the adherend include electronic components, and examples of the electronic components include semiconductor wafers. Examples of the semiconductor wafer include a semiconductor wafer in which regions divided into a grid pattern (hereinafter also referred to as grid-shaped divided areas) are formed on one surface side, and circuits are formed in each of the grid-shaped divided areas. An electrode portion is arranged along with the pattern. When the electronic component is a semiconductor wafer as described above, the protective layer 1 is bonded to one surface of the semiconductor wafer. In this way, when the protective layer 1 is bonded to one surface of the semiconductor wafer and the semiconductor wafer is divided (cut) to obtain a plurality of semiconductor wafers, it is possible to suppress the formation of the semiconductor wafer near the divided portion (cut portion). Fine foreign matter generated by powdering a portion of the circle adheres to each circuit pattern formed on the one surface (circuit pattern formed in each of the grid-shaped divided areas), and each electrode portion arranged on the one surface (arranged in The electrode portion of each of the aforementioned grid-shaped divided areas).

前述第2離型紙3,亦可為具備長邊方向及短邊方向之長條帶狀。 保護片材10,可具備一帶狀第2離型紙3及與保護對象面具有相同形狀之複數個保護層1,且該複數個保護層1可朝第2離型紙3之長邊方向排列配置、亦可在該長邊方向相鄰之保護層1之間設置一定間隔。 此外,此時,第1離型紙2,亦可與第2離型紙3同樣為帶狀。 The aforementioned second release paper 3 may also be in the shape of a long strip having a long side direction and a short side direction. The protective sheet 10 can be provided with a strip-shaped second release paper 3 and a plurality of protective layers 1 having the same shape as the surface to be protected, and the plurality of protective layers 1 can be arranged in a longitudinal direction of the second release paper 3 , a certain interval can also be provided between adjacent protective layers 1 in the longitudinal direction. In addition, at this time, the first release paper 2 may also be in the shape of a strip like the second release paper 3 .

前述第2離型紙3,不只長邊方向,短邊方向之尺寸亦可大於保護層1。 亦即,保護片材10,亦可第2離型紙3比保護層1之外周緣還要超出外側,且第2離型紙3之超出部分係沿保護層1之全周產生。 The size of the aforementioned second release paper 3 can be larger than the size of the protective layer 1 not only in the long side direction but also in the short side direction. That is, in the protective sheet 10 , the second release paper 3 may extend beyond the outer periphery of the protective layer 1 , and the excess part of the second release paper 3 may occur along the entire circumference of the protective layer 1 .

保護片材10,係可用例如以下方法製作。 (1)使用塗布器等,將含有水溶性高分子化合物及多餘液體成分之水溶性樹脂組成物在第2離型紙3上塗布指定厚度(例如5μm~30μm)。 (2)將塗布後之水溶性樹脂組成物以指定溫度乾燥指定時間(例如110℃2分鐘)。藉此,在第2離型紙3上形成含有水溶性高分子化合物之保護層1。 (3)保護層1中,在配置有第2離型紙3之面的相反面(保護層1之露出面),以指定溫度(例如70℃)貼合第1離型紙2。 The protective sheet 10 can be produced by, for example, the following method. (1) Use an applicator or the like to apply a water-soluble resin composition containing a water-soluble polymer compound and excess liquid components on the second release paper 3 to a specified thickness (for example, 5 μm to 30 μm). (2) Dry the coated water-soluble resin composition at a specified temperature for a specified time (for example, 110°C for 2 minutes). Thereby, the protective layer 1 containing the water-soluble polymer compound is formed on the second release paper 3 . (3) In the protective layer 1, laminate the first release paper 2 at a specified temperature (for example, 70°C) on the opposite surface (the exposed surface of the protective layer 1) to the surface on which the second release paper 3 is arranged.

本實施型態之保護片材10中,保護層1,作為含有水溶性高分子化合物及多餘液體成分之水溶性樹脂組成物,理想係使用使前述水溶性高分子化合物分散於水者(以下,稱為保護層形成組成物)製作。 前述保護層形成組成物中,相對於水100質量份,理想為含有前述水溶性高分子化合物5質量份以上80質量份以下,更理想為含有10質量份以上70質量份以下,更加理想為含有15質量份以上60質量份以下。 此外,前述保護層形成組成物中,理想係呈前述水溶性高分子化合物溶解於水之狀態。 又,前述保護層形成組成物中,前述水溶性高分子化合物,可為藉由以溫度20~90℃進行處理而成為溶解於水中之狀態。 進一步地,前述保護層形成組成物,在25℃時之黏度理想為0.03Pa・s以上,更理想為0.05Pa・s以上,更加理想為0.1Pa・s以上。 藉由在25℃時之黏度為上述下限值以上,將前述保護層形成組成物塗布於第1離型紙2上而在該第1離型紙2上形成保護層1時,可抑制保護層1之厚度容易變動之情形。 此外,前述保護層形成組成物,在25℃時之黏度理想為15Pa・s以下,更理想為10Pa・s以下,更加理想為5Pa・s以下。 藉由在25℃時之黏度為上述之上限值以下,可提升將前述保護層形成組成物塗布於第1離型紙2上時之塗布性。 又,25℃時之前述保護層形成組成物之黏度,係在使用英弘精機公司製之數位黏度計(製品名「DV-I Prime」)作為測定裝置下,可藉由使用LV-3轉軸、採用旋轉數50rpm之條件進行測定。 In the protective sheet 10 of this embodiment, the protective layer 1 is preferably made of a water-soluble resin composition containing a water-soluble polymer compound and an excess liquid component, in which the water-soluble polymer compound is dispersed in water (hereinafter, (called a protective layer forming composition). The protective layer forming composition preferably contains 5 to 80 parts by mass of the water-soluble polymer compound relative to 100 parts by mass of water, more preferably 10 to 70 parts by mass, and even more preferably 100 parts by mass or more and 70 parts by mass or less. 15 parts by mass or more and 60 parts by mass or less. Furthermore, in the protective layer-forming composition, it is preferable that the water-soluble polymer compound is dissolved in water. In addition, in the protective layer forming composition, the water-soluble polymer compound may be in a state of being dissolved in water by processing at a temperature of 20 to 90°C. Furthermore, the viscosity of the protective layer-forming composition at 25°C is preferably 0.03 Pa・s or more, more preferably 0.05 Pa・s or more, and even more preferably 0.1 Pa・s or more. By having the viscosity at 25° C. or more than the above lower limit, when the protective layer forming composition is coated on the first release paper 2 and the protective layer 1 is formed on the first release paper 2, the protective layer 1 can be suppressed. The thickness is easy to change. In addition, the viscosity of the protective layer-forming composition at 25°C is preferably 15 Pa・s or less, more preferably 10 Pa・s or less, and even more preferably 5 Pa・s or less. By having the viscosity at 25° C. below the above-mentioned upper limit, the coating properties when the protective layer-forming composition is applied to the first release paper 2 can be improved. In addition, the viscosity of the protective layer-forming composition at 25°C can be measured by using a digital viscometer (product name "DV-I Prime") manufactured by Eiko Seiki Co., Ltd. by using an LV-3 rotating shaft, The measurement was carried out under the conditions of a rotation speed of 50 rpm.

作為前述水溶性高分子化合物,可列舉例如聚乙烯醇(PVA)、聚乙烯吡咯烷酮(PVP)、水溶性聚酯(PES)、聚環氧乙烷(PEO)等。 前述水溶性高分子化合物,係可單獨使用聚乙烯醇、聚乙烯吡咯烷酮、水溶性聚酯、聚環氧乙烷等,或組合使用此等之二種以上。 作為前述水溶性高分子化合物,理想為使用選自聚乙烯醇、水溶性聚酯、以及聚環氧乙烷所成群中至少一種,更理想為使用聚乙烯醇。 Examples of the water-soluble polymer compound include polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), water-soluble polyester (PES), polyethylene oxide (PEO), and the like. The aforementioned water-soluble polymer compound may be polyvinyl alcohol, polyvinylpyrrolidone, water-soluble polyester, polyethylene oxide, etc., or two or more thereof may be used in combination. As the water-soluble polymer compound, at least one selected from the group consisting of polyvinyl alcohol, water-soluble polyester, and polyethylene oxide is preferably used, and polyvinyl alcohol is more preferably used.

前述聚乙烯醇,理想為皂化度50以上98以下,更理想為60以上90以下。 藉由皂化度在上述數值範圍內,除了前述聚乙烯醇可表現充分水溶性,使前述保護層形成組成物含有前述聚乙烯醇時,對第1剝離襯墊2上之前述保護層形成組成物之塗布可操作性良好地實施。 前述聚乙烯醇之皂化度,可藉由質子核磁共振光譜法( 1H-NMR測定法)測定。 又,測定樣品中含有添加劑,且源自該添加劑之波峰與用於算出皂化度之波峰重疊時,係對前述測定樣品施以甲醇萃取等而分離前述添加劑後,測定前述聚乙烯醇之皂化度。 前述聚乙烯醇之皂化度,可用以下條件測定。 <測定條件> ・分析裝置 FT-NMR : Bruker Biospin, AVANCE III-400 ・觀測頻率 400MHz(1H) ・測定溶劑 重水、或重二甲基亞碸(重DMSO) ・測定溫度 80℃ ・化學位移基準 外部標準TSP-d4(0.00ppm)(重水測定時) 測定溶劑(2.50ppm)(重DMSO測定時) 又,前述聚乙烯醇之皂化度,係使用源自乙烯醇單元(VOH) 之亞甲基之波峰(重水:2.0~1.0ppm、重DMSO:1.9~1.0ppm) 、及源自乙酸乙烯酯單元(VAc) 之乙醯基之波峰(重水:2.1ppm附近、重DMSO:2.0ppm附近),基於以下公式算出。 以下之公式中,[VOH(-CH 2-)]係指源自乙烯醇單元中之-CH 2-之波峰強度;[Vac(CH 3CO-)]係指源自乙酸乙烯酯單元中之CH 3CO-之波峰強度。 The polyvinyl alcohol preferably has a saponification degree of not less than 50 and not more than 98, more preferably not less than 60 and not more than 90. When the saponification degree is within the above numerical range, in addition to the polyvinyl alcohol exhibiting sufficient water solubility, when the protective layer-forming composition contains the polyvinyl alcohol, the protective layer-forming composition on the first release liner 2 The coating can be implemented with good operability. The saponification degree of the aforementioned polyvinyl alcohol can be measured by proton nuclear magnetic resonance spectroscopy ( 1 H-NMR measurement method). In addition, when the measurement sample contains an additive and the peak derived from the additive overlaps with the peak used to calculate the saponification degree, the measurement sample is subjected to methanol extraction or the like to separate the additive, and then the saponification degree of the polyvinyl alcohol is measured. . The saponification degree of the aforementioned polyvinyl alcohol can be measured under the following conditions. <Measurement conditions> ・Analysis device FT-NMR: Bruker Biospin, AVANCE III-400 ・Observation frequency 400MHz (1H) ・Measurement solvent heavy water, or heavy dimethylsulfoxide (heavy DMSO) ・Measurement temperature 80°C ・Chemical shift standard External standard TSP-d4 (0.00ppm) (when measuring heavy water) Measurement solvent (2.50ppm) (when measuring heavy DMSO) In addition, the saponification degree of polyvinyl alcohol mentioned above is based on the methylene group derived from the vinyl alcohol unit (VOH). The peak of the acetyl group (heavy water: around 2.0-1.0ppm, heavy DMSO: 1.9-1.0ppm), and the acetyl group derived from the vinyl acetate unit (VAc) (heavy water: around 2.1ppm, heavy DMSO: around 2.0ppm), Calculated based on the following formula. In the following formula, [VOH(-CH 2 -)] refers to the peak intensity derived from -CH 2 - in the vinyl alcohol unit; [Vac(CH 3 CO-)] refers to the peak intensity derived from the vinyl acetate unit. CH 3 CO- peak intensity.

[數1] [Number 1]

前述聚乙烯醇,平均聚合度理想為100以上1000以下,更理想為100以上800以下。 藉由平均聚合度在上述數值範圍內,除了前述聚乙烯醇可表現充分水溶性,使前述保護層形成組成物含有前述聚乙烯醇時,可操作性良好地實施對第1離型紙2上之前述保護層形成組成物之塗布。 前述聚乙烯醇之平均聚合度,可藉由水系凝膠滲透層析(GPC)測定。 前述聚乙烯醇之平均聚合度,可用以下條件測定。 <測定條件> ・分析裝置 Agilent, 1260Infinity ・管柱 TSKgel G6000PWXL(東曹公司製)以及TSKgel G3000PWXL(東曹公司製) 上述2支管柱係串聯連接。 ・管柱溫度 40℃ ・溶析液 0.2M之硝酸鈉水溶液 ・注入量 100μL ・檢測器 示差折射計(RI) ・標準樣品 PEG標準樣品以及PVA標準樣品 具體之測定,係用以下方法進行。 (1)藉由使用PEG標準樣品之GPC測定,算出被測定樣品(PVA)以及PVA標準樣品各自之質量平均分子量Mw。又,PVA標準樣品,係已知平均聚合度。 (2)使用PVA標準樣品之平均聚合度、以及算出之PVA標準樣品之質量平均分子量Mw製作檢量線。 (3)使用製作之檢量線,由被測定樣品(PVA)之質量平均分子量Mw求得被測定樣品(PVA)之平均聚合度。 The average degree of polymerization of the polyvinyl alcohol is preferably from 100 to 1,000, and more preferably from 100 to 800. Since the average degree of polymerization is within the above numerical range, in addition to the polyvinyl alcohol exhibiting sufficient water solubility, when the protective layer-forming composition contains the polyvinyl alcohol, the first release paper 2 can be effectively processed with good operability. Coating of the aforementioned protective layer forming composition. The average degree of polymerization of the aforementioned polyvinyl alcohol can be measured by aqueous gel permeation chromatography (GPC). The average degree of polymerization of the aforementioned polyvinyl alcohol can be measured under the following conditions. <Measurement conditions> ・Analysis device Agilent, 1260Infinity ・Pipe string: TSKgel G6000PWXL (manufactured by Tosoh Corporation) and TSKgel G3000PWXL (manufactured by Tosoh Corporation) The above two pipe strings are connected in series. ・Tube string temperature 40℃ ・Eluate: 0.2M sodium nitrate aqueous solution ・Injection volume: 100μL ・Detector: Differential refractometer (RI) ・Standard sample: PEG standard sample and PVA standard sample The specific measurement is carried out by the following method. (1) Calculate the mass average molecular weight Mw of each of the sample to be measured (PVA) and the PVA standard sample by GPC measurement using a PEG standard sample. In addition, the PVA standard sample has a known average degree of polymerization. (2) Use the average degree of polymerization of the PVA standard sample and the calculated mass average molecular weight Mw of the PVA standard sample to create a calibration line. (3) Use the prepared calibration curve to calculate the average degree of polymerization of the sample to be measured (PVA) from the mass average molecular weight Mw of the sample to be measured (PVA).

此外,作為前述水溶性高分子,使用前述聚乙烯醇時,可組合使用皂化度相異之複數個聚乙烯醇、亦可組合使用平均聚合度相異之複數個聚乙烯醇。Furthermore, when using the polyvinyl alcohol as the water-soluble polymer, a plurality of polyvinyl alcohols having different saponification degrees may be used in combination, or a plurality of polyvinyl alcohols having different average polymerization degrees may be used in combination.

前述水溶性聚酯,係具有多元羧酸之殘基及多元醇之殘基。 前述水溶性聚酯,係例如含有多元羧酸成分及多元醇成分之單體成分之聚合生成物。 又,前述水溶性聚酯具有水溶性,係可基於技術常識判斷。 The aforementioned water-soluble polyester has a residue of a polycarboxylic acid and a residue of a polyhydric alcohol. The water-soluble polyester is, for example, a polymerization product of a monomer component containing a polycarboxylic acid component and a polyol component. In addition, it can be judged based on technical common sense that the aforementioned water-soluble polyester has water solubility.

前述水溶性聚酯,理想係滿足以下(1)~(4)中至少一者。 (1)在以前述水溶性聚酯所形成之厚度20μm之薄膜之表面整體用常溫(23±2℃)水以0.005mpA之噴霧壓噴霧20分鐘時,此薄膜全溶解於水。 (2) 在以前述水溶性聚酯所形成之厚度20μm之薄膜之表面整體用50℃水以0.005mpA之噴霧壓噴霧10分鐘時,此薄膜全溶解於水。 (3)將前述水溶性聚酯及常溫水以水溶性聚酯:常溫水=1:5之質量比混合獲得混合液,對該混合液照射超音波20分鐘時,前述水溶性聚酯全溶解於水。 (4) 將前述水溶性聚酯及50℃水以水溶性聚酯:50℃水=1:5之質量比混合獲得混合液,對該混合液照射超音波10分鐘時,前述水溶性聚酯全溶解於水。 The water-soluble polyester preferably satisfies at least one of the following (1) to (4). (1) When the entire surface of a 20 μm thick film formed of the water-soluble polyester is sprayed with water at room temperature (23±2°C) at a spray pressure of 0.005 MPA for 20 minutes, the film is completely dissolved in the water. (2) When the entire surface of a 20 μm thick film formed of the water-soluble polyester is sprayed with 50°C water at a spray pressure of 0.005 MPA for 10 minutes, the film is completely dissolved in the water. (3) Mix the aforementioned water-soluble polyester and normal temperature water at a mass ratio of water-soluble polyester: normal temperature water = 1:5 to obtain a mixed solution. When the mixed solution is irradiated with ultrasonic waves for 20 minutes, the aforementioned water-soluble polyester is completely dissolved. in water. (4) Mix the aforementioned water-soluble polyester and 50°C water at a mass ratio of water-soluble polyester: 50°C water = 1:5 to obtain a mixed solution. When the mixed solution is irradiated with ultrasonic waves for 10 minutes, the aforementioned water-soluble polyester Totally soluble in water.

保護層1之厚度,理想為2μm以上70μm以下,更理想為3μm以上50μm以下,更加理想為5μm以上40μm以下。 保護層1之厚度,係可使用例如針盤量規(PEACOCK公司製,型式R-205),藉由測定隨機選擇之任意5點之厚度,並將此等之厚度算術平均而求得。 The thickness of the protective layer 1 is preferably not less than 2 μm and not more than 70 μm, more preferably not less than 3 μm and not more than 50 μm, and even more preferably not less than 5 μm and not more than 40 μm. The thickness of the protective layer 1 can be obtained by measuring the thickness of five randomly selected points using, for example, a dial gauge (manufactured by PEACOCK, model R-205), and averaging the thicknesses arithmetic.

作為第1離型紙2,可列舉例如使用聚對苯二甲酸乙二酯(PET)等樹脂所製作之樹脂片材。 以如上所述之樹脂片材構成第1離型紙2時,前述樹脂片材中,為了適當調整與保護層1之黏附力,至少可對貼合於保護層1之面施以如上述說明之表面處理。 此外,作為第2離型紙3,與第1離型紙2同樣,可列舉例如使用聚對苯二甲酸乙二酯(PET)等樹脂所製作之樹脂片材。 以如上所述之樹脂片材構成第2離型紙3時,前述樹脂片材中,為了適當調整與保護層1之黏附力,至少可對貼合於保護層1之面施以如上述說明之表面處理。 Examples of the first release paper 2 include a resin sheet made of resin such as polyethylene terephthalate (PET). When the first release paper 2 is composed of the above-mentioned resin sheet, in order to appropriately adjust the adhesion force between the resin sheet and the protective layer 1, at least the surface that is attached to the protective layer 1 can be subjected to the above-described method. Surface treatment. In addition, examples of the second release paper 3 include, like the first release paper 2 , a resin sheet made of resin such as polyethylene terephthalate (PET). When the second release paper 3 is composed of the above-mentioned resin sheet, in order to appropriately adjust the adhesion force between the resin sheet and the protective layer 1, at least the surface that is attached to the protective layer 1 can be subjected to the above-described method. Surface treatment.

第1離型紙2之厚度為T A,第2離型紙3之厚度為T B時,厚度T A以及厚度T B理想係滿足以下關係式: T A<T B35μm<T B<80μm。 When the thickness of the first release paper 2 is TA and the thickness of the second release paper 3 is TB , the thickness TA and the thickness TB ideally satisfy the following relationship: T A <T B 35 μm <T B <80 μm.

離型紙,通常厚度越厚,抗彎強度(彎曲剛性)越高。 並且,離型紙,彈性強度越高,越難往厚度方向彎曲。 於此,如上述說明,在半導體晶圓等之黏附體之保護對象面,貼合藉由剝離第1離型紙2而露出之保護層1之一表面。 並且,第1離型紙2,係從外側(未配置有保護層1之側)被施加吸引力等外力,而從保護層1之一表面被剝離。 如上所述之情形,在第1離型紙2因吸引等而產生彎曲,因產生此彎曲導致第1離型紙2之一部分從保護層1之一表面浮起。 並且,以該浮起部分作為基點,第1離型紙2,變得可從保護層1之一表面被剝離。 如上所述,從保護層1之一表面剝離第1離型紙2時,第2離型紙3亦容易朝內側(配置有保護層1之側)產生彎曲、第2離型紙3從保護層1之另一表面浮起係不理想。 因此,第1離型紙2之厚度T A及第2離型紙3之厚度T B,如上所述,理想係滿足T A<T B之關係式。 此外,將保護層1之一表面貼合於前述保護對象面後,第2離型紙3,通常從保護層1之另一表面被剝離。 因此,從將保護層1之一表面貼合於前述保護對象面後,第2離型紙3容易剝離之觀點而言,第2離型紙3之厚度T B,如上所述,理想係滿足35μm<T B<80μm之關係式。 藉此,因可使第2離型紙3具有適當彈性強度,從保護層1之另一表面剝離第2離型紙3時,可抑制第2離型紙3以保護層1之一部分附著之狀態下被剝離,亦即,可抑制非期望剝離產生。 Generally, the thicker the release paper, the higher the flexural strength (bending rigidity). Moreover, the higher the elastic strength of the release paper, the more difficult it is to bend in the thickness direction. Here, as described above, one surface of the protective layer 1 exposed by peeling off the first release paper 2 is bonded to the protection target surface of the adherend such as the semiconductor wafer. Furthermore, the first release paper 2 is peeled off from one surface of the protective layer 1 by applying an external force such as an attraction force from the outside (the side where the protective layer 1 is not disposed). As described above, the first release paper 2 is bent due to attraction or the like, and this bending causes a part of the first release paper 2 to float from one surface of the protective layer 1 . Then, using this raised portion as a base point, the first release paper 2 becomes peelable from one surface of the protective layer 1 . As mentioned above, when the first release paper 2 is peeled off from one surface of the protective layer 1, the second release paper 3 is also prone to bending inward (the side where the protective layer 1 is disposed). Another surface that floats is not ideal. Therefore, the thickness TA of the first release paper 2 and the thickness TB of the second release paper 3 ideally satisfy the relationship of TA <T B as mentioned above. In addition, after one surface of the protective layer 1 is bonded to the surface to be protected, the second release paper 3 is usually peeled off from the other surface of the protective layer 1 . Therefore, from the viewpoint that the second release paper 3 can be easily peeled off after one surface of the protective layer 1 is bonded to the surface to be protected, the thickness T B of the second release paper 3 should ideally satisfy 35 μm< as mentioned above. The relational expression of T B <80μm. In this way, the second release paper 3 can be provided with appropriate elastic strength, and when the second release paper 3 is peeled off from the other surface of the protective layer 1, the second release paper 3 can be prevented from being attached to a part of the protective layer 1. Peeling, that is, the occurrence of undesired peeling can be suppressed.

此外,藉由使第1離型紙2之厚度T A與第2離型紙3之厚度T B相異,從側面以目視確認保護片材10時,容易識別第1離型紙2以及第2離型紙3。 In addition, by making the thickness TA of the first release paper 2 and the thickness TB of the second release paper 3 different, when the protective sheet 10 is visually recognized from the side, the first release paper 2 and the second release paper can be easily identified. 3.

第1離型紙2之厚度T A,可為15μm以上,亦可為20μm以上,亦可為25μm以下。 此外,第1離型紙2之厚度T A,可為未滿40μm,亦可為35μm以下。 進一步地,第2離型紙3之厚度T B,可為40μm以上,亦可為45μm以上,亦可為50μm以上,亦可為60μm以上。 此外,第2離型紙3之厚度T B,可為75μm以下,亦可為70μm以下。 第1離型紙2以及第2離型紙3之厚度,係可以與保護層1之厚度同樣方式求得。 The thickness TA of the first release paper 2 may be 15 μm or more, 20 μm or more, or 25 μm or less. In addition, the thickness TA of the first release paper 2 may be less than 40 μm or less than 35 μm. Furthermore, the thickness TB of the second release paper 3 may be 40 μm or more, 45 μm or more, 50 μm or more, or 60 μm or more. In addition, the thickness TB of the second release paper 3 may be 75 μm or less, or may be 70 μm or less. The thickness of the first release paper 2 and the second release paper 3 can be obtained in the same manner as the thickness of the protective layer 1 .

從容易藉由視覺辨識第1離型紙2以及第2離型紙3之觀點而言,第1離型紙2及第2離型紙3亦可具有不同顏色。 亦可將第1離型紙2以及第2離型紙3雙方著色,例如將第1離型紙2著色為黑色、將第2離型紙3著色為白色等,使第1離型紙2及第2離型紙3藉由視覺之識別性提升。 此外,第1離型紙2以及第2離型紙3雙方皆為無色透明時,亦可將第1離型紙2或第2離型紙3中一方著色,使第1離型紙2及第2離型紙3之識別性提升。 作為用以著色第1離型紙2以及第2離型紙3之著色劑,可使用各種周知之著色劑。 作為前述著色劑,可列舉染料及顏料等。 又,染料,係意指具有溶解於水或有機溶劑等之性質之著色劑;顔料,係意指具有不溶解於水或有機溶劑等之性質之著色劑。 From the viewpoint of easy visual identification of the first release paper 2 and the second release paper 3, the first release paper 2 and the second release paper 3 may also have different colors. Both the first release paper 2 and the second release paper 3 can also be colored, for example, the first release paper 2 is colored black, the second release paper 3 is colored white, etc., so that the first release paper 2 and the second release paper 3. Improved visual recognition. In addition, when both the first release paper 2 and the second release paper 3 are colorless and transparent, one of the first release paper 2 or the second release paper 3 can also be colored to make the first release paper 2 and the second release paper 3 The recognition is improved. As the coloring agent for coloring the first release paper 2 and the second release paper 3, various well-known coloring agents can be used. Examples of the colorant include dyes, pigments, and the like. In addition, dye means a coloring agent having a property of being soluble in water, an organic solvent, etc.; and a pigment means a coloring agent having a property of being insoluble in water, an organic solvent, etc.

本說明書所揭露之事項包含如下。The matters disclosed in this manual include the following.

(1) 一種保護片材,其係具備: 保護層; 第1離型紙,其係配置於前述保護層之一表面;及 第2離型紙,其係配置於前述保護層之另一表面;且 前述保護層,係含有水溶性高分子化合物; 前述第1離型紙對前述保護層之剝離力為P A,前述第2離型紙對前述保護層之剝離力為P B時, 剝離力P A及剝離力P B滿足以下關係式: P A<P B(1) A protective sheet having: a protective layer; a first release paper arranged on one surface of the aforementioned protective layer; and a second release paper arranged on the other surface of the aforementioned protective layer; and The aforementioned protective layer contains a water-soluble polymer compound; when the peeling force of the aforementioned first release paper to the aforementioned protective layer is P A and the peeling force of the aforementioned second release paper to the aforementioned protective layer is P B , the peeling force P A and The peeling force P B satisfies the following relationship: P A <P B .

根據該構成,可充分兼顧在使一側的剝離片材剝離時抑制前述保護層從另一側的剝離片材浮起的發生、及抑制前述保護層非期望剝離。According to this configuration, when the release sheet on one side is peeled off, it is possible to fully achieve both suppression of the occurrence of the protective layer floating from the release sheet on the other side and suppression of unintended peeling of the protective layer.

(2) 如(1)所記載之保護片材,其中, 前述第1離型紙之厚度為T A,前述第2離型紙之厚度為T B時, 厚度T A及厚度T B滿足以下關係式: T A<T B35μm<T B<80μm。 (2) The protective sheet as described in (1), wherein the thickness of the first release paper is TA and the thickness of the second release paper is TB , the thickness TA and the thickness TB satisfy the following relational expression : T A <T B 35μm <T B <80μm.

根據該構成,可更充分兼顧在使一側的剝離片材剝離時抑制前述保護層從另一側的剝離片材浮起的發生、及抑制前述保護層非期望剝離。 此外,容易以視覺識別一側的剝離片材及另一側的剝離片材。 According to this configuration, it is possible to more fully achieve both the suppression of the occurrence of the protective layer lifting from the other side of the release sheet when the one side of the release sheet is peeled off, and the suppression of the unintended peeling of the above-mentioned protective layer. In addition, it is easy to visually identify the release sheet on one side and the release sheet on the other side.

又,本發明之保護片材並不限定於前述實施型態。此外,本發明之保護片材並不限定於前述之作用效果。本發明之保護片材能夠在不脫離本發明的主旨的範圍內進行各種變更。 [實施例] In addition, the protective sheet of the present invention is not limited to the aforementioned embodiment. In addition, the protective sheet of the present invention is not limited to the above-mentioned effects. The protective sheet of the present invention can be variously modified without departing from the gist of the present invention. [Example]

接著,列舉實施例進一步具體說明本發明。以下實施例係用以進一步詳細說明本發明,並非限定本發明之範圍。Next, the present invention will be further described in detail with reference to Examples. The following examples are used to further illustrate the present invention in detail, but do not limit the scope of the present invention.

[實施例1] 在容器內製作使聚乙烯醇(皂化度65、平均聚合度240)分散於水之水分散溶液。 又,以下,聚乙烯醇亦稱為PVA。 接著,將含有該水分散溶液之容器放入90℃之水浴中,藉由攪拌該水分散容器使PVA溶解於水,獲得PVA溶解組成物。 接著,在具有施以矽酮離型處理之面(以下,亦稱為矽酮離型處理面)之第2離型紙(三菱化學公司製之商品名「DIAFOIL MRV75」,厚度75μm)之離型處理面上,使用塗布器以厚度5μm塗布前述PVA溶解組成物。 接著,藉由將塗布前述PVA溶解組成物之第2離型紙以110℃乾燥2分鐘,在前述第2離型紙上形成保護層。 接著,在前述保護層上,疊合具有矽酮離型處理面之第1離型紙(三菱化學公司製之商品名「DIAFOIL MRA25」,厚度25μm),獲得依序積層有前述第2離型紙、前述保護層、以及前述第1離型紙之積層體後,將該積層體以70℃進行加熱處理。 又,前述第1離型紙,係將矽酮離型處理面疊合於前述保護層之露出面。 藉此,獲得實施例1之保護片材。 此外,以下,DIAFOIL MRV75簡記為「MRV75」,DIAFOIL MRA25簡記為「MRA25」。 [Example 1] A water dispersion solution in which polyvinyl alcohol (saponification degree 65, average polymerization degree 240) is dispersed in water is prepared in a container. In addition, below, polyvinyl alcohol is also called PVA. Next, the container containing the water dispersion solution was placed in a 90° C. water bath, and the water dispersion container was stirred to dissolve PVA in water to obtain a PVA dissolved composition. Next, a second release paper (trade name "DIAFOIL MRV75" manufactured by Mitsubishi Chemical Corporation, thickness 75 μm) having a surface to which silicone release treatment is applied (hereinafter also referred to as a silicone release treatment surface) is released. On the treated surface, the PVA dissolving composition was applied with a thickness of 5 μm using an applicator. Next, the second release paper coated with the PVA dissolving composition was dried at 110° C. for 2 minutes to form a protective layer on the second release paper. Next, on the protective layer, a first release paper with a silicone release treatment surface (trade name "DIAFOIL MRA25" manufactured by Mitsubishi Chemical Corporation, thickness 25 μm) was laminated to obtain the above-mentioned second release paper, After the laminated body of the aforementioned protective layer and the aforementioned first release paper is formed, the laminated body is heated at 70°C. Furthermore, the first release paper has a silicone release-treated surface laminated on the exposed surface of the protective layer. Thus, the protective sheet of Example 1 was obtained. In addition, below, DIAFOIL MRV75 is abbreviated as “MRV75” and DIAFOIL MRA25 is abbreviated as “MRA25”.

前述聚乙烯醇之皂化度以及平均聚合度,遵照在上述實施型態項目中說明之方法測定。The saponification degree and average degree of polymerization of the polyvinyl alcohol are measured according to the method described in the above embodiment item.

[實施例2] 除了使用東洋紡公司製之商品名「Crisper CN500-50」作為前述第2離型紙,使用三菱化學公司製之商品名「DIAFOIL MRA38」作為前述第1離型紙,且前述保護層之厚度為10μm以外,以與實施例1同樣方式,獲得實施例2之保護片材。 又,作為前述第2離型紙之Crisper CN500-50,係具有以不含矽酮化合物之非矽酮系剝離劑施以離型處理之面(以下,亦稱為非矽酮離型處理面),厚度為50μm。 此外,作為前述第1離型紙之DIAFOIL MRA38,係與前述MRA75以及前述MRA25同樣具有矽酮離型處理面,厚度為38μm。 進一步地,將前述第1離型紙之矽酮離型處理面貼合於前述保護層之一表面,將前述第2離型紙之非矽酮離型處理面貼合於前述保護層之另一表面。 此外,以下,Crisper CN500-50簡記為「CN500-50」,DIAFOIL MRA38簡記為「MRA38」。 [Example 2] In addition to using the trade name "Crisper CN500-50" manufactured by Toyobo Co., Ltd. as the aforementioned second release paper, using the trade name "DIAFOIL MRA38" manufactured by Mitsubishi Chemical Corporation as the aforementioned first release paper, and the thickness of the aforementioned protective layer is 10 μm, In the same manner as in Example 1, the protective sheet of Example 2 was obtained. In addition, Crisper CN500-50 as the second release paper has a surface that has been subjected to release treatment with a non-silicone release agent that does not contain a silicone compound (hereinafter, also referred to as a non-silicone release surface). , thickness is 50μm. In addition, DIAFOIL MRA38, which is the first release paper, has a silicone release-treated surface like the MRA75 and MRA25, and has a thickness of 38 μm. Further, the silicone release treated surface of the first release paper is bonded to one surface of the protective layer, and the non-silicone release treated surface of the second release paper is bonded to the other surface of the protective layer. . In addition, below, Crisper CN500-50 is abbreviated as "CN500-50", and DIAFOIL MRA38 is abbreviated as "MRA38".

[實施例3] 除了使用東洋紡公司製之商品名「Crisper CN100-38」作為前述第1離型紙,且前述保護層之厚度為30μm以外,以與實施例2同樣方式,獲得實施例3之保護片材。 又,作為前述第1離型紙之Crisper CN100-38,係與Crisper CN500-50同樣具有非矽酮離型處理面,厚度為38μm。 此外,以下,Crisper CN100-38簡記為「CN100-38」。 [Example 3] The protective sheet of Example 3 was obtained in the same manner as in Example 2, except that the trade name "Crisper CN100-38" manufactured by Toyobo Co., Ltd. was used as the first release paper, and the thickness of the protective layer was 30 μm. In addition, Crisper CN100-38 as the first release paper has a non-silicone release treated surface like Crisper CN500-50, and its thickness is 38 μm. In addition, below, Crisper CN100-38 is abbreviated as "CN100-38".

[實施例4] 除了使用東洋紡公司製之商品名「Crisper CN100-38」作為前述第2離型紙,且前述保護層之厚度為5μm以外,以與實施例3同樣方式,獲得實施例4之保護片材。 [Example 4] The protective sheet of Example 4 was obtained in the same manner as in Example 3, except that the trade name "Crisper CN100-38" manufactured by Toyobo Co., Ltd. was used as the second release paper, and the thickness of the protective layer was 5 μm.

[比較例1] 除了使用東麗公司製之商品名「Lumirror(註冊商標)#38-S10」作為前述第1離型紙,亦使用東麗公司製之商品名「Lumirror(註冊商標)#50-S10」作為前述第2離型紙,且保護層之厚度為10μm以外,以與實施例1同樣方式,獲得比較例1之保護片材。 又,作為前述第1離型紙之Lumirror(註冊商標)#38-S10,係未施以任何離型處理,厚度為38μm。 此外,作為前述第2離型紙之Lumirror(註冊商標)#50-S10,係亦未施以任何離型處理,厚度為50μm。 進一步地,以下,Lumirror(註冊商標)#38-S10簡記為「#38-S10」、Lumirror(註冊商標)#50-S10簡記為「#50-S10」。 又,「#38-S10」以及「#50-S10」,係同樣為聚酯膜。 [Comparative example 1] In addition to using the trade name "Lumirror (registered trademark) #38-S10" manufactured by Toray Corporation as the aforementioned first release paper, the trade name "Lumirror (registered trademark) #50-S10" manufactured by Toray Corporation is also used as the aforementioned first release paper. 2 release paper, and the thickness of the protective layer is other than 10 μm, in the same manner as Example 1, obtain the protective sheet of Comparative Example 1. In addition, Lumirror (registered trademark) #38-S10, which is the first release paper, has not been subjected to any release treatment and has a thickness of 38 μm. In addition, the aforementioned second release paper, Lumirror (registered trademark) #50-S10, has not been subjected to any release treatment and has a thickness of 50 μm. Furthermore, below, Lumirror (registered trademark) #38-S10 is abbreviated as "#38-S10", and Lumirror (registered trademark) #50-S10 is abbreviated as "#50-S10". In addition, "#38-S10" and "#50-S10" are also polyester films.

[比較例2] 除了使用三菱化學公司製之商品名「DIAFOIL MRA50」作為前述第2離型紙以外,以與實施例2同樣方式,獲得比較例2之保護片材。 又,作為前述第2離型紙之DIAFOIL MRA50,係與前述MRV75、前述MRA25、以及前述MRA38同樣具有矽酮離型處理面,厚度為50μm。 此外,以下,DIAFOIL MRA50簡記為「MRA50」。 [Comparative example 2] The protective sheet of Comparative Example 2 was obtained in the same manner as in Example 2, except that "DIAFOIL MRA50", a trade name manufactured by Mitsubishi Chemical Corporation, was used as the second release paper. In addition, DIAFOIL MRA50, which is the second release paper, has a silicone release-treated surface like the above-mentioned MRV75, the above-mentioned MRA25, and the above-mentioned MRA38, and has a thickness of 50 μm. In addition, below, DIAFOIL MRA50 is abbreviated as “MRA50”.

<剝離力> 針對各例之保護片材,測定前述第1離型紙對前述保護層之剝離力P A、以及前述第2離型紙對前述保護層之剝離力P B。 剝離力P A以及剝離力P B,係遵照在上述實施型態項目說明之方法實施。 在以下表1,針對各例之保護片材,表示測定剝離力P A以及剝離力P B之結果。 此外,在以下表1,針對各例之保護片材,亦表示剝離力P B對剝離力P A之比R。 <Peel force> For the protective sheet of each example, the peeling force P A of the first release paper to the protective layer, and the peeling force P B of the second release paper to the protective layer were measured. The peeling force P A and the peeling force PB are implemented in accordance with the method described in the above implementation type item. Table 1 below shows the results of measuring the peeling force P A and the peeling force P B for the protective sheets of each example. In addition, Table 1 below also shows the ratio R of the peeling force P B to the peeling force P A for the protective sheet of each example.

<保護層之非期望剝離> 剝離力之測定中,藉由目視觀察從前述保護層剝離之離型紙之表面,遵照以下基準評價保護層之非期望剝離。 優:在離型紙之表面以目視未確認到保護層。 不佳:在離型紙之表面以目視確認到保護層之一部分。 在以下表1,表示保護層之非期望剝離之評價結果。 <Unintended peeling off of protective layer> In the measurement of the peeling force, the surface of the release paper peeled off from the protective layer was visually observed, and undesired peeling of the protective layer was evaluated in accordance with the following criteria. Excellent: No protective layer was visually confirmed on the surface of the release paper. Poor: Part of the protective layer was visually confirmed on the surface of the release paper. Table 1 below shows the evaluation results of undesired peeling of the protective layer.

<保護層之浮起> 在溫度23±2℃、且相對溼度55±5%RH之環境下將各例之保護片材放置24小時後,以目視觀察保護層是否有從各離型紙(第1離型紙以及第2離型紙)浮起。 接著,遵照以下基準,評價保護層之浮起。 優:不論從第1離型紙以及第2離型紙以目視均完全未確認到保護層之浮起。此外,即使在將保護片材暴露於上述環境(溫度23±2℃、且相對溼度55±5%RH)下24小時後,用手將第1離型紙從保護層剝離時,以目視亦完全未確認到保護層從第2離型紙浮起。 佳:不論從第1離型紙以及第2離型紙以目視均完全未確認到保護層之浮起。另一方面,將保護片材暴露於上述環境24小時後,用手將第1離型紙從保護層剝離時,以目視確認到保護層從第2離型紙稍微浮起。 不佳:從第1離型紙以及第2離型紙至少一方以目視確認到保護層之浮起。 對保護層之浮起的評價結果示於以下表1。 <Lifting of protective layer> After placing the protective sheets of each example for 24 hours at a temperature of 23±2℃ and a relative humidity of 55±5%RH, visually observe whether the protective layer has separated from each release paper (the first release paper and the second release paper). Paper) floats. Next, the lifting of the protective layer was evaluated based on the following criteria. Excellent: No lifting of the protective layer was visually confirmed from either the first release paper or the second release paper. In addition, even after exposing the protective sheet to the above-mentioned environment (temperature 23±2°C and relative humidity 55±5%RH) for 24 hours, the first release paper was peeled off from the protective layer by hand. It was not confirmed that the protective layer was lifted from the second release paper. Good: No lifting of the protective layer was visually confirmed from either the first release paper or the second release paper. On the other hand, after the protective sheet was exposed to the above environment for 24 hours, when the first release paper was peeled off from the protective layer by hand, it was visually confirmed that the protective layer was slightly lifted from the second release paper. Poor: The lifting of the protective layer was visually confirmed from at least one of the first release paper and the second release paper. The evaluation results of the lifting of the protective layer are shown in Table 1 below.

[表1] [Table 1]

從表1可知,如各實施例之保護片材,針對第1離型紙對保護層之剝離力P A、以及第2離型紙對保護層之剝離力P B滿足P A<P B,且P B≦2000mN/25mm之關係式者,可兼顧抑制保護層之非期望剝離及抑制保護層之浮起。 相對於此,可知如各比較例之保護片材,未滿足上述關係式者,無法兼顧抑制保護層之非期望剝離及抑制保護層之浮起。 此外,比R為2.0以上之實施例1~3之保護片材之保護層之浮起的評價結果與比R未滿2.0之各比較例之保護片材之保護層之浮起的評價結果進行比較後,可知實施例1~3之保護片材可獲得特別良好之結果。 又,比較例1之保護片材,因剝離力P A之值以及剝離力P B之值過高,無法評價保護層之浮起。 因此,針對比較例1之保護片材,在表1中將保護層之浮起的評價記載為「無法評價」。 It can be seen from Table 1 that for the protective sheet of each embodiment, the peeling force P A of the first release paper to the protective layer and the peeling force P B of the second release paper to the protective layer satisfy P A < P B , and P The relationship formula of B ≦2000mN/25mm can both suppress the undesired peeling of the protective layer and suppress the floating of the protective layer. On the other hand, it was found that the protective sheet of each comparative example, which does not satisfy the above-mentioned relational expression, cannot simultaneously suppress the unintended peeling of the protective layer and suppress the floating of the protective layer. In addition, the evaluation results of the lifting of the protective layer of the protective sheets of Examples 1 to 3 with a ratio R of 2.0 or more were compared with the evaluation results of the lifting of the protective layer of the protective sheets of the protective sheets of each comparative example with a ratio R of less than 2.0. After comparison, it can be seen that the protective sheets of Examples 1 to 3 can obtain particularly good results. In addition, in the protective sheet of Comparative Example 1, the value of the peeling force P A and the value of the peeling force P B were too high, and the lifting of the protective layer could not be evaluated. Therefore, regarding the protective sheet of Comparative Example 1, the evaluation of the floating of the protective layer in Table 1 is described as "unevaluable".

1:保護層 2:第1離型紙 3:第2離型紙 10:保護片材 1: Protective layer 2: 1st release paper 3: 2nd release paper 10:Protective sheet

〔圖1〕係表示本發明之一實施型態之保護片材之構成之示意剖面圖。 〔圖2〕係表示將保護片材之保護層貼合於半導體晶圓等電子零件之保護對象面之安裝裝置之構成之剖面圖。 [Fig. 1] is a schematic cross-sectional view showing the structure of a protective sheet according to an embodiment of the present invention. [Figure 2] is a cross-sectional view showing the structure of a mounting device for bonding a protective layer of a protective sheet to a surface to be protected of electronic components such as semiconductor wafers.

1:保護層 1: Protective layer

2:第1離型紙 2: 1st release paper

3:第2離型紙 3: 2nd release paper

10:保護片材 10:Protective sheet

Claims (2)

一種保護片材,其係具備: 保護層; 第1離型紙,其係配置於該保護層之一表面;及 第2離型紙,其係配置於該保護層之另一表面;且 該保護層,係含有水溶性高分子化合物; 該第1離型紙對該保護層之剝離力為P A,第2離型紙對該保護層之剝離力為P B時, 剝離力P A及剝離力P B滿足以下關係式: P A<P BP B≦2000mN/25mm。 A protective sheet, which has: a protective layer; a first release paper, which is arranged on one surface of the protective layer; and a second release paper, which is arranged on the other surface of the protective layer; and the protective layer , contains a water-soluble polymer compound; when the peeling force of the first release paper to the protective layer is P A and the peeling force of the second release paper to the protective layer is P B , the peeling force P A and peeling force P B The following relationship is satisfied: P A <P B P B ≦2000mN/25mm. 如請求項1所述之保護片材,其中, 該第1離型紙之厚度為T A,該第2離型紙之厚度為T B時, 厚度T A及厚度T B滿足以下關係式: T A<T B35μm<T B<80μm。 The protective sheet as described in claim 1, wherein the thickness of the first release paper is TA and the thickness of the second release paper is TB , the thickness TA and the thickness TB satisfy the following relationship: TATB 35μm< TB <80μm.
TW112122439A 2022-07-06 2023-06-15 Protective sheet TW202402537A (en)

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JP2022109059A JP2024007757A (en) 2022-07-06 2022-07-06 Protective sheet

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