TW202238699A - Support sheet, composite sheet for forming protective film, and manufacturing method of device wherein the support sheet is capable of taking into account of both poor drawing out of the sheet and identifiability of laser marking when viewed through a substrate - Google Patents

Support sheet, composite sheet for forming protective film, and manufacturing method of device wherein the support sheet is capable of taking into account of both poor drawing out of the sheet and identifiability of laser marking when viewed through a substrate Download PDF

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TW202238699A
TW202238699A TW111108503A TW111108503A TW202238699A TW 202238699 A TW202238699 A TW 202238699A TW 111108503 A TW111108503 A TW 111108503A TW 111108503 A TW111108503 A TW 111108503A TW 202238699 A TW202238699 A TW 202238699A
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protective film
film
adhesive layer
forming
sheet
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山本大輔
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日商琳得科股份有限公司
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    • C—CHEMISTRY; METALLURGY
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/403—Adhesives in the form of films or foils characterised by release liners characterised by the structure of the release feature
    • 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
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture 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
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H01L21/561—Batch processing
    • 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
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H01L23/3157—Partial encapsulation or coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/544—Marks applied to semiconductor devices or parts, e.g. registration marks, alignment structures, wafer maps
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2223/00—Details relating to semiconductor or other solid state devices covered by the group H01L23/00
    • H01L2223/544—Marks applied to semiconductor devices or parts
    • H01L2223/54453—Marks applied to semiconductor devices or parts for use prior to dicing

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  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dicing (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Physical Vapour Deposition (AREA)
  • Laser Beam Processing (AREA)
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Abstract

The present invention provides a support sheet capable of taking into account of both poor drawing out of the sheet and identifiability of laser marking when viewed through a substrate, a composite sheet for forming a protective film including the support sheet and the protective film forming film, and a manufacturing method of a semiconductor device and other devices. The support sheet has a substrate and an adhesive layer formed on one main surface of the substrate. The arithmetic average height Sa1 of a quadrilateral area of 4.91 mm×4.90 mm on the main surface of the substrate on which no adhesive layer is formed is greater than 0.50 [mu]m. The glossiness value of the main surface on which no adhesive layer is formed is more than 20 at an incident angle of 60DEG. In addition, the composite sheet for forming the protective film is provided with the support sheet and the protective film forming film.

Description

支撐片、保護膜形成用複合片及裝置的製造方法Support sheet, composite sheet for forming protective film, and manufacturing method of device

本發明涉及支撐片、保護膜形成用複合片及裝置的製造方法。特別涉及在加工半導體晶圓等工件時用於固定工件的支撐片、具有該支撐片與適合用於保護半導體晶圓等工件或保護對工件進行加工而得到的半導體晶片等加工物的保護膜形成膜的保護膜形成用複合片、以及半導體晶片等裝置的製造方法。The present invention relates to a method for manufacturing a support sheet, a composite sheet for forming a protective film, and a device. In particular, it relates to a support sheet for fixing a workpiece when processing a workpiece such as a semiconductor wafer, and a protective film suitable for protecting a workpiece such as a semiconductor wafer or protecting a processed product such as a semiconductor wafer obtained by processing the workpiece. A method for manufacturing a composite sheet for forming a protective film of a film, and a device such as a semiconductor wafer.

近年來，採用被稱為所謂倒裝(face down)方式的安裝方法進行半導體裝置的製造。在倒裝方式中，使用在電路面上具有凸塊(bump)等電極的半導體晶片將電極與基板接合。因此，有時會露出半導體晶片的與電路面相反一側的背面。In recent years, semiconductor devices have been manufactured using a mounting method called a so-called face down method. In the flip-chip method, electrodes are bonded to a substrate using a semiconductor wafer having electrodes such as bumps on a circuit surface. Therefore, the back surface of the semiconductor wafer opposite to the circuit surface may be exposed.

有時在該露出的半導體晶片的背面，形成作為保護膜的由有機材料構成的樹脂膜，並將這樣的帶保護膜的半導體晶片安裝到半導體裝置中。保護膜用於在切割步驟及其後續步驟中防止半導體晶片發生碎裂或缺損等崩邊(chipping)。In some cases, a resin film made of an organic material is formed as a protective film on the back surface of the exposed semiconductor wafer, and such a semiconductor wafer with a protective film is mounted in a semiconductor device. The protective film is used to prevent chipping, such as chipping or chipping, of the semiconductor wafer during the dicing step and its subsequent steps.

為了形成這樣的保護膜，可使用在支撐片上具備保護膜形成膜(保護膜形成層)而成的保護膜形成用複合片。作為支撐片，例如可使用在樹脂製的基材上層疊黏著劑層等而成的層疊片。此外，單獨的支撐片也可發揮半導體晶圓等的切割片的功能。對於保護膜形成用複合片，除了保護膜形成膜具有形成保護膜的能力以外，支撐片還可發揮切割片的功能，因此可以說保護膜形成用複合片是將保護膜形成膜與切割片一體化的片。In order to form such a protective film, the composite sheet for protective film formation which provided the protective film forming film (protective film forming layer) on a support sheet can be used. As the support sheet, for example, a laminated sheet obtained by laminating an adhesive layer or the like on a resin base material can be used. In addition, a single support sheet can also function as a dicing sheet for a semiconductor wafer or the like. For the composite sheet for protective film formation, in addition to the ability of the protective film forming film to form a protective film, the support sheet can also function as a dicing sheet. Therefore, it can be said that the composite sheet for protective film formation is a combination of a protective film forming film and a dicing sheet. sliced.

作為用於支撐片的基材，通常其在與其他構件相接觸的面具有凹凸形狀。這是因為，若不具有該凹凸形狀，從捲繞支撐片而成的卷中拉出支撐片時，基材會與形成在黏著劑層上的剝離膜發生貼附而黏連，致使難以從卷中拉出支撐片。因此，若基材的與其他構件相接觸的面具有凹凸形狀，則接觸面的面積減小，因此可抑制黏連。As a base material used for a support sheet, it usually has uneven|corrugated shape on the surface which contacts another member. This is because, if the uneven shape is not present, when the support sheet is pulled out from the roll formed by winding the support sheet, the base material will adhere to and stick to the release film formed on the adhesive layer, making it difficult to remove the support sheet from the adhesive layer. Pull out the support sheet from the roll. Therefore, if the surface of the base material that is in contact with other members has a concave-convex shape, the area of the contact surface is reduced, so that sticking can be suppressed.

此外，在支撐片的黏著劑層上形成有保護膜形成膜的保護膜形成用複合片也相同。即，從捲繞保護膜形成用複合片而成的卷中拉出保護膜形成用複合片時，基材與形成在保護膜形成膜上的剝離膜會發生貼附而黏連，因此基材在與剝離膜相接觸的面具有凹凸形狀。In addition, the same applies to the composite sheet for protective film formation in which the protective film forming film was formed on the adhesive layer of the support sheet. That is, when the composite sheet for protective film formation is pulled out from the roll formed by winding the composite sheet for protective film formation, the base material and the release film formed on the protective film formation film will stick and stick together, so the base material The surface in contact with the release film has unevenness.

另一方面，為了識別半導體晶圓或半導體晶片，會藉由例如雷射打標而在半導體晶圓或保護膜形成膜的表面打標出標記或文字等。該雷射打標藉由從支撐片所具備的基材的未形成黏著劑層的一面側射入雷射而進行。因此，若未形成黏著劑層的面具有凹凸形狀，則雷射會在該面上發生散射或漫反射從而導致標記變得不清晰。On the other hand, in order to identify a semiconductor wafer or a semiconductor chip, marks or characters are marked on the surface of the semiconductor wafer or the protective film forming film by, for example, laser marking. This laser marking is performed by injecting laser light from the side on which the adhesive layer is not formed of the base material included in the support sheet. Therefore, if the surface on which the adhesive layer is not formed has unevenness, the laser light will be scattered or diffusely reflected on the surface, and the mark will become unclear.

專利文獻1中記載了一種在支撐片或支撐片的黏著劑層上具備保護膜形成膜的保護膜形成用複合片，所述支撐片具備基材與層疊在基材上的黏著劑層，在所述保護膜形成用複合片中，其具備黏著劑層的一側的表面的表面粗糙度(Ra)為0.4μm以下，基材的與具備黏著劑層的一側相反一側的表面的表面粗糙度(Ra)大於具備黏著劑層的一側的表面的表面粗糙度、且該表面粗糙度為0.053~0.48μm。並記載了根據該支撐片或保護膜形成用複合片，能夠使雷射打標的辨認性良好且能夠抑制黏連。 現有技術文獻 專利文獻 Patent Document 1 describes a composite sheet for forming a protective film having a protective film forming film on a support sheet including a base material and an adhesive layer laminated on the base material, or on an adhesive layer of the support sheet. In the composite sheet for forming a protective film, the surface roughness (Ra) of the surface on the side provided with the adhesive layer is 0.4 μm or less, and the surface of the surface of the substrate opposite to the side provided with the adhesive layer is The roughness (Ra) is larger than the surface roughness of the surface having the adhesive layer, and the surface roughness is 0.053 to 0.48 μm. It also describes that according to the support sheet or the composite sheet for protective film formation, the visibility of laser marking can be improved and blocking can be suppressed. prior art literature patent documents

專利文獻1：國際公開2017/163971號公報Patent Document 1: International Publication No. 2017/163971

本發明要解決的技術問題The technical problem to be solved in the present invention

然而，即使是專利文獻1中記載的支撐片或保護膜形成用複合片，也存在難以更穩定地兼顧因黏連引起的片的拉出不良與隔著基材觀察時雷射打標的辨認性的問題。However, even with the support sheet or the composite sheet for forming a protective film described in Patent Document 1, it is difficult to achieve a more stable balance between the poor drawing-out of the sheet due to sticking and the visibility of laser marking when viewed through the base material. The problem.

本發明是鑒於該實際狀況而完成的，目的在於提供一種能夠兼顧片的拉出不良與隔著基材觀察時的雷射打標的辨認性的支撐片、具備該支撐片與保護膜形成膜的保護膜形成用複合片、以及半導體裝置等裝置的製造方法。 解決技術問題的技術機構 The present invention has been made in view of this actual situation, and an object thereof is to provide a support sheet capable of achieving both poor drawing out of the sheet and laser marking visibility when observed through a base material, and a support sheet comprising the support sheet and a protective film forming film. A method for manufacturing a composite sheet for forming a protective film and a device such as a semiconductor device. Technological bodies that solve technical problems

本發明的方案如下所述。 [1]一種支撐片，其具有基材與形成在基材的一個主面上的黏著劑層， 基材的未形成黏著劑層的主面上的4.91mm×4.90mm的四邊形區域的算數平均高度Sa1大於0.50μm， 未形成黏著劑層的主面在入射角為60°時的光澤度值為20以上。 [2]根據[1]所述的支撐片，其中，未形成黏著劑層的主面上的4.91mm×4.90mm的四邊形區域是由300個作為0.36mm×0.27mm的四邊形區域的小區域合成而得到的大區域， 將各小區域的算數平均高度中的最小算數平均高度至第20小的算數平均高度的平均值設為Sa2時，Sa2為0.43μm以下。 [3]根據[1]或[2]所述的支撐片，其中，作為Sa1相對於Sa2之比的Sa1/Sa2為1.40以上。 [4]根據[1]~[3]中任一項所述的支撐片，其中，不在未形成黏著劑層的主面上形成其他層。 [5]一種保護膜形成用複合片，其具有[1]~[4]中任一項所述的支撐片與形成在支撐片的黏著劑層上的保護膜形成膜。 [6]一種套件，其具有[1]~[4]中任一項所述的支撐片與用於貼附於支撐片的黏著劑層的表面的保護膜形成膜。 [7]一種裝置的製造方法，其具有： 將捲繞成卷狀的[1]~[4]中任一項所述的支撐片放卷並拉出的步驟， 將所拉出的支撐片貼附於工件的步驟， 對工件進行雷射打標的步驟，及 加工工件從而得到工件的加工物的步驟。 [8]一種裝置的製造方法，其具有： 將捲繞成卷狀的[5]所述的保護膜形成用複合片放卷並拉出的步驟， 將所拉出的保護膜形成用複合片的保護膜形成膜貼附於工件背面的步驟， 將所貼附的保護膜形成膜製成保護膜的步驟， 對保護膜或保護膜形成膜進行雷射打標的步驟，及 將背面具有保護膜或保護膜形成膜的工件單顆化，從而得到多個帶保護膜或保護膜形成膜的工件的加工物的步驟。 發明效果 The scheme of the present invention is as follows. [1] A support sheet having a base material and an adhesive layer formed on one main surface of the base material, The arithmetic average height Sa1 of the 4.91mm×4.90mm quadrilateral region on the main surface of the substrate on which no adhesive layer is formed is greater than 0.50μm, The gloss value of the main surface on which no adhesive layer is formed is 20 or more at an incident angle of 60°. [2] The support sheet according to [1], wherein the quadrangular area of 4.91 mm x 4.90 mm on the main surface on which the adhesive layer is not formed is composed of 300 small areas that are quadrangular areas of 0.36 mm x 0.27 mm And the resulting large area, When the average value of the arithmetic mean height from the smallest arithmetic mean height to the 20th smallest arithmetic mean height among the arithmetic mean heights of each small region is Sa2, Sa2 is 0.43 micrometers or less. [3] The support sheet according to [1] or [2], wherein Sa1/Sa2, which is a ratio of Sa1 to Sa2, is 1.40 or more. [4] The support sheet according to any one of [1] to [3], wherein no other layer is formed on the main surface on which the adhesive layer is not formed. [5] A composite sheet for forming a protective film, comprising the support sheet according to any one of [1] to [4] and a protective film forming film formed on the adhesive layer of the support sheet. [6] A kit comprising the support sheet according to any one of [1] to [4] and a protective film forming film to be attached to the surface of the adhesive layer of the support sheet. [7] A method of manufacturing a device, comprising: a step of unrolling and pulling out the support sheet according to any one of [1] to [4] wound into a roll, a step of attaching the pulled out supporting sheet to the workpiece, the steps of laser marking the workpiece, and The step of processing a workpiece to obtain a processed product of the workpiece. [8] A method of manufacturing a device, comprising: A step of unwinding and pulling out the composite sheet for forming a protective film described in [5] wound into a roll, a step of attaching the drawn protective film forming film of the protective film forming composite sheet to the back surface of the workpiece, the step of making the attached protective film forming film into a protective film, a step of laser marking the protective film or the protective film forming film, and A step of singulating the workpiece having a protective film or a protective film forming film on the back surface to obtain a plurality of workpieces with a protective film or a protective film forming film. Invention effect

根據本發明，能夠提供一種可兼顧片的拉出不良與隔著基材進行觀察時的雷射打標的辨認性的支撐片、具備該支撐片與保護膜形成膜的保護膜形成用複合片、以及半導體裝置等裝置的製造方法。According to the present invention, it is possible to provide a supporting sheet capable of achieving both poor drawing out of the sheet and laser marking visibility when observed through a base material, a composite sheet for forming a protective film comprising the supporting sheet and a protective film forming film, And a method for manufacturing devices such as semiconductor devices.

具體實施方式detailed description

以下，基於具體的實施方案，利用附圖對本發明進行詳細說明。首先，對本說明書中所使用的主要的術語進行說明。Hereinafter, based on specific embodiments, the present invention will be described in detail using the drawings. First, main terms used in this specification will be described.

工件為貼附本實施方案的支撐片或保護膜形成用複合片並進行加工的板狀體。作為工件，例如可列舉出晶圓、面板。具體而言，可列舉出半導體晶圓、半導體面板。作為工件的加工物，例如可列舉出將晶圓單顆化而得到的晶片。具體而言，可例示出將半導體晶圓單顆化而得到的半導體晶片。此時，保護膜形成在晶圓及晶片的背面側。The workpiece is a plate-like body processed by attaching the supporting sheet or the composite sheet for forming a protective film according to the present embodiment. Examples of the workpiece include wafers and panels. Specifically, a semiconductor wafer and a semiconductor panel are mentioned. Examples of the workpiece to be processed include wafers obtained by singulating wafers. Specifically, a semiconductor wafer obtained by singulating a semiconductor wafer can be exemplified. At this time, the protective film is formed on the wafer and the back side of the wafer.

晶圓等工件的“表面”是指形成有電路、凸塊等凸狀電極等的面；“背面”是指未形成電路、電極(例如凸塊等凸狀電極)等的面。The "surface" of a workpiece such as a wafer refers to the surface on which circuits and protruding electrodes such as bumps are formed; the "back surface" refers to the surface on which no circuits or electrodes (such as protruding electrodes such as bumps) are formed.

晶圓的單顆化是指按照每個電路分割晶圓從而得到晶片。Wafer singulation refers to dividing the wafer into individual circuits to obtain wafers.

在本說明書中，例如“(甲基)丙烯酸酯”是指用於表示“丙烯酸酯”及“甲基丙烯酸酯”這兩者的術語，其他類似術語也相同。In this specification, for example, "(meth)acrylate" is a term used to indicate both "acrylate" and "methacrylate", and other similar terms are also the same.

“能量射線”是指紫外線、電子束等，優選為紫外線。"Energy rays" means ultraviolet rays, electron beams, etc., preferably ultraviolet rays.

剝離膜為以可剝離的方式支撐黏著劑層或保護膜形成膜的膜。對於膜，不限定其厚度，也用作包含片的概念。The peeling film is a film that supports the adhesive layer or the protective film forming film in a peelable manner. Regarding the film, the thickness thereof is not limited, and it is also used as a concept including a sheet.

與保護膜形成膜用組合物等組合物相關的說明中的質量比為基於有效成分(固體成分)的質量比，除另有說明外，不計入溶劑。The mass ratio in the description of compositions such as the protective film-forming composition is based on the active ingredient (solid content), and the solvent is not included unless otherwise specified.

(1. 支撐片) 本實施方案的支撐片用於在加工工件時對工件進行固定。例如，在切斷工件而得到多個工件的加工物時，將該片貼附於工件而使用。因此，本實施方案的支撐片可用作切割片。此外，也可以如同後述的保護膜形成用複合片，在支撐片上形成對工件或工件的加工物賦予特定性能的功能層。 (1. Support piece) The supporting sheet of this embodiment is used to fix the workpiece when processing the workpiece. For example, when cutting a workpiece to obtain a processed product of a plurality of workpieces, the sheet is used by being attached to the workpiece. Therefore, the support sheet of this embodiment can be used as a cutting sheet. Moreover, like the composite sheet for protective film formation mentioned later, the functional layer which imparts specific performance to a workpiece|work or the processed object of a workpiece|work may be formed on a support sheet.

如圖1所示，本實施方案的支撐片1具有基材2、形成在基材的一個主面2a上的黏著劑層3。在本實施方案中，優選不在基材2的未形成黏著劑層的主面2b上形成其他層。即，優選基材2的未形成黏著劑層的主面2b為露出於外部的露出面。As shown in FIG. 1 , the support sheet 1 of the present embodiment has a base material 2 and an adhesive layer 3 formed on one main surface 2 a of the base material. In the present embodiment, it is preferable not to form other layers on the main surface 2b of the substrate 2 on which the adhesive layer is not formed. That is, it is preferable that the main surface 2b of the substrate 2 on which the adhesive layer is not formed is an exposed surface exposed to the outside.

本實施方案的支撐片可以為長邊方向的長度相對於短邊方向的長度非常長的長條狀片的形態。此外，也可以為捲繞該長條狀片而成的片卷的形態。The support sheet of this embodiment may be in the form of a long sheet whose length in the longitudinal direction is very long relative to the length in the short direction. Moreover, the form of the sheet roll which wound this elongated sheet may be sufficient.

當捲繞支撐片時，優選在黏著劑層3的表面3a形成有剝離膜。藉由在黏著劑層的表面形成有剝離膜，即使在捲繞支撐片而形成片卷時，也能夠防止基材、黏著劑層的表面3a及基材的未形成黏著劑層的主面2b之間的貼附。When winding up the support sheet, it is preferable that a release film is formed on the surface 3 a of the adhesive layer 3 . By forming the release film on the surface of the adhesive layer, even when the support sheet is wound to form a sheet roll, it is possible to prevent the base material, the surface 3a of the adhesive layer, and the main surface 2b of the base material on which the adhesive layer is not formed. attachment between.

(2. 保護膜形成用複合片) 本實施方案的保護膜形成用複合片藉由將保護膜形成膜貼附於工件並將保護膜形成膜製成保護膜，從而用於對工件或工件的加工物進行保護。 (2. Composite sheet for protective film formation) The protective film forming composite sheet of this embodiment is used to protect a workpiece or a processed object of a workpiece by attaching a protective film forming film to a workpiece and making the protective film forming film into a protective film.

如圖2所示，本實施方案的保護膜形成用複合片10具有保護膜形成膜4、支撐保護膜形成膜4的支撐片1、用於將保護膜形成用複合片10黏合於環形框架等夾具的夾具用黏著劑層5。支撐片1與在(1)中說明的支撐片相同，其具有基材2與形成在基材2的一個主面2a上的黏著劑層3。保護膜形成膜4形成在黏著劑層3的表面3a上。夾具用黏著劑層5形成在保護膜形成膜4的主面4a的周邊部。As shown in FIG. 2 , the composite sheet 10 for forming a protective film according to this embodiment has a protective film forming film 4 , a support sheet 1 for supporting the protective film forming film 4 , a composite sheet 10 for forming a protective film to a ring frame, and the like. The adhesive layer 5 for the jig of the jig. The support sheet 1 is the same as that described in (1), and has a base material 2 and an adhesive layer 3 formed on one main surface 2 a of the base material 2 . The protective film forming film 4 is formed on the surface 3 a of the adhesive layer 3 . The adhesive layer 5 for a jig is formed in the peripheral part of the main surface 4a of the protective film forming film 4. As shown in FIG.

與(1)相同，在本實施方案中，優選不在基材2的未形成黏著劑層的主面2b上形成其他層。即，優選基材2的未形成黏著劑層的主面2b為露出於外部的露出面。As in (1), in this embodiment, it is preferable not to form another layer on the main surface 2b of the substrate 2 on which the adhesive layer is not formed. That is, it is preferable that the main surface 2b of the substrate 2 on which the adhesive layer is not formed is an exposed surface exposed to the outside.

此外，與(1)相同，本實施方案的保護膜形成用複合片可以為長邊方向的長度相對於短邊方向的長度非常長的長條狀片的形態。此外，也可以為捲繞該長條狀片而成的片卷的形態。Moreover, similarly to (1), the composite sheet for protective film formation of this embodiment may be the form of the elongated sheet whose length in the longitudinal direction is very long with respect to the length in the short direction. Moreover, the form of the sheet roll which wound this elongated sheet may be sufficient.

當捲繞保護膜形成用複合片時，優選在保護膜形成膜4的表面4a及夾具用黏著劑層5的表面形成有剝離膜。藉由在黏著劑層的表面形成有剝離膜，即使捲繞保護膜形成用複合片而形成片卷時，也能夠防止保護膜形成膜4的表面4a及夾具用黏著劑層5的表面與基材的未形成黏著劑層的主面2b之間的貼附。When winding up the composite sheet for protective film formation, it is preferable that a peeling film is formed on the surface 4a of the protective film forming film 4 and the surface of the adhesive agent layer 5 for clips. By forming the peeling film on the surface of the adhesive layer, even when the protective film forming composite sheet is wound to form a sheet roll, it is possible to prevent the surface 4a of the protective film forming film 4 and the surface of the adhesive layer 5 for jigs from contacting the substrate. The attachment between the main surfaces 2b of the materials on which the adhesive layer is not formed.

然而，在將卷狀的帶剝離膜的保護膜形成用複合片放卷並為了貼附於工件而將其拉出時，有時位於該剝離膜的半徑方向的正下方的保護膜形成用複合片會貼附在形成於保護膜形成膜的表面的剝離膜上，從而無法拉出保護膜形成用複合片。同樣地，在將卷狀的帶剝離膜的支撐片放卷並為了貼附於工件而將其拉出時，有時位於該剝離膜的半徑方向的正下方的支撐片會貼附在形成於黏著劑層的表面的剝離膜上，從而無法拉出支撐片。However, when a roll-shaped protective film-forming composite sheet with a release film is unrolled and pulled out to be attached to a workpiece, the protective film-forming composite sheet located directly below the release film in the radial direction may Since the sheet is stuck to the release film formed on the surface of the protective film forming film, the composite sheet for protective film forming cannot be pulled out. Similarly, when a roll-shaped support sheet with a release film is unrolled and pulled out to be attached to a workpiece, the support sheet located immediately below the radial direction of the release film may be attached to the The release film on the surface of the adhesive layer, so that the support sheet cannot be pulled out.

為了防止這樣的拉出不良，優選在支撐片及保護膜形成用複合片所具備的基材的未形成黏著劑層的主面2b上形成細小的凹凸。藉由形成該凹凸，可減少基材的主面2b與剝離膜之間的接觸面積，降低支撐片或保護膜形成用複合片對剝離膜的貼附。In order to prevent such a pull-out failure, it is preferable to form fine irregularities on the main surface 2b on which the adhesive layer is not formed of the base material included in the support sheet and the composite sheet for protective film formation. By forming the unevenness, the contact area between the main surface 2b of the base material and the release film can be reduced, and the sticking of the support sheet or the composite sheet for protective film formation to the release film can be reduced.

然而，對於作為工件的晶圓或將晶圓單顆化而得到的晶片，為了提高識別性，有時會對晶圓或晶片進行打標。此時，有直接對晶圓或晶片進行打標的情況、或對貼附於晶圓或晶片的保護膜進行打標的情況。無論哪種情況，通常均藉由照射雷射進行打標(雷射打標)。However, for a wafer as a workpiece or a wafer obtained by singulating the wafer, the wafer or wafer may be marked in order to improve identification. At this time, marking may be performed directly on the wafer or wafer, or marking may be performed on a protective film attached to the wafer or wafer. In either case, marking is generally performed by irradiating laser light (laser marking).

進行雷射打標時，晶圓或晶片位於圖1所示的黏著劑層的表面3a上、或位於圖2所示的保護膜形成膜的主面4a上，因此雷射從基材的主面2b側入射並透射支撐片1而到達晶圓或晶片。此時，若在基材的主面2b上形成有凹凸，則雷射會發生散射或漫反射從而使標記變得不清晰。When performing laser marking, the wafer or chip is positioned on the surface 3a of the adhesive layer shown in FIG. 1, or on the main surface 4a of the protective film forming film shown in FIG. The incident surface 2b side and transmits the support sheet 1 to reach the wafer or chip. At this time, if the irregularities are formed on the main surface 2b of the base material, the laser light will be scattered or diffusely reflected to make the mark unclear.

此外，為了確認實施在晶圓或晶片上的打標，存在將支撐片剝離後對標記進行觀察的情況、或隔著支撐片對標記進行觀察的情況。當隔著支撐片觀察標記時，由於利用顯微鏡等從基材的主面2b側對標記進行觀察，因此若觀察光發生散射或漫反射，則有時無法清晰地辨認標記。In addition, in order to confirm the marking performed on the wafer or on the wafer, the mark may be observed after peeling off the support sheet, or the mark may be observed through the support sheet. When the mark is observed through the support sheet, since the mark is observed from the main surface 2 b side of the base material with a microscope or the like, the mark may not be clearly recognized when observation light is scattered or diffusely reflected.

因此，支撐片的基材的未形成黏著劑層的面的表面狀態，會對支撐片或保護膜形成用複合片的拉出性與雷射打標的辨認性造成影響，這兩者是相反的特性。即，非常不易兼顧這兩者。Therefore, the surface condition of the base material of the support sheet on which the adhesive layer is not formed affects the pull-out performance of the support sheet or the protective film forming composite sheet and the visibility of laser marking, which are opposite. characteristic. That is, it is very difficult to balance both.

因此，在本實施方案中，藉由按照以下方式控制支撐片的基材的表面性狀，能夠兼顧拉出性與雷射打標的辨認性。以下，對本實施方案的支撐片及保護膜形成用複合片的構成要素進行詳細說明。Therefore, in this embodiment, by controlling the surface texture of the base material of a support sheet as follows, both pull-out property and the visibility of a laser marking can be made compatible. Hereinafter, the constituent elements of the support sheet and the composite sheet for protective film formation of this embodiment are demonstrated in detail.

(3. 基材) 支撐片的基材在加工工件時經由黏著劑層支撐工件。基材可以由一個樹脂膜所構成的單層膜構成，也可以由多個樹脂膜層疊而成的多層膜構成。 (3. Substrate) The base material of the supporting sheet supports the workpiece through the adhesive layer when the workpiece is processed. The base material may be composed of a single-layer film composed of one resin film, or may be composed of a multi-layer film composed of a plurality of resin films laminated.

然而，優選不在基材的與形成有黏著劑層的主面相反一側的主面(未形成黏著劑層的主面)上形成其他層。因此，優選基材的未形成黏著劑層的主面為露出於外部的露出面。However, it is preferable not to form another layer on the main surface of the substrate opposite to the main surface on which the adhesive layer is formed (the main surface on which the adhesive layer is not formed). Therefore, it is preferable that the main surface of the base material on which the adhesive layer is not formed is an exposed surface exposed to the outside.

形成該其他層時存在耗費成本的問題。此外，對於與其他層相接觸的面，還存在其他層所含的成分發生偏移而附著於該與其他層相接觸的面的風險。特別是當支撐片或保護膜形成用複合片為片卷的形態時，由於其他層與剝離膜的背面相接觸，因此顯現上述風險的可能性大。There is a problem of cost in forming this other layer. In addition, as for the surface in contact with another layer, there is also a risk that the components contained in the other layer may shift and adhere to the surface in contact with the other layer. In particular, when the supporting sheet or the protective film-forming composite sheet is in the form of a sheet roll, since other layers are in contact with the back surface of the release film, the possibility of the above-mentioned risk appearing is high.

只要能夠在使用保護膜形成用複合片的各步驟中適當地發揮功能，則基材的厚度沒有特別限定。基材的厚度優選20~200μm、更優選40~170μm、特別優選50~140μm的範圍。The thickness of the base material is not particularly limited as long as it can function appropriately in each step of using the composite sheet for protective film formation. The thickness of the substrate is preferably in the range of 20 to 200 μm, more preferably 40 to 170 μm, particularly preferably 50 to 140 μm.

(3.1 基材的光澤性)(3.1 Gloss of substrate)

在本實施方案中，基材的與形成有黏著劑層的主面相反一側的主面(圖1及2中的主面2b)在入射角為60°時的光澤度值為20以上。藉由使入射角為60°時的光澤度值在上述範圍內，即使隔著支撐片觀察標記，也因可抑制觀察光的散射或漫反射而能夠清晰地辨認標記。In this embodiment, the main surface (the main surface 2 b in FIGS. 1 and 2 ) of the substrate opposite to the main surface on which the adhesive layer is formed has a gloss value of 20 or more at an incident angle of 60°. When the gloss value at an incident angle of 60° is within the above range, even when the mark is observed through the support sheet, the mark can be clearly recognized by suppressing scattering or diffuse reflection of observation light.

入射角為60°時的光澤度值優選為25以上，更優選為35以上，進一步優選為45以上。另一方面，該光澤度值的上限值沒有特別限制，但例如優選為140以下，更優選為110以下，進一步優選為80以下。The gloss value at an incident angle of 60° is preferably 25 or higher, more preferably 35 or higher, and still more preferably 45 or higher. On the other hand, the upper limit of the glossiness value is not particularly limited, but is, for example, preferably 140 or less, more preferably 110 or less, and still more preferably 80 or less.

入射角為60°時的光澤度值可依據JIS Z 8741進行測定。即，用與JIS Z 8741所規定的測定方法相同的方法進行測定，但測定條件可以不同。具體的測定方法在實施例中進行說明。The gloss value at an incident angle of 60° can be measured in accordance with JIS Z 8741. That is, the measurement is performed by the same method as that specified in JIS Z 8741, but the measurement conditions may be different. The specific measurement method is described in the examples.

(3.2 基材的表面性狀) 在本實施方案中，將基材的與形成有黏著劑層的主面(一個主面)相反一側的主面(未形成黏著劑層的主面：圖1及2中的主面2b)的表面性狀控制為特定的形狀。 (3.2 Surface properties of substrate) In this embodiment, the main surface of the substrate opposite to the main surface (one main surface) on which the adhesive layer is formed (the main surface on which the adhesive layer is not formed: main surface 2b in FIGS. 1 and 2 ) The surface texture is controlled for a specific shape.

具體而言，若將基材的未形成黏著劑層的主面上的4.91mm×4.90mm的四邊形區域的算數平均高度設為Sa1，則Sa1大於0.50μm。算數平均高度(Arithmetical mean height of the surface)是ISO25178中所規定的表面粗糙度參數之一，其為測定面上的峰高及谷深的絕對值的平均值。Sa1表示抑制了局部凹凸的影響的整個測定面的平均的表面粗糙度。Specifically, when the arithmetic mean height of the quadrangular region of 4.91 mm×4.90 mm on the main surface of the base material on which the adhesive layer is not formed is Sa1, Sa1 is larger than 0.50 μm. Arithmetical mean height of the surface is one of the surface roughness parameters stipulated in ISO25178, which is the average value of the absolute values of peak height and valley depth on the measurement surface. Sa1 represents the average surface roughness of the entire measurement surface in which the influence of local unevenness is suppressed.

藉由使Sa1在上述範圍內，從整個主面來看，基材的未形成黏著劑層的主面的表面粗糙度相對較粗糙。其結果，由於能夠減少與剝離膜之間的接觸面積，因此可抑制拉出不良。When Sa1 is within the above range, the surface roughness of the main surface of the base material on which the adhesive layer is not formed is relatively rough when viewed from the entire main surface. As a result, since the contact area with the release film can be reduced, it is possible to suppress failure in pulling out.

Sa1優選為0.55μm以上，更優選為0.60μm以上，進一步優選為0.65μm以上。另一方面，只要上述的光澤度值在上述範圍內，則Sa1的上限值沒有限制，但優選為1.2μm以下。Sa1 is preferably 0.55 μm or more, more preferably 0.60 μm or more, still more preferably 0.65 μm or more. On the other hand, as long as the above-mentioned glossiness value is within the above-mentioned range, the upper limit of Sa1 is not limited, but is preferably 1.2 μm or less.

Sa1為以4.91mm×4.90mm的四邊形區域為測定面而得到的表面粗糙度。Sa1 is the surface roughness obtained by using a quadrilateral area of 4.91 mm×4.90 mm as a measurement surface.

此外，在本實施方案中，除了上述的Sa1以外，還優選對將測定上述Sa1的區域進行細分而得到的狹窄區域中的表面粗糙度進行控制。In addition, in the present embodiment, in addition to the above-mentioned Sa1, it is preferable to control the surface roughness in narrow regions obtained by subdividing the region where the above-mentioned Sa1 is measured.

具體而言，首先，將未形成黏著劑層的主面上的4.91mm×4.90mm的四邊形區域設定為合成0.36mm×0.27mm的四邊形區域而得到的區域。因此，4.91mm×4.90mm的四邊形區域為大區域，0.36mm×0.27mm的四邊形區域為小區域。Specifically, first, a quadrangular region of 4.91 mm×4.90 mm on the main surface where the adhesive layer is not formed is set as a region obtained by synthesizing a quadrangular region of 0.36 mm×0.27 mm. Therefore, a quadrilateral area of 4.91 mm×4.90 mm is a large area, and a quadrilateral area of 0.36 mm×0.27 mm is a small area.

如圖3所示，4.91mm×4.90mm的四邊形區域50為將X軸方向上的15列0.36mm×0.27mm的四邊形區域60、Y軸方向上的20行0.36mm×0.27mm的四邊形區域60合成而得到的區域，即合成300個0.36mm×0.27mm的四邊形區域60而得到的區域。因此，大區域50由300個小區域60構成。As shown in FIG. 3 , the quadrilateral area 50 of 4.91mm×4.90mm is composed of 15 columns of quadrilateral areas 60 of 0.36mm×0.27mm in the X-axis direction and 20 rows of quadrilateral areas 60 of 0.36mm×0.27mm in the Y-axis direction. The synthesized region is a region obtained by synthesizing 300 quadrilateral regions 60 of 0.36 mm×0.27 mm. Therefore, the large area 50 is composed of 300 small areas 60 .

在本實施方案中，計算出各個0.36mm×0.27mm的四邊形區域60內的算數平均高度。即，測定各小區域60內的算數平均高度，從而得到300個算數平均高度。在300個算數平均高度中，選擇出最小的算數平均高度至第20小的算數平均高度。即，在對大區域50進行細分而得到的300個小區域60中，選擇出20個平滑的(表面粗糙度小的)小區域。對所選擇的20個小區域的算數平均高度求平均並將其設為Sa2。在本實施方案中，Sa2為0.43μm以下。In the present embodiment, the arithmetic mean height in each quadrilateral area 60 of 0.36 mm×0.27 mm is calculated. That is, the arithmetic mean height in each small region 60 is measured to obtain 300 arithmetic mean heights. Among the 300 arithmetic mean heights, select the smallest arithmetic mean height to the 20th smallest arithmetic mean height. That is, among the 300 small regions 60 obtained by subdividing the large region 50, 20 smooth (small surface roughness) small regions are selected. The arithmetic mean heights of the selected 20 small areas are averaged and set as Sa2. In the present embodiment, Sa2 is 0.43 μm or less.

如上所述，Sa1為以整個大區域50為測定面而得到的表面粗糙度，相反，Sa2為大區域50中的局部區域的表面粗糙度。通常，表面的凹凸以大致均勻的形式存在，當小區域為上述大小時，在各狹窄區域中凹凸以大致均勻的形式存在。其結果，各小區域的表面粗糙度沒有太大差別，Sa2接近於合成小區域而得到的區域的表面粗糙度，即接近於大區域的表面粗糙度。As described above, Sa1 is the surface roughness obtained by using the entire large region 50 as a measurement surface, and on the contrary, Sa2 is the surface roughness of a local region in the large region 50 . Usually, the unevenness of the surface exists substantially uniformly, and when the small regions have the above-mentioned size, the unevenness exists substantially uniformly in each narrow region. As a result, there was not much difference in the surface roughness of the small regions, and Sa2 was close to the surface roughness of a region obtained by synthesizing the small regions, that is, close to the surface roughness of the large region.

因此，當表面的凹凸以大致均勻的形式存在時，即使在300個小區域60中選擇20個表面粗糙度小的小區域，其表面粗糙度的平均值Sa2仍接近於大區域的表面粗糙度Sa1。Therefore, when the unevenness of the surface exists in a substantially uniform form, even if 20 small areas with small surface roughness are selected among the 300 small areas 60, the average value Sa2 of the surface roughness is still close to the surface roughness of the large area. Sa1.

對此，在本實施方案中，雖然Sa1大於0.50μm，但Sa2為0.43μm以下。因此，Sa1及Sa2同時在上述的範圍內意味著，在未形成黏著劑層的主面中，存在使整個大區域50的表面粗糙度在上述範圍內的大的凹凸，同時還存在多個表面粗糙度小的區域。換而言之，表示在未形成黏著劑層的主面中，在相對較平滑的面上稀疏地分佈有相對較大的凹凸。On the other hand, in this embodiment, although Sa1 is larger than 0.50 μm, Sa2 is 0.43 μm or less. Therefore, both Sa1 and Sa2 within the above-mentioned ranges mean that, on the main surface where the adhesive layer is not formed, there are large irregularities such that the surface roughness of the entire large region 50 falls within the above-mentioned ranges, and there are also a plurality of surfaces. Areas of low roughness. In other words, it means that relatively large irregularities are sparsely distributed on the relatively smooth surface of the main surface on which no adhesive layer is formed.

因此，能夠利用相對較大的凹凸來減少與剝離膜之間的接觸面積，同時能夠利用平滑的區域來抑制雷射的散射或漫反射從而使標記更清晰(即，能夠使雷射打標性良好)，進一步，更易於增大光澤度值。即，藉由使未形成黏著劑層的主面具有與表面凹凸以大致均勻的形式存在的面不同的表面性狀，能夠兼顧作為相反特性的拉出性與雷射打標性。Therefore, relatively large unevenness can be used to reduce the contact area with the release film, and at the same time, smooth areas can be used to suppress scattering or diffuse reflection of the laser to make the mark clearer (that is, it is possible to improve the laser marking property). Good), further, it is easier to increase the gloss value. That is, by making the main surface on which no adhesive layer is formed have a different surface texture from the surface with substantially uniform surface irregularities, it is possible to achieve both pull-out properties and laser marking properties which are opposite characteristics.

Sa2優選為0.35μm以下，更優選為0.30μm以下。另一方面，只要上述的光澤度值在上述範圍內，則Sa2的下限值沒有限制，但優選為0.10μm以上。Sa2 is preferably 0.35 μm or less, more preferably 0.30 μm or less. On the other hand, the lower limit of Sa2 is not limited as long as the above-mentioned glossiness value is within the above-mentioned range, but is preferably 0.10 μm or more.

此外，在本實施方案中，優選Sa1相對於Sa2之比(Sa1/Sa2)為1.40以上。藉由使Sa1/Sa2在上述範圍內，能夠以高水準兼顧拉出性與雷射打標性。Furthermore, in the present embodiment, it is preferable that the ratio of Sa1 to Sa2 (Sa1/Sa2) is 1.40 or more. By setting Sa1/Sa2 within the above range, it is possible to achieve both pull-out property and laser marking property at a high level.

Sa1/Sa2更優選為1.70以上，進一步優選為2.0以上，特別優選為2.3以上。Sa1/Sa2 is more preferably 1.70 or more, still more preferably 2.0 or more, particularly preferably 2.3 or more.

基材的未形成黏著劑層的主面的表面性狀能夠藉由以下方式進行測定。在使用相互正交的X軸及Y軸將未形成黏著劑層的主面表示為XY平面時，能夠以垂直於XY平面的Z軸方向上的位移表示未形成黏著劑層的主面的表面性狀。即，可以以三維(X,Y,Z)形狀來表示未形成黏著劑層的主面的表面粗糙度。The surface properties of the main surface of the substrate on which the adhesive layer is not formed can be measured as follows. When the main surface on which no adhesive layer is formed is expressed as an XY plane by using mutually orthogonal X-axis and Y-axis, the surface of the main surface on which no adhesive layer is formed can be expressed by displacement in the Z-axis direction perpendicular to the XY plane traits. That is, the surface roughness of the main surface on which the adhesive layer is not formed can be expressed in a three-dimensional (X, Y, Z) shape.

因此，可由測定區域中的Z軸方向上的位移的測定結果計算出作為表面粗糙度參數的算數平均高度。在本實施方案中，優選使用非接觸式白光干涉顯微鏡進行表面性狀的測定。Therefore, the arithmetic mean height as a surface roughness parameter can be calculated from the measurement result of the displacement in the Z-axis direction in the measurement area. In this embodiment, it is preferable to use a non-contact white light interference microscope for the measurement of the surface properties.

在白光干涉顯微鏡中，從白色光源照射出的光分為2條光路，一條照射到參照鏡，另一條照射到試驗樣本表面，使從這兩者反射出的光在相機中成像。在所得到的圖像中，藉由將因試驗樣本表面的凹凸引起的光程差而產生的干涉條紋的資訊轉換為高度資訊，從而可得到試驗樣本表面的三維形狀。In the white light interference microscope, the light irradiated from the white light source is divided into two light paths, one is irradiated to the reference mirror, and the other is irradiated to the surface of the test sample, so that the light reflected from the two is imaged in the camera. In the obtained image, the three-dimensional shape of the surface of the test sample can be obtained by converting the information of interference fringes generated by the optical path difference caused by the unevenness of the test sample surface into height information.

在以三維形狀資料的形式得到的測定面的表面性狀的測定結果中，主要包括起因於測定面的形狀的因素、起因於測定面的表面粗糙度的因素及起因於測定面的起伏的因素。因此，測定面的表面性狀的測定結果為合成這些因素而得到的輪廓曲面。這些因素可利用週期(波長)的長度進行區分，起因於表面粗糙度的因素的週期短(波長短)，起因於形狀的因素的週期長(波長長)，起因於起伏的因素則具有介於二者之間的週期。The measurement results of the surface properties of the measurement surface obtained in the form of three-dimensional shape data mainly include factors due to the shape of the measurement surface, factors due to the surface roughness of the measurement surface, and factors due to waviness of the measurement surface. Therefore, the measurement result of the surface texture of the measurement surface is a contoured surface obtained by combining these factors. These factors can be distinguished by the length of the period (wavelength). The factor due to surface roughness has a short period (short wavelength), the factor due to shape has a long period (long wavelength), and the factor due to waviness has a range between period between the two.

從所得到測定結果中去除起因於形狀的因素和起因於起伏的因素，進行獲得由起因於表面粗糙度的因素構成的表面粗糙度曲面的操作。根據所得到的表面粗糙度曲面，依據ISO25178所規定的方法，計算出算數平均高度。即，可以利用與ISO25178所規定的方法相同的方法進行測定，但也可以用與ISO25178所記載的條件不同的條件進行測定。An operation of obtaining a surface roughness curved surface composed of factors resulting from surface roughness is performed by removing factors due to shape and factors due to waviness from the obtained measurement results. Based on the obtained surface roughness surface, the arithmetic mean height is calculated according to the method stipulated in ISO25178. That is, although measurement can be performed by the same method as the method prescribed|regulated by ISO25178, it can also measure by the conditions different from the conditions described in ISO25178.

由測定結果得到表面粗糙度曲面的操作，能夠藉由公知的濾波處理、平坦化處理等而進行。例如，能夠使用白光干涉顯微鏡附帶的解析軟體或市售的解析軟體。The operation of obtaining the surface roughness curved surface from the measurement results can be performed by known filtering processing, flattening processing, and the like. For example, analysis software attached to a white light interference microscope or commercially available analysis software can be used.

測定主面的表面性狀時，優選將白光干涉顯微鏡的倍率設為20~110倍，更優選設為50倍。When measuring the surface properties of the main surface, the magnification of the white light interference microscope is preferably 20 to 110 times, more preferably 50 times.

另外，大區域50藉由合成300個小區域60而得到，但此時如圖4所示，各小區域是以周邊部重疊的狀態合成的。即，若著眼於構成大區域50的一個小區域(60a)，則小區域60a的周邊部和與小區域60a相接的小區域60b~60i的各自的周邊部重疊。藉由設置這樣的重疊區域OA，能夠確保彼此相接的小區域的邊界部分的表面粗糙度的連續性。若不設置重疊區域OA而合成小區域60，則有可能包含作為干擾的實際的表面性狀中不存在的凹凸。In addition, the large area 50 is obtained by synthesizing 300 small areas 60 , but at this time, as shown in FIG. 4 , the small areas are synthesized in a state in which their peripheral parts overlap. That is, focusing on one small region ( 60 a ) constituting the large region 50 , the peripheral portion of the small region 60 a overlaps with the respective peripheral portions of the small regions 60 b to 60 i adjacent to the small region 60 a. By providing such an overlapping area OA, it is possible to ensure the continuity of the surface roughness of the boundary portion of the small areas that are in contact with each other. If the small area 60 is synthesized without providing the overlapping area OA, unevenness that does not exist in the actual surface texture may be included as disturbance.

(3.3 基材的材質) 作為基材的材質，只要是在工件加工時能夠經由黏著劑層支撐工件的材料且易於透射用於雷射打標的雷射的材料，則沒有特別限制。通常基材由以樹脂類的材料為主要材料的膜(以下稱為“樹脂膜”)構成。作為用於雷射打標的雷射的波長，優選為1064nm、532nm、355nm及266nm，從標記的清晰度或通用性的角度出發，更優選為532nm。 (3.3 Material of base material) The material of the base material is not particularly limited as long as it is a material that can support the workpiece through the adhesive layer during workpiece processing and is a material that easily transmits the laser used for laser marking. Usually, the base material is composed of a film mainly made of a resin material (hereinafter referred to as "resin film"). The wavelength of the laser used for laser marking is preferably 1064 nm, 532 nm, 355 nm, and 266 nm, and more preferably 532 nm from the viewpoint of marking clarity or versatility.

作為樹脂膜的具體實例，可列舉出低密度聚乙烯(LDPE)膜、線性低密度聚乙烯(LLDPE)膜、高密度聚乙烯(HDPE)膜等聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、乙烯-降莰烯共聚物膜、降莰烯樹脂膜等聚烯烴類膜；乙烯-醋酸乙烯酯共聚物膜、乙烯-(甲基)丙烯酸共聚物膜、乙烯-(甲基)丙烯酸酯共聚物膜等乙烯類共聚物膜；聚氯乙烯膜、氯乙烯共聚物膜等聚氯乙烯類膜；聚對苯二甲酸乙二醇酯膜、聚對苯二甲酸丁二醇酯膜等聚酯類膜；聚氨酯膜；聚醯亞胺膜；聚苯乙烯膜；聚碳酸酯膜；氟樹脂膜等。此外，也可以使用這些膜的交聯膜、離聚物膜等改性膜。基材可以是由這些膜中的一種構成的膜，也可以是進一步組合這些膜中的兩種以上而得到的層疊膜。Specific examples of the resin film include polyethylene films such as low-density polyethylene (LDPE) films, linear low-density polyethylene (LLDPE) films, and high-density polyethylene (HDPE) films, polypropylene films, and polybutylene films. , polybutadiene film, polymethylpentene film, ethylene-norbornene copolymer film, norbornene resin film and other polyolefin films; ethylene-vinyl acetate copolymer film, ethylene-(meth)acrylic acid Ethylene-based copolymer films such as copolymer films and ethylene-(meth)acrylate copolymer films; polyvinyl chloride films such as polyvinyl chloride films and vinyl chloride copolymer films; polyethylene terephthalate films, Polyester films such as polybutylene terephthalate films; polyurethane films; polyimide films; polystyrene films; polycarbonate films; fluororesin films, etc. In addition, modified membranes such as crosslinked membranes and ionomer membranes of these membranes can also be used. The substrate may be a film composed of one of these films, or a laminated film obtained by further combining two or more of these films.

在上述膜中，從易於得到本發明的拉出性的效果且易於使用於切割步驟等角度出發，優選聚乙烯膜、聚丙烯膜、乙烯-醋酸乙烯酯共聚物膜、乙烯-(甲基)丙烯酸酯共聚物膜、聚氯乙烯膜、聚對苯二甲酸丁二醇酯膜，其中優選耐熱性優異的聚丙烯膜。Among the above-mentioned films, polyethylene films, polypropylene films, ethylene-vinyl acetate copolymer films, ethylene-(methyl) Among the acrylate copolymer films, polyvinyl chloride films, and polybutylene terephthalate films, polypropylene films excellent in heat resistance are preferable.

(4. 黏著劑層) 支撐片的黏著劑層可以由非能量射線固化性黏著劑構成，也可以由能量射線固化性黏著劑構成。但是，優選黏著劑層由易於透射用於雷射打標的雷射的材料構成。 (4. Adhesive layer) The adhesive layer of the support sheet may be composed of a non-energy ray-curable adhesive or an energy ray-curable adhesive. However, it is preferred that the adhesive layer is composed of a material that is easily transparent to the laser used for laser marking.

作為非能量射線固化性黏著劑，優選具有所需的黏著力及再剝離性的物質，例如能夠使用丙烯酸類黏著劑、橡膠類黏著劑、矽酮類黏著劑、氨基甲酸酯類黏著劑、聚酯類黏著劑、聚乙烯基醚類黏著劑等。As the non-energy ray-curable adhesive, it is preferable to have a desired adhesive force and re-peelability. For example, acrylic adhesives, rubber adhesives, silicone adhesives, urethane adhesives, polyester adhesives, etc. can be used. Ester adhesives, polyvinyl ether adhesives, etc.

其中，優選與保護膜形成膜的密合性高且能夠在切割步驟等中有效地抑制工件或工件的加工物的脫落的丙烯酸類黏著劑。此外，從易於控制帶保護膜的工件的加工物的拾取適性的角度出發，也優選丙烯酸類黏著劑。Among them, an acrylic adhesive having high adhesion to the protective film-forming film and capable of effectively suppressing the peeling of the workpiece or a processed product of the workpiece in a dicing step or the like is preferable. Moreover, an acrylic adhesive is also preferable from the viewpoint of being easy to control the pick-up suitability of the workpiece of the workpiece|work with a protective film.

為了對主要成分(例如，丙烯酸聚合物)進行交聯，優選非能量射線固化性黏著劑包含異氰酸酯類交聯劑、環氧類交聯劑等交聯劑。In order to crosslink the main component (for example, acrylic polymer), it is preferable that the non-energy ray-curable adhesive contains crosslinking agents such as isocyanate crosslinking agents and epoxy crosslinking agents.

另一方面，能量射線固化性黏著劑的黏著力會因能量射線照射而下降，因此在需要使工件或工件的加工物與支撐片分離時，能夠藉由照射能量射線而將其輕鬆分離。On the other hand, since the adhesive force of the energy ray-curable adhesive is lowered by energy ray irradiation, when it is necessary to separate the workpiece or the processed product of the workpiece from the support sheet, it can be easily separated by irradiating the energy ray.

構成黏著劑層的能量射線固化性黏著劑可以將具有能量射線固化性的聚合物作為主要成分，也可以將不具有能量射線固化性的聚合物與能量射線固化性的單體和/或低聚物的混合物作為主要成分。The energy ray-curable adhesive constituting the adhesive layer may contain an energy ray-curable polymer as a main component, or may contain a non-energy ray-curable polymer and an energy ray-curable monomer and/or oligomer. A mixture of substances as the main ingredient.

作為具有能量射線固化性的聚合物，例如，可例示出引入了能量射線固化性基團的(甲基)丙烯酸酯(共聚物)聚合物等。作為能量射線固化性的單體和/或低聚物，可例示出多元醇與(甲基)丙烯酸的酯。此外，除了含有具有能量射線固化性的成分以外，能量射線固化性黏著劑還可以含有光聚合引發劑、交聯劑等添加劑。As a polymer having energy ray curability, for example, a (meth)acrylate (copolymer) polymer into which an energy ray curable group is introduced can be illustrated. Esters of polyols and (meth)acrylic acid can be exemplified as energy ray curable monomers and/or oligomers. In addition, the energy ray-curable adhesive may contain additives such as a photopolymerization initiator and a crosslinking agent in addition to the energy ray-curable component.

只要能夠在使用保護膜形成用複合片的各步驟中適當地發揮功能，則對黏著劑層的厚度沒有特別限定。具體而言，黏著劑層的厚度優選為1~50μm、2~30μm、2~20μm、3~10μm、3~8μm。The thickness of the pressure-sensitive adhesive layer is not particularly limited as long as it can function appropriately in each step of using the composite sheet for protective film formation. Specifically, the thickness of the adhesive layer is preferably 1 to 50 μm, 2 to 30 μm, 2 to 20 μm, 3 to 10 μm, or 3 to 8 μm.

(5. 保護膜形成膜) 保護膜形成用複合片的保護膜形成膜藉由貼附於工件並製成保護膜，從而形成用於保護工件或工件的加工物的保護膜。 (5. Protective film forming film) The protective film forming film of the composite sheet for protective film formation forms the protective film for protecting a workpiece|work or the processed object of a workpiece|work by adhering to a workpiece and making it into a protective film.

“製成保護膜”是指，使保護膜形成膜成為具有充分的保護工件或工件的加工物的特性的狀態。具體而言，當保護膜形成膜為固化性時，“製成保護膜”是指，使未固化的保護膜形成膜成為固化物。換而言之，製成了保護膜的保護膜形成膜為保護膜形成膜的固化物，與保護膜形成膜不同。"Creating a protective film" means bringing the protective film forming film into a state having sufficient properties to protect a workpiece or a processed product of the workpiece. Specifically, when the protective film-forming film is curable, "forming a protective film" means making an uncured protective film-forming film into a cured product. In other words, the protective-film-forming film on which the protective film is formed is a cured product of the protective-film-forming film, and is different from the protective-film-forming film.

在固化性保護膜形成膜上重疊工件後，使保護膜形成膜固化，由此能夠使保護膜牢固地黏合於工件，能夠形成具有耐久性的保護膜。After laminating the workpiece on the curable protective film forming film, the protective film forming film can be cured, whereby the protective film can be firmly adhered to the workpiece, and a durable protective film can be formed.

另一方面，當保護膜形成膜不含有固化性成分而以非固化的狀態進行使用時，從保護膜形成膜被貼附於工件的時刻起，該保護膜形成膜即被製成了保護膜。換而言之，製成保護膜後的保護膜形成膜與保護膜形成膜相同。On the other hand, when the protective film-forming film does not contain curable components and is used in a non-cured state, the protective film-forming film is made into a protective film from the moment the protective film-forming film is attached to the workpiece. . In other words, the protective film-forming film formed as a protective film is the same as the protective film-forming film.

在不追求高保護性能時，無需使保護膜形成膜固化，因此保護膜形成膜易於使用。When high protective performance is not pursued, the protective film forming film does not need to be cured, so the protective film forming film is easy to use.

在本實施方案中，保護膜形成膜優選為固化性。因此，保護膜優選為固化物。作為固化物，例如可例示出熱固化物、能量射線固化物。在本實施方案中，保護膜更優選為熱固化物。In the present embodiment, the protective film-forming film is preferably curable. Therefore, the protective film is preferably a cured product. As a hardened|cured material, a thermosetting material and an energy-beam cured material can be illustrated, for example. In the present embodiment, the protective film is more preferably a thermally cured product.

此外，優選保護膜形成膜在常溫(23℃)下具有黏著性、或藉由加熱而發揮黏著性。由此，在保護膜形成膜上重疊工件時可將二者貼合。因此，能夠確保在使保護膜形成膜固化之前進行定位。Moreover, it is preferable that the protective film forming film has adhesiveness at normal temperature (23 degreeC), or develops adhesiveness by heating. Thereby, both can be bonded together when a workpiece|work is superimposed on a protective film forming film. Therefore, positioning can be ensured before hardening a protective film forming film.

保護膜形成膜可以由一層(單層)構成，也可以由兩層以上的多個層構成。當保護膜形成膜具有多個層時，這些多個層可以彼此相同也可以彼此不同，構成這些多個層的層的組合沒有特別限制。The protective film forming film may be composed of one layer (single layer), or may be composed of a plurality of layers of two or more layers. When the protective film forming film has a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of layers constituting the plurality of layers is not particularly limited.

在本實施方案中，優選保護膜形成膜為一層(單層)。一層的保護膜形成膜，在厚度方面可獲得高精度，因此易於生產。此外，若保護膜形成膜由多個層構成，則需要考慮層間的密合性及各層的伸縮性，存在由此導致從被黏物上剝離的風險。當保護膜形成膜為一層時，能夠降低上述的風險，設計的自由度也會增高。此外，在發生溫度變化的步驟(回流焊處理時或使用裝置時)中，還能夠降低因層間的熱伸縮性差異而發生層間剝離的風險。In the present embodiment, it is preferable that the protective film forming film is one layer (single layer). The protective film of one layer forms a film, and high precision can be obtained in terms of thickness, so it is easy to produce. In addition, when the protective film forming film is composed of a plurality of layers, it is necessary to consider the adhesiveness between the layers and the stretchability of each layer, and there is a risk of peeling from the adherend due to this. When the protective film is formed in one layer, the above-mentioned risks can be reduced, and the degree of freedom in design can also be increased. In addition, it is also possible to reduce the risk of interlayer delamination due to differences in thermal stretchability between layers in steps where temperature changes occur (during reflow processing or when using devices).

保護膜形成膜的厚度沒有特別限制，但優選為100μm以下、70μm以下、45μm以下、30μm以下。此外，保護膜形成膜的厚度優選為5μm以上、10μm以上、15μm以上。若保護膜形成膜的厚度在上述範圍內，則所得到的保護膜的保護性能良好。The thickness of the protective film-forming film is not particularly limited, but is preferably 100 μm or less, 70 μm or less, 45 μm or less, and 30 μm or less. In addition, the thickness of the protective film-forming film is preferably 5 μm or more, 10 μm or more, or 15 μm or more. When the thickness of a protective film forming film exists in the said range, the protective performance of the protective film obtained will become favorable.

另外，保護膜形成膜的厚度是指保護膜形成膜整體的厚度。例如，由多個層構成的保護膜形成膜的厚度是指構成保護膜形成膜的所有層的合計厚度。In addition, the thickness of a protective film forming film means the thickness of the whole protective film forming film. For example, the thickness of the protective film forming film which consists of several layers means the total thickness of all the layers which comprise a protective film forming film.

以下，對形成在作為工件的加工物的晶片上的保護膜進行說明。具體而言，使用圖5所示的帶保護膜的晶片70，對將保護膜形成膜製成保護膜而形成的保護膜進行說明。Hereinafter, a protective film formed on a wafer as a workpiece to be processed will be described. Specifically, using the wafer 70 with a protective film shown in FIG. 5 , a protective film formed by making a protective film forming film a protective film will be described.

如圖5所示，帶保護膜的晶片70在晶片6a的背面側(圖5中的上方側)形成有保護膜40，在晶片6a的表面側(圖5中的下方側)形成有凸狀電極6b。As shown in FIG. 5, the wafer 70 with a protective film has a protective film 40 formed on the back side (upper side in FIG. 5) of the wafer 6a, and a convex shape is formed on the front side (lower side in FIG. 5) of the wafer 6a. Electrode 6b.

在晶片6a的表面側形成有電路，凸狀電極6b以與電路電連接的方式而形成。作為凸狀電極6b，可例示出凸塊、柱形電極(pillar electrode)等。A circuit is formed on the surface side of the wafer 6a, and the protruding electrode 6b is formed so as to be electrically connected to the circuit. A bump, a pillar electrode, etc. can be illustrated as the convex electrode 6b.

在本實施方案中，帶保護膜的晶片70以形成有凸狀電極6b的面朝向晶片搭載用基板的方式配置在晶片搭載用基板上。藉由規定的加熱處理(例如，回流焊處理)，將凸狀電極6b與該基板電接合及機械接合，從而將帶保護膜的晶片70安裝在該基板上。In the present embodiment, the wafer 70 with a protective film is placed on the wafer mounting substrate such that the surface on which the protruding electrodes 6b are formed faces the wafer mounting substrate. The wafer 70 with a protective film is mounted on the substrate by electrically and mechanically bonding the protruding electrodes 6 b to the substrate by predetermined heat treatment (for example, reflow treatment).

(5.1 保護膜形成膜用組合物) 只要保護膜具有上述的物理特性，則保護膜形成膜的組成沒有特別限定。在本實施方案中，優選構成保護膜形成膜的組合物(保護膜形成膜用組合物)為至少含有聚合物成分(A)、固化性成分(B)及填充材料(E)的樹脂組合物。聚合物成分可視為聚合性化合物進行聚合反應而形成的成分。此外，固化性成分為可進行固化(聚合)反應的成分。另外，在本發明中，聚合反應也包括縮聚反應。 (5.1 Composition for Forming a Protective Film) The composition of the protective film forming film is not particularly limited as long as the protective film has the above-mentioned physical properties. In this embodiment, it is preferable that the composition constituting the protective film forming film (the composition for forming a protective film) is a resin composition containing at least a polymer component (A), a curable component (B) and a filler (E). . The polymer component can be regarded as a component formed by the polymerization reaction of a polymerizable compound. In addition, a curable component is a component which can undergo a curing (polymerization) reaction. In addition, in the present invention, the polymerization reaction also includes polycondensation reaction.

此外，聚合物成分中所含的成分有時也屬於固化性成分。在本實施方案中，當保護膜形成膜用組合物含有這種既屬於聚合物成分又屬於固化性成分的成分時，視為保護膜形成膜用組合物含有聚合物成分及固化性成分這兩者。In addition, components contained in polymer components may also belong to curable components. In this embodiment, when the composition for forming a protective film contains such a component as both a polymer component and a curable component, it is considered that the composition for forming a protective film contains both a polymer component and a curable component. By.

(5.1.1 聚合物成分) 聚合物成分(A)在使保護膜形成膜具有膜形成性(成膜性)的同時，還賦予其適度的黏性(tack)，從而確保將保護膜形成膜均一地貼附於工件。聚合物成分的重均分子量通常為5萬~200萬，優選為10萬~150萬，特別優選在20萬~100萬的範圍內。作為這樣的聚合物成分，例如可以使用丙烯酸樹脂、氨基甲酸酯樹脂、苯氧基樹脂、矽酮樹脂、飽和聚酯樹脂等，特別優選使用丙烯酸樹脂。 (5.1.1 Polymer composition) The polymer component (A) not only imparts film-forming properties (film-forming properties) to the protective film-forming film, but also imparts appropriate tack to ensure uniform adhesion of the protective film-forming film to the workpiece. The weight-average molecular weight of the polymer component is usually 50,000 to 2 million, preferably 100,000 to 1.5 million, particularly preferably 200,000 to 1 million. As such a polymer component, for example, acrylic resins, urethane resins, phenoxy resins, silicone resins, saturated polyester resins, etc. can be used, and acrylic resins are particularly preferably used.

另外，在本說明書中，只要沒有特別說明，則“重均分子量”是指藉由凝膠滲透色譜(GPC)法測定的聚苯乙烯換算值。在基於該方法而進行的測定中，例如使用在TOSOH CORPORATION製造的高速GPC裝置“HLC-8120GPC”上依次連接高速色譜柱“TSK guard column H XL-H”、“TSK Gel GMH XL”、“TSK Gel G2000 H XL”(以上均為TOSOH CORPORATION製造)而成的設備，在色譜柱溫度為40℃、進液速度為1.0mL/分鐘的條件下，將示差折射率計作為檢測器而進行測定。 In addition, in this specification, unless otherwise indicated, "weight average molecular weight" means the polystyrene conversion value measured by the gel permeation chromatography (GPC) method. In the measurement based on this method, for example, high-speed chromatography columns "TSK guard column H XL -H", "TSK Gel GMH XL ", "TSK Gel GMH XL ", "TSK Gel G2000 H XL " (all of the above are manufactured by TOSOH CORPORATION) was used for measurement using a differential refractometer as a detector under conditions of a column temperature of 40°C and a liquid feed rate of 1.0mL/min.

作為丙烯酸樹脂，例如可列舉出由(甲基)丙烯酸酯單體與衍生自(甲基)丙烯酸衍生物的結構單元構成的(甲基)丙烯酸酯共聚物。其中，作為(甲基)丙烯酸酯單體，可優選列舉出烷基的碳原子數為1~18的(甲基)丙烯酸烷基酯，具體可列舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯等。此外，作為(甲基)丙烯酸衍生物，例如可列舉出(甲基)丙烯酸、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸羥基乙酯等。As an acrylic resin, the (meth)acrylate copolymer which consists of a (meth)acrylate monomer and the structural unit derived from a (meth)acrylic acid derivative is mentioned, for example. Among them, as the (meth)acrylate monomer, preferably an alkyl (meth)acrylate having an alkyl group of 1 to 18 carbon atoms, specifically methyl (meth)acrylate, (meth)acrylate, base) ethyl acrylate, propyl (meth)acrylate, butyl (meth)acrylate, etc. Moreover, as a (meth)acrylic acid derivative, (meth)acrylic acid, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate, etc. are mentioned, for example.

在本實施方案中，優選使用甲基丙烯酸縮水甘油酯等向丙烯酸樹脂中引入縮水甘油基。引入了縮水甘油基的丙烯酸樹脂與後述的作為熱固性成分的環氧樹脂的相容性得到提高，有易於得到具有穩定性能的保護膜形成膜的傾向。此外，在本實施方案中，為了控制對工件的黏合性或黏著物性，優選使用丙烯酸羥基乙酯等向丙烯酸樹脂中引入羥基。In the present embodiment, glycidyl methacrylate or the like is preferably used to introduce glycidyl groups into the acrylic resin. The compatibility of the glycidyl group-introduced acrylic resin with the epoxy resin as a thermosetting component described later tends to be improved, and a protective film-forming film having stable performance tends to be easily obtained. Furthermore, in the present embodiment, in order to control adhesiveness or stickiness to a workpiece, it is preferable to introduce hydroxyl groups into the acrylic resin using hydroxyethyl acrylate or the like.

丙烯酸樹脂的玻璃化轉變溫度優選為-70℃~40℃、-35℃~35℃、-20℃~30℃、-10℃~25℃、-5℃~20℃。藉由使丙烯酸樹脂的玻璃化轉變溫度在上述範圍內，保護膜形成膜的黏性適度提高，同時保護膜形成膜對工件的黏著力得到提高，且保護膜對工件的黏合力適度提高。The glass transition temperature of the acrylic resin is preferably -70°C to 40°C, -35°C to 35°C, -20°C to 30°C, -10°C to 25°C, and -5°C to 20°C. When the glass transition temperature of the acrylic resin is within the above range, the viscosity of the protective film-forming film is moderately improved, and at the same time, the adhesive force of the protective film-forming film to the workpiece is improved, and the adhesive force of the protective film to the workpiece is moderately improved.

當丙烯酸樹脂具有m種(m為2以上的整數)結構單元時，能夠藉由以下方式計算出該丙烯酸樹脂的玻璃化轉變溫度。即，分別對衍生出丙烯酸樹脂中的結構單元的m種單體依次賦予1至m的任一不重複的序號而將其命名為“單體m”時，能夠使用以下所示的Fox公式計算出丙烯酸樹脂的玻璃化轉變溫度(Tg)。 [數學式1]

Figure 02_image001
式中，Tg為丙烯酸樹脂的玻璃化轉變溫度；m為2以上的整數；Tg k為單體m的均聚物的玻璃化轉變溫度；W k為丙烯酸樹脂中的衍生自單體m的結構單元m的質量分數，其中，W k滿足下式。 [數學式2]
Figure 02_image003
式中，m及W k與所述m及W k相同。 When the acrylic resin has m types (m is an integer greater than or equal to 2) of structural units, the glass transition temperature of the acrylic resin can be calculated in the following manner. That is, when the m types of monomers derived from the structural units in the acrylic resin are sequentially assigned any non-repeating serial number from 1 to m and named as "monomer m", it can be calculated using the Fox formula shown below The glass transition temperature (Tg) of the acrylic resin. [mathematical formula 1]
Figure 02_image001
In the formula, Tg is the glass transition temperature of the acrylic resin; m is an integer above 2; Tg k is the glass transition temperature of the homopolymer of the monomer m; W k is the structure derived from the monomer m in the acrylic resin The mass fraction of unit m, where W k satisfies the following formula. [mathematical formula 2]
Figure 02_image003
In the formula, m and W k are the same as the aforementioned m and W k .

作為Tg k，可使用高分子資料手冊、黏著手冊或聚合物手冊(Polymer Handbook)等中所記載的值。例如，丙烯酸甲酯的均聚物的Tg k為10℃、丙烯酸正丁酯的均聚物的Tg k為-54℃、甲基丙烯酸甲酯的均聚物的Tg k為105℃、丙烯酸2-羥基乙酯的均聚物的Tg k為-15℃、甲基丙烯酸縮水甘油酯的均聚物的Tg k為41℃、丙烯酸2-乙基己酯的均聚物的Tg k為-70℃。 As Tg k , a value described in a polymer data handbook, an adhesive handbook, or a polymer handbook (Polymer Handbook), etc. can be used. For example, the Tg k of the homopolymer of methyl acrylate is 10°C, the Tg k of the homopolymer of n-butyl acrylate is -54°C, the Tg k of the homopolymer of methyl methacrylate is 105°C, and the Tg k of the homopolymer of acrylic acid 2 The Tg k of the homopolymer of -hydroxyethyl ester is -15°C, the Tg k of the homopolymer of glycidyl methacrylate is 41°C, and the Tg k of the homopolymer of 2-ethylhexyl acrylate is -70 ℃.

將保護膜形成膜用組合物的總重量設為100質量份時的聚合物成分的含量優選為5~80質量份、8~70質量份、10~60質量份、12~55質量份、14~50質量份、15~45質量份。藉由使聚合物成分的含量在上述範圍內，則易於控制保護膜形成膜的黏性。The content of the polymer component when the total weight of the composition for forming a protective film is 100 parts by mass is preferably 5 to 80 parts by mass, 8 to 70 parts by mass, 10 to 60 parts by mass, 12 to 55 parts by mass, 14 parts by mass, ~50 parts by mass, 15~45 parts by mass. By making content of a polymer component into the said range, it becomes easy to control the viscosity of a protective film forming film.

(5.1.2 熱固性成分) 固化性成分(B)藉由使保護膜形成膜固化而形成硬質的保護膜。作為固化性成分，能夠使用熱固性成分、能量射線固化性成分或這些成分的混合物。當藉由照射能量射線而進行固化時，本實施方案的保護膜形成膜的透光率因含有後述的填充材料及著色劑等而下降。因此，例如當保護膜形成膜的厚度變厚時，能量射線固化容易變得不充分。 (5.1.2 Thermosetting components) The curable component (B) forms a hard protective film by hardening the protective film forming film. As the curable component, a thermosetting component, an energy ray-curable component, or a mixture of these components can be used. When curing is performed by irradiating energy rays, the light transmittance of the protective film-forming film according to this embodiment decreases due to the inclusion of a filler, a colorant, and the like described later. Therefore, for example, when the thickness of the protective film forming film becomes thicker, energy ray curing tends to become insufficient.

另一方面，熱固性的保護膜形成膜即使其厚度變厚，也可藉由加熱而充分固化，因此能夠形成保護性能高的保護膜。此外，能夠藉由使用加熱爐等通常的加熱工具而將多個保護膜形成膜一併加熱，從而使其熱固化。On the other hand, even if the thickness of a thermosetting protective film-forming film becomes thick, it can fully harden by heating, Therefore The protective film with high protective performance can be formed. In addition, a plurality of protective film forming films can be collectively heated and thermally cured using common heating tools such as a heating furnace.

因此，在本實施方案中，期望固化性成分為熱固性。即，本實施方案的保護膜形成膜優選為熱固性。Therefore, in the present embodiment, it is desirable that the curable component is thermosetting. That is, the protective film-forming film of the present embodiment is preferably thermosetting.

可藉由以下方法判斷保護膜形成膜是否為熱固性。首先，將常溫(23℃)的保護膜形成膜加熱至大於常溫的溫度，接著冷卻至常溫，從而製成加熱·冷卻後的保護膜形成膜。接著，在相同溫度下對加熱·冷卻後的保護膜形成膜的硬度與加熱前的保護膜形成膜的硬度進行比較，此時在加熱·冷卻後的保護膜形成膜更硬的情況下，判斷該保護膜形成膜為熱固性。Whether or not the protective film forming film is thermosetting can be judged by the following method. First, a protective film forming film at normal temperature (23° C.) was heated to a temperature higher than normal temperature, and then cooled to normal temperature to prepare a heated and cooled protective film forming film. Next, at the same temperature, the hardness of the protective film forming film after heating and cooling is compared with the hardness of the protective film forming film before heating. At this time, when the protective film forming film after heating and cooling is harder, it is judged that This protective film forming film is thermosetting.

作為熱固性成分，例如優選使用環氧樹脂、熱固性聚醯亞胺樹脂、不飽和聚酯樹脂及它們的混合物。另外，熱固性聚醯亞胺樹脂是藉由進行熱固化而形成聚醯亞胺樹脂的、低分子量且低黏性的單體或前驅體聚合物的統稱。熱固性聚醯亞胺樹脂的非限制性的具體實例記載於例如日本纖維學會雜誌“纖維與工業”(繊維學會誌「繊維と工業」), Vol.50, No.3 (1994), P106-P118中。As the thermosetting component, for example, epoxy resins, thermosetting polyimide resins, unsaturated polyester resins, and mixtures thereof are preferably used. In addition, the thermosetting polyimide resin is a generic term for low molecular weight and low viscosity monomers or precursor polymers that form polyimide resins by thermal curing. Non-limiting specific examples of thermosetting polyimide resins are described in, for example, the Journal of the Textile Society of Japan "Fiber and Industry" (Journal of the Japan Textile Society "繊维と工业"), Vol.50, No.3 (1994), P106-P118 middle.

作為熱固性成分的環氧樹脂具有受熱時發生三維網狀化從而形成牢固的覆膜的性質。作為這樣的環氧樹脂，可使用公知的各種環氧樹脂。在本實施方案中，環氧樹脂的分子量(式量)優選為300以上且小於50000、300以上且小於10000、300以上且小於5000、300以上且小於3000。此外，環氧樹脂的環氧當量優選為50~5000g/eq，更優選為100~2000g/eq，進一步優選為150~1000g/eq。Epoxy resin, which is a thermosetting component, has the property of forming a three-dimensional network when heated to form a strong coating. As such an epoxy resin, various well-known epoxy resins can be used. In this embodiment, the molecular weight (formula weight) of the epoxy resin is preferably 300 to less than 50,000, 300 to less than 10,000, 300 to less than 5,000, and 300 to less than 3,000. In addition, the epoxy equivalent of the epoxy resin is preferably 50 to 5000 g/eq, more preferably 100 to 2000 g/eq, and still more preferably 150 to 1000 g/eq.

作為這樣的環氧樹脂，具體而言可列舉出雙酚A、雙酚F、間苯二酚、苯基酚醛清漆、甲酚酚醛清漆等酚類的縮水甘油醚；丁二醇、聚乙二醇、聚丙二醇等醇類的縮水甘油醚；鄰苯二甲酸、間苯二甲酸、四氫鄰苯二甲酸等羧酸的縮水甘油醚；用縮水甘油基取代苯胺異氰脲酸酯等的與氮原子鍵合的活性氫而成的縮水甘油基型或烷基縮水甘油基型的環氧樹脂；如二氧化乙烯基環己烯、3,4-環氧環己基甲基-3,4-二環己烷羧酸酯、2-(3,4-環氧)環己基-5,5-螺(3,4-環氧)環己烷-間二氧六環等那樣，藉由例如將分子內的碳碳雙鍵氧化而引入了環氧基的所謂的脂環型環氧化物。除此以外，還可以使用具有聯苯骨架、雙環己二烯骨架、萘骨架等的環氧樹脂。Specific examples of such epoxy resins include glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol, phenyl novolac, and cresol novolak; Glycidyl ethers of alcohols such as alcohol and polypropylene glycol; glycidyl ethers of carboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidyl substituted aniline isocyanurate, etc. Glycidyl-type or alkylglycidyl-type epoxy resins with active hydrogen bonded to nitrogen atoms; such as vinyl dioxide cyclohexene, 3,4-epoxycyclohexylmethyl-3,4- Dicyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-dioxane, etc., by, for example, A so-called alicyclic epoxide in which an epoxy group is introduced by oxidation of the carbon-carbon double bond in the molecule. In addition, epoxy resins having a biphenyl skeleton, a bicyclohexadiene skeleton, a naphthalene skeleton, and the like can also be used.

當使用熱固性成分作為固化性成分(B)時，優選同時使用作為助劑的固化劑(C)。作為針對環氧樹脂的固化劑，優選熱活性型潛伏性環氧樹脂固化劑。“熱活性型潛伏性環氧樹脂固化劑”是指，在常溫(23℃)下不易與環氧樹脂反應、藉由加熱至某溫度以上而活化從而與環氧樹脂反應的類型的固化劑。熱活性型潛伏性環氧樹脂固化劑的活化方法有：藉由基於加熱的化學反應而產生活性物質(陰離子、陽離子)的方法；在常溫左右穩定地分散於環氧樹脂中而在高溫下與環氧樹脂相容·溶解，從而引發固化反應的方法；利用分子篩密封型的固化劑在高溫下進行洗脫而引發固化反應的方法；利用微膠囊的方法等。When a thermosetting component is used as the curable component (B), it is preferable to use a curing agent (C) as an auxiliary agent together. As the curing agent for the epoxy resin, a thermally active latent epoxy resin curing agent is preferable. "Heat-activated latent epoxy resin curing agent" refers to a type of curing agent that does not easily react with epoxy resin at normal temperature (23° C.) and is activated by heating above a certain temperature to react with epoxy resin. The activation methods of thermally active latent epoxy resin curing agents include: the method of generating active substances (anions, cations) through a chemical reaction based on heating; Epoxy resins are compatible and dissolved, thereby initiating a curing reaction; a method of eluting a molecular sieve-sealed curing agent at a high temperature to initiate a curing reaction; a method of using microcapsules, etc.

在所例示的方法中，優選在常溫左右穩定地分散於環氧樹脂中而在高溫下與環氧樹脂相容·溶解從而引發固化反應的方法。Among the exemplified methods, it is preferable to stably disperse in the epoxy resin at about room temperature, and to be compatible and dissolved with the epoxy resin at high temperature to initiate a curing reaction.

作為熱活性型潛伏性環氧樹脂固化劑的具體實例，可列舉出各種鎓鹽、二元酸二醯肼化合物、二氰二胺、胺加合物(amine adduct)固化劑、咪唑化合物等高熔點活性氫化合物等。這些熱活性型潛伏性環氧樹脂固化劑可以單獨使用一種，或者也可以組合使用兩種以上。在本實施方案中，特別優選二氰二胺。Specific examples of heat-activated latent epoxy resin curing agents include various onium salts, dibasic acid dihydrazide compounds, dicyandiamide, amine adduct (amine adduct) curing agents, imidazole compounds, etc. Melting point active hydrogen compounds, etc. These thermoactive latent epoxy resin curing agents may be used alone or in combination of two or more. In this embodiment, dicyandiamine is particularly preferred.

此外，作為針對環氧樹脂的固化劑，還優選酚醛樹脂。作為酚醛樹脂，可無特別限制地使用烷基酚、多元酚、萘酚等酚類與醛類的縮合物等。具體而言，可以使用苯酚酚醛清漆樹脂、鄰甲酚酚醛清漆樹脂、對甲酚酚醛清漆樹脂、叔丁基苯酚酚醛清漆樹脂、雙環戊二烯甲酚樹脂、聚對乙烯基苯酚樹脂、雙酚A型酚醛清漆樹脂或它們的改性物等。In addition, as a curing agent for epoxy resins, phenolic resins are also preferable. As the phenolic resin, condensates of phenols such as alkylphenols, polyhydric phenols, and naphthols and aldehydes can be used without particular limitation. Specifically, phenol novolak resins, o-cresol novolac resins, p-cresol novolak resins, tert-butylphenol novolac resins, dicyclopentadiene cresol resins, poly-p-vinylphenol resins, bisphenol Type A novolak resins or their modified products, etc.

這些酚醛樹脂中所含的酚羥基易於藉由加熱而與上述環氧樹脂的環氧基進行加成反應，從而能夠形成抗衝擊性高的固化物。The phenolic hydroxyl group contained in these phenolic resins is easy to add reaction with the epoxy group of the said epoxy resin by heating, and can form the hardened|cured material with high impact resistance.

相對於100質量份的環氧樹脂，固化劑(C)的含量優選為0.01~30質量份、0.1~20質量份、0.2~15質量份、0.3~10質量份。藉由將固化劑(C)的含量設為上述範圍，保護膜的網狀結構變得緻密，因此易於得到作為保護膜的保護工件的性能。The content of the curing agent (C) is preferably 0.01 to 30 parts by mass, 0.1 to 20 parts by mass, 0.2 to 15 parts by mass, or 0.3 to 10 parts by mass relative to 100 parts by mass of the epoxy resin. Since the network structure of a protective film becomes dense by making content of a hardening|curing agent (C) into the said range, it becomes easy to acquire the performance which protects a workpiece|work as a protective film.

使用二氰二胺作為固化劑(C)時，優選進一步同時使用固化促進劑(D)。作為固化促進劑，例如優選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(一個以上的氫原子被除氫原子以外的基團取代的咪唑)。其中，特別優選2-苯基-4,5-二羥基甲基咪唑。When dicyandiamine is used as the curing agent (C), it is preferable to further use a curing accelerator (D) together. As curing accelerators, for example, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- Imidazoles such as 4-methyl-5-hydroxymethylimidazole (imidazoles in which one or more hydrogen atoms are replaced by groups other than hydrogen atoms). Among them, 2-phenyl-4,5-dihydroxymethylimidazole is particularly preferable.

相對於100質量份的環氧樹脂，固化促進劑的含量優選為0.01~30質量份、0.1~20質量份、0.2~15質量份、0.3~10質量份。藉由將固化促進劑(D)的含量設為上述範圍，保護膜的網狀結構變得緻密，因此易於得到作為保護膜的保護工件的性能。The content of the curing accelerator is preferably 0.01 to 30 parts by mass, 0.1 to 20 parts by mass, 0.2 to 15 parts by mass, or 0.3 to 10 parts by mass relative to 100 parts by mass of the epoxy resin. Since the network structure of a protective film becomes dense by making content of a hardening accelerator (D) into the said range, it becomes easy to acquire the performance which protects a workpiece|work as a protective film.

將保護膜形成膜用組合物的總重量設為100質量份時的熱固性成分及固化劑的合計含量，優選為3~80質量份、5~60質量份、7~50質量份、9~40質量份、10~30質量份。若以該比例摻合熱固性成分與固化劑，則在固化前表現出適度的黏性，並能夠穩定地進行貼附操作。此外，在固化後，易於得到作為保護膜的保護工件的性能。The total content of the thermosetting component and the curing agent when the total weight of the composition for forming a protective film is 100 parts by mass is preferably 3 to 80 parts by mass, 5 to 60 parts by mass, 7 to 50 parts by mass, or 9 to 40 parts by mass. parts by mass, 10 to 30 parts by mass. If the thermosetting component and the curing agent are blended in this ratio, it will exhibit moderate viscosity before curing, and it will be possible to perform the sticking operation stably. In addition, after curing, the property of protecting workpieces as a protective film is easily obtained.

(5.1.3 能量射線固化性成分) 當固化性成分(B)為能量射線固化性成分時，能量射線固化性成分優選未固化，優選具有黏著性，更優選未固化且具有黏著性。 (5.1.3 Energy ray curable components) When the curable component (B) is an energy ray curable component, the energy ray curable component is preferably uncured, preferably has adhesiveness, more preferably is uncured and has adhesiveness.

能量射線固化性成分是藉由照射能量射線而固化的成分，也是用於對保護膜形成膜賦予成膜性或柔性等的成分。The energy ray-curable component is a component that is cured by irradiating an energy ray, and is also a component for imparting film-forming properties, flexibility, and the like to a protective film-forming film.

作為能量射線固化性成分，例如優選具有能量射線固化性基團的化合物。作為這樣的化合物，可列舉出公知的具有能量射線固化性基團的化合物。As the energy ray curable component, for example, a compound having an energy ray curable group is preferable. As such a compound, the compound which has a well-known energy-ray curable group is mentioned.

(5.1.4 填充材料) 藉由使保護膜形成膜含有填充材料(E)，變得易於調整將保護膜形成膜製成保護膜而得到的保護膜的熱膨脹係數，藉由使該熱膨脹係數接近於工件的熱膨脹係數，使用保護膜形成膜而得到的帶保護膜的晶片的黏合可靠性進一步得以提高。此外，藉由使保護膜形成膜含有填充材料(E)，可得到硬質的保護膜，能夠進一步降低保護膜的吸濕率，帶保護膜的晶片的黏合可靠性會進一步得以提高。 (5.1.4 Filling material) By making the protective film forming film contain the filler (E), it becomes easy to adjust the thermal expansion coefficient of the protective film obtained by making the protective film forming film into a protective film, and by making the thermal expansion coefficient close to the thermal expansion coefficient of the workpiece, use The bonding reliability of the wafer with a protective film obtained by forming a protective film is further improved. In addition, by making the protective film forming film contain the filler (E), a hard protective film can be obtained, the moisture absorption rate of the protective film can be further reduced, and the bonding reliability of the wafer with the protective film can be further improved.

填充材料(E)可以為有機填充材料及無機填充材料中的任一種，但從高溫下的形狀穩定性的角度出發，優選為無機填充材料。The filler (E) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler from the viewpoint of shape stability at high temperature.

作為優選的無機填充材料，例如可列舉出二氧化矽、氧化鋁、滑石、碳酸鈣、紅氧化鐵、碳化矽、氮化硼等的粉末；將這些無機填充材料球形化而成的珠子；這些無機填充材料的表面改性物；這些無機填充材料的單晶纖維；玻璃纖維等。其中，優選二氧化矽及進行了表面改性的二氧化矽。進行了表面改性的二氧化矽優選利用偶聯劑進行表面改性，更優選利用矽烷偶聯劑進行表面改性。As preferred inorganic fillers, for example, powders of silica, alumina, talc, calcium carbonate, red iron oxide, silicon carbide, boron nitride, etc.; beads obtained by spheroidizing these inorganic fillers; these Surface modification of inorganic filler materials; single crystal fibers of these inorganic filler materials; glass fibers, etc. Among them, silicon dioxide and surface-modified silicon dioxide are preferable. The surface-modified silica is preferably surface-modified with a coupling agent, and more preferably surface-modified with a silane coupling agent.

填充材料的平均粒徑優選為0.02~10μm、0.05~5μm、0.10~3μm。The average particle size of the filler is preferably 0.02 to 10 μm, 0.05 to 5 μm, or 0.10 to 3 μm.

藉由將填充材料的平均粒徑的範圍設為上述範圍，保護膜形成膜用組合物的操作性變得良好。其結果，易於使保護膜形成膜用組合物及保護膜形成膜的質量穩定。By making the range of the average particle diameter of a filler into the said range, the handleability of the composition for protective film forming films becomes favorable. As a result, it becomes easy to stabilize the quality of the composition for protective film forming films and a protective film forming film.

另外，在本說明書中，只要沒有特別說明，則“平均粒徑”是指，藉由雷射衍射散射法而求出的細微性分佈曲線中的累計值為50%時的粒徑(D50)的值。In addition, in this specification, unless otherwise specified, the "average particle diameter" refers to the particle diameter (D50) when the cumulative value in the fineness distribution curve obtained by the laser diffraction scattering method is 50%. value.

將保護膜形成膜用組合物的總重量設為100質量份時的填充材料的含量優選為15~80質量份、30~75質量份、40~70質量份、45~65質量份。The content of the filler when the total weight of the composition for forming a protective film is 100 parts by mass is preferably 15 to 80 parts by mass, 30 to 75 parts by mass, 40 to 70 parts by mass, and 45 to 65 parts by mass.

藉由將填充材料的含量的下限值設為上述值，使用保護膜形成膜而得到的帶保護膜的晶片的黏合可靠性得到進一步提高。此外，藉由將填充材料的含量的上限值設為上述值，保護膜形成膜對工件的的黏著力得到提高，保護膜對工件的黏合力適度提高。By making the lower limit of the content of the filler into the above-mentioned value, the bonding reliability of the wafer with a protective film obtained by forming a film using a protective film is further improved. Moreover, by making the upper limit of content of a filler into the said value, the adhesive force of a protective film forming film to a workpiece improves, and the adhesive force of a protective film to a workpiece improves moderately.

(5.1.5 偶聯劑) 保護膜形成膜優選含有偶聯劑(F)。藉由含有偶聯劑，在保護膜形成膜固化後，能夠在不損傷保護膜的耐熱性的情況下，提高保護膜與工件之間的黏合性，同時還能夠提高耐水性(耐濕熱性)。作為偶聯劑，從其通用性與成本優勢的角度出發，優選矽烷偶聯劑。 (5.1.5 Coupling agent) The protective film forming film preferably contains a coupling agent (F). By containing a coupling agent, after the protective film forming film is cured, the adhesion between the protective film and the workpiece can be improved without impairing the heat resistance of the protective film, and water resistance (moisture and heat resistance) can also be improved. . As the coupling agent, silane coupling agent is preferred in view of its versatility and cost advantages.

作為矽烷偶聯劑，例如可列舉出γ-縮水甘油醚氧基丙基三甲氧基矽烷、γ-縮水甘油醚氧基丙基甲基二乙氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-(甲基丙烯醯氧基丙基)三甲氧基矽烷、γ-氨基丙基三甲氧基矽烷、N-6-(氨基乙基)-γ-氨基丙基三甲氧基矽烷、N-6-(氨基乙基)-γ-氨基丙基甲基二乙氧基矽烷、N-苯基-γ-氨基丙基三甲氧基矽烷、γ-脲基丙基三乙氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-巰基丙基甲基二甲氧基矽烷、雙(3-三乙氧基矽基丙基)四硫化物、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、咪唑矽烷等。這些矽烷偶聯劑可以單獨使用一種，或者也可以混合使用兩種以上。Examples of silane coupling agents include γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropylmethyldiethoxysilane, β-(3,4-epoxy Cyclohexyl)ethyltrimethoxysilane, γ-(methacryloxypropyl)trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)-γ-amino Propyltrimethoxysilane, N-6-(aminoethyl)-γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyl Triethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane Oxysilane, Methyltriethoxysilane, Vinyltrimethoxysilane, Vinyltriacetyloxysilane, Imidazolesilane, etc. These silane coupling agents may be used alone or in combination of two or more.

將保護膜形成膜用組合物的總重量設為100質量份時的偶聯劑的含量優選為0.01~20質量份、0.1~10質量份、0.2~5質量份、0.3~3質量份。The content of the coupling agent when the total weight of the composition for forming a protective film is 100 parts by mass is preferably 0.01 to 20 parts by mass, 0.1 to 10 parts by mass, 0.2 to 5 parts by mass, or 0.3 to 3 parts by mass.

(5.1.6 著色劑) 保護膜形成膜優選含有著色劑(G)。由此，晶片等工件的加工物的背面被遮蓋，因此能夠遮罩電子設備內產生的各種電磁波，從而能夠減少晶片等工件的加工物的故障。此外，雷射打標的辨認性會進一步提高。 (5.1.6 Colorants) It is preferable that a protective film forming film contains a coloring agent (G). Thereby, since the back surface of workpieces such as wafers is covered, various electromagnetic waves generated in electronic equipment can be shielded, and failures of workpieces such as wafers can be reduced. In addition, the visibility of laser marking will be further improved.

作為著色劑(G)，例如能夠使用有機類顏料、有機類染料、無機類顏料等公知的著色劑。在本實施方案中，優選無機類顏料。As the colorant (G), known colorants such as organic pigments, organic dyes, and inorganic pigments can be used, for example. In this embodiment, inorganic-based pigments are preferred.

作為無機類顏料，例如可列舉出炭黑、鈷類色素、鐵類色素、鉻類色素、鈦類色素、釩類色素、鋯類色素、鉬類色素、釕類色素、鉑類色素、ITO(氧化銦錫)類色素、ATO(氧化銻錫)類色素等。其中，特別優選使用炭黑。藉由炭黑能夠遮罩寬波長範圍的電磁波。Examples of inorganic pigments 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, ITO ( Indium tin oxide) pigments, ATO (antimony tin oxide) pigments, etc. Among them, carbon black is particularly preferably used. Electromagnetic waves in a wide wavelength range can be shielded by carbon black.

保護膜形成膜中的著色劑(特別是炭黑)的摻合量因保護膜形成膜的厚度而異，例如保護膜形成膜的厚度為20μm時，將保護膜形成膜用組合物的總重量設為100質量份時的著色劑的含量優選為0.01~10質量份、0.03~7質量份、0.05~4質量份。The blending amount of the colorant (especially carbon black) in the protective film-forming film varies depending on the thickness of the protective film-forming film. For example, when the thickness of the protective film-forming film is 20 μm, the total weight of the composition for protective film-forming film The content of the coloring agent is preferably 0.01 to 10 parts by mass, 0.03 to 7 parts by mass, or 0.05 to 4 parts by mass per 100 parts by mass.

著色劑(特別是炭黑)的平均粒徑優選為1~500nm、3~100nm、5~50nm。若著色劑的平均粒徑在上述範圍內，則易於將透光率控制在所需範圍內。The average particle diameter of the colorant (especially carbon black) is preferably 1 to 500 nm, 3 to 100 nm, or 5 to 50 nm. When the average particle diameter of the coloring agent is within the above-mentioned range, it is easy to control the light transmittance within the desired range.

(5.1.7 其他添加劑) 在不損害本發明的效果的範圍內，保護膜形成膜用組合物可以含有作為其他添加劑的例如光聚合引發劑、交聯劑、增塑劑、抗靜電劑、抗氧化劑、吸雜劑、增黏劑、剝離劑等。 (5.1.7 Other additives) The protective film-forming film composition may contain, as other additives, photopolymerization initiators, crosslinking agents, plasticizers, antistatic agents, antioxidants, gettering agents, Adhesives, strippers, etc.

(6. 夾具用黏著劑層) 作為構成夾具用黏著劑層的黏著劑，優選具有所需的黏著力及再剝離性的黏著劑，例如能夠使用丙烯酸類黏著劑、橡膠類黏著劑、矽酮類黏著劑、氨基甲酸酯類黏著劑、聚酯類黏著劑、聚乙烯基醚類黏著劑等。其中，優選與環形框架等夾具的密合性高、能夠在切割步驟等中有效地抑制保護膜形成用複合片從環形框架等上剝離的丙烯酸類黏著劑。另外，還可以在夾具用黏著劑層的厚度方向中夾有作為芯材的基材。 (6. Adhesive layer for jig) As the adhesive constituting the adhesive layer for jigs, adhesives having required adhesive force and re-peelability are preferable, for example, acrylic adhesives, rubber adhesives, silicone adhesives, and urethane adhesives can be used. adhesives, polyester adhesives, polyvinyl ether adhesives, etc. Among them, an acrylic adhesive that has high adhesion to a jig such as a ring frame and can effectively suppress peeling of the protective film-forming composite sheet from the ring frame or the like in a cutting step or the like is preferable. Moreover, you may interpose the base material which is a core material in the thickness direction of the adhesive agent layer for jigs.

從對環形框架等夾具的黏合性的角度出發，夾具用黏著劑層的厚度優選為5~200μm，特別優選為10~100μm。From the viewpoint of adhesiveness to jigs such as ring frames, the thickness of the adhesive layer for jigs is preferably 5 to 200 μm, particularly preferably 10 to 100 μm.

(7. 剝離膜) 剝離膜優選配置於支撐片的黏著劑層的表面及保護膜形成用複合片的保護膜形成膜的表面。剝離膜可以由一層(單層)或兩層以上的基材構成，從控制剝離性的角度出發，還可以對基材的表面進行剝離處理。即，可以對基材的表面進行改性，也可以在基材的表面上形成並非來源於基材的材料(剝離劑層)。 (7. Peel film) The release film is preferably disposed on the surface of the adhesive layer of the support sheet and the surface of the protective film forming film of the protective film forming composite sheet. The release film may be composed of one layer (single layer) or two or more layers of base materials, and the surface of the base material may be subjected to a release treatment from the viewpoint of controlling release properties. That is, the surface of the substrate may be modified, or a material not derived from the substrate (release agent layer) may be formed on the surface of the substrate.

作為基材，只要是能夠支撐保護膜形成膜直至將保護膜形成膜貼附於工件時為止的材料，則沒有特別限定，通常由以樹脂類的材料為主要材料的膜構成。在本實施方案中，從環境安全性、成本等角度出發，優選聚對苯二甲酸乙二醇酯膜。基材也可以含有著色劑、阻燃劑、增塑劑、抗靜電劑、潤滑劑、填料等各種添加劑。The substrate is not particularly limited as long as it can support the protective film-forming film until the protective film-forming film is attached to the workpiece, and is usually composed of a film mainly composed of a resin material. In this embodiment, a polyethylene terephthalate film is preferable from the viewpoints of environmental safety, cost, and the like. The substrate may also contain various additives such as colorants, flame retardants, plasticizers, antistatic agents, lubricants, and fillers.

剝離劑層可藉由在基材的一個面上塗佈包含剝離劑層用組合物的塗佈劑，然後使該塗膜乾燥及固化而得到。剝離劑層用組合物只要是能夠給基材賦予與保護膜形成膜之間的剝離性的材料，則沒有特別限制。在本實施方案中，剝離劑層用組合物，例如優選醇酸類脫模劑、矽酮類脫模劑、氟類脫模劑、不飽和聚酯類脫模劑、聚烯烴類脫模劑、石蠟類脫模劑，其中，優選矽酮類脫模劑。The release agent layer can be obtained by applying a coating agent containing a composition for a release agent layer on one surface of a substrate, and drying and curing the coating film. The release agent layer composition is not particularly limited as long as it is a material that can impart releasability to the base material and the protective film forming film. In this embodiment, the release agent layer composition is preferably, for example, an alkyd release agent, a silicone release agent, a fluorine release agent, an unsaturated polyester release agent, a polyolefin release agent, Among the paraffin-based release agents, silicone-based release agents are preferred.

剝離膜的厚度沒有特別限制，但優選為15~100μm，進一步優選為25~80μm，更優選為35~60μm。The thickness of the release film is not particularly limited, but is preferably 15 to 100 μm, more preferably 25 to 80 μm, and still more preferably 35 to 60 μm.

(8. 支撐片及保護膜形成用複合片的製造方法) 支撐片例如可藉由以下方法製造。首先，準備支撐片的基材。基材可藉由下述方法而得到，即在將原料組合物熔融混煉並利用擠出機擠出片狀的基材時，使基材在軟質的狀態下與經過印花加工等規定的凹凸處理的輥接觸，從而形成上述的表面性狀。此外，也可以使作為原料的基材藉由經過印花加工等規定的凹凸處理的輥與未經凹凸處理的輥之間，將形成在輥上的凹凸轉印至該基材上，從而得到具有上述表面性狀的基材。 (8. Manufacturing method of support sheet and protective film forming composite sheet) A support sheet can be manufactured by the following method, for example. First, the base material of the support sheet is prepared. The base material can be obtained by a method in which the material composition is melt-kneaded and the sheet-like base material is extruded by an extruder, and the base material is in a soft state with predetermined irregularities such as printing processing. The treated rolls are brought into contact so as to form the above-mentioned surface texture. In addition, it is also possible to transfer the unevenness formed on the roll to the base material by passing the base material as a raw material between a roll that has undergone a predetermined uneven treatment such as printing processing and a roll that has not been unevenly treated, thereby obtaining a Substrates with the above-mentioned surface texture.

作為規定的凹凸處理，例如可例示出磨石研磨；液體珩磨處理等濕噴射處理(wet blasting)；噴砂處理等乾噴射處理(dry blasting)。磨石研磨是對輥的表面進行研磨的處理，通常為使輥的表面平滑的處理。濕噴射處理及乾噴射處理是對輥的表面噴射研磨材料，從而使輥的表面狀態發生變化的處理，通常為在輥的表面形成凹凸的處理。凹凸的大小可藉由改變研磨材料的材質或粒徑等而進行控制。Examples of predetermined unevenness processing include grinding stone grinding; wet blasting such as liquid honing; and dry blasting such as sand blasting. Stone grinding is a process of grinding the surface of a roll, and is usually a process of smoothing the surface of the roll. The wet blasting treatment and the dry blasting treatment are treatments for changing the surface state of the roll by spraying an abrasive on the surface of the roll, and are usually a process for forming unevenness on the surface of the roll. The size of the unevenness can be controlled by changing the material or particle size of the abrasive.

因此，藉由將使表面平滑的處理與形成凹凸的處理進行組合，能夠得到表面經過規定的凹凸處理的輥。Therefore, by combining the treatment for smoothing the surface and the treatment for forming unevenness, a roller having a predetermined unevenness treatment on the surface can be obtained.

接著，製備構成黏著劑層的黏著劑組合物或用溶劑稀釋了該黏著劑組合物的組合物(將所述兩種組合物稱為“塗佈劑”)。使用輥塗機、刮刀塗佈機、輥刀塗佈機、氣刀塗佈機、模塗機、棒塗機、凹版塗佈機、幕塗機等塗佈機，將所得到的塗佈劑塗佈於第一剝離膜的剝離面，並根據需要使其乾燥，從而在第一剝離膜上形成黏著劑層。接著，將黏著劑層的露出面與上述所準備的基材的不具有上述表面性狀的主面貼合，從而製作在黏著劑層的表面上具有第一剝離膜的支撐片。Next, an adhesive composition constituting the adhesive layer or a composition obtained by diluting the adhesive composition with a solvent (these two compositions are referred to as "coating agent") is prepared. The obtained coating agent is coated with a coating machine such as a roll coater, a knife coater, a roll coater, an air knife coater, a die coater, a rod coater, a gravure coater, or a curtain coater. Apply to the peeling surface of the 1st peeling film, and if necessary, make it dry, and form an adhesive layer on the 1st peeling film. Next, the exposed surface of the adhesive layer was bonded to the main surface of the prepared base material that did not have the above-mentioned surface texture, thereby producing a support sheet having a first release film on the surface of the adhesive layer.

此處，。當黏著劑層由能量射線固化性黏著劑構成時，可以在該階段對黏著劑層照射能量射線從而使黏著劑層固化，也可以在與保護膜形成膜層疊後使黏著劑層固化。此外，當在與保護膜形成膜層疊後使黏著劑層固化時，可以在切割步驟前使黏著劑層固化，也可以在切割步驟後使黏著劑層固化。Here,. When the adhesive layer is composed of an energy ray-curable adhesive, the adhesive layer may be cured by irradiating the adhesive layer with energy rays at this stage, or may be cured after being laminated with the protective film forming film. Furthermore, when the adhesive layer is cured after being laminated with the protective film forming film, the adhesive layer may be cured before the dicing step, or may be cured after the dicing step.

作為能量射線，通常使用紫外線、電子束等。能量射線的照射量因能量射線的種類而異，例如採用紫外線時，以光量計優選為50~1000mJ/cm 2，特別優選為100~500mJ/cm 2。此外，採用電子束時，能量射線的照射量優選為10~1000krad左右。 As the energy rays, ultraviolet rays, electron beams, and the like are generally used. The irradiation amount of energy rays varies depending on the type of energy rays. For example, when ultraviolet rays are used, it is preferably 50 to 1000 mJ/cm 2 in terms of light intensity, and particularly preferably 100 to 500 mJ/cm 2 . In addition, when electron beams are used, the irradiation dose of energy rays is preferably about 10 to 1000 krad.

保護膜形成用複合片能夠藉由例如能夠藉由以下方式製造：分別製作上述所製作的支撐片與包含保護膜形成膜的層疊體後，使用支撐片及層疊體而將保護膜形成膜與支撐片層疊。The composite sheet for forming a protective film can be produced by, for example, manufacturing the above-produced support sheet and a laminate including the protective film forming film, and then forming the protective film forming film and the supporting film using the support sheet and the laminate. slices stacked.

首先，製備上述的保護膜形成膜用組合物或用溶劑稀釋該保護膜形成膜用組合物而得到的組合物(將所述兩種組合物稱為“塗佈劑”)。接著，在第二剝離膜的剝離面上塗佈塗佈劑並根據需要使其乾燥，從而在第二剝離膜上形成保護膜形成膜。接著，將第三剝離膜的剝離面貼合於保護膜形成膜的露出面，從而得到層疊體。First, the above-mentioned composition for forming a protective film or a composition obtained by diluting the composition for forming a protective film with a solvent (these two compositions are referred to as "coating agent") is prepared. Next, a coating agent is applied on the release surface of the second release film and dried as necessary to form a protective film-forming film on the second release film. Next, the peeling surface of the 3rd peeling film was bonded to the exposed surface of the protective film forming film, and the laminated body was obtained.

藉由以上方法得到支撐片及層疊體後，在剝離支撐片的第一剝離膜的同時，剝離層疊體中的第三剝離膜，並將露出的支撐片的黏著劑層與露出的保護膜形成膜貼合。根據需要，在剝離第二剝離膜後，將形成在第四剝離膜上的夾具用黏著劑層與所露出的保護膜形成膜或黏著劑層的周邊部貼合。由此，得到圖2所示的保護膜形成用複合片。After the support sheet and the laminate are obtained by the above method, while the first release film of the support sheet is peeled off, the third release film in the laminate is peeled off, and the exposed adhesive layer of the support sheet and the exposed protective film are formed. film fit. If necessary, after peeling off the 2nd peeling film, the adhesive layer for clips formed on the 4th peeling film is bonded to the peripheral part of the exposed protective film forming film or adhesive layer. Thereby, the composite sheet for protective film formation shown in FIG. 2 was obtained.

對於所得到的支撐片及保護膜形成用複合片，根據所要貼附的工件的大小對寬度方向的兩側進行裁切從而調整寬度方向的大小，並利用捲繞裝置施加規定的張力、進行捲繞，從而形成片卷。For the obtained support sheet and protective film forming composite sheet, both sides in the width direction are cut according to the size of the workpiece to be attached to adjust the size in the width direction, and a predetermined tension is applied by a winding device, and rolled up. wound to form a roll.

(9. 裝置的製造方法) 作為使用了本實施方案的支撐片及保護膜形成用複合片的裝置的製造方法的一個實例，對製造帶保護膜的晶片的方法進行說明，所述帶保護膜的晶片藉由對貼附有保護膜形成膜的晶圓進行加工而得到。 (9. Manufacturing method of device) As an example of a method of manufacturing a device using the support sheet and protective film-forming composite sheet of this embodiment, a method of manufacturing a wafer with a protective film by attaching a The wafer on which the protective film is formed is processed.

本實施方案的裝置的製造方法至少具有以下的步驟1~步驟5： 步驟1：將捲繞成卷狀的保護膜形成用複合片放卷並拉出的步驟； 步驟2：將所拉出的保護膜形成用複合片的保護膜形成膜貼附於晶圓背面的步驟； 步驟3：將所貼附的保護膜形成膜製成保護膜的步驟； 步驟4：對保護膜或保護膜形成膜進行雷射打標的步驟； 步驟5：將背面具有保護膜或保護膜形成膜的晶圓單顆化，從而得到多個帶保護膜或保護膜形成膜的晶片的步驟。 The manufacturing method of the device of the present embodiment has at least the following steps 1 to 5: Step 1: the step of unwinding and pulling out the composite sheet for forming the protective film wound into a roll; Step 2: a step of attaching the protective film forming film of the pulled out protective film forming composite sheet to the back surface of the wafer; Step 3: a step of making the attached protective film forming film into a protective film; Step 4: a step of laser marking the protective film or the protective film forming film; Step 5: A step of singulating the wafer having the protective film or the protective film forming film on the back surface to obtain a plurality of wafers with the protective film or the protective film forming film.

另外，由上述可知，步驟3可以在步驟5之前進行，也可以在步驟5之後進行。In addition, it can be known from the above that step 3 can be performed before step 5 or after step 5.

利用圖6對具有上述步驟1~步驟5的裝置的製造方法進行說明。The manufacturing method of the device having the above steps 1 to 5 will be described with reference to FIG. 6 .

首先，將捲繞成卷狀的保護膜形成用複合片放卷並將保護膜形成用複合片拉出(步驟1)。此時，對於支撐片的基材，因以上述方式控制了未形成黏著劑層的主面的表面性狀，因此基材與形成在保護膜形成膜上的剝離膜之間不會發生黏連。其結果，能夠抑制保護膜形成用複合片的拉出不良。First, the composite sheet for protective film formation wound into a roll is unwound, and the composite sheet for protective film formation is pulled out (step 1). At this time, as for the base material of the support sheet, since the surface properties of the main surface on which the adhesive layer is not formed are controlled as described above, no sticking occurs between the base material and the release film formed on the protective film forming film. As a result, it is possible to suppress the failure to pull out the composite sheet for protective film formation.

然後，如圖6所示，將所拉出的保護膜形成用複合片10的保護膜形成膜4貼附於晶圓6的背面(步驟2)。此時，可以利用環形框架7對保護膜形成膜4的外周部進行固定。在本實施方案中，如圖6所示，由於在保護膜形成膜4的外周部設置有夾具用黏著劑層5，因此將夾具用黏著劑層5貼附於環形框架7。晶圓6貼附於保護膜形成膜4的與黏著劑層3的貼附面相反的面。在將保護膜形成膜4貼附於晶圓6時，也可以根據需要對保護膜形成膜4進行加熱，從而使其發揮黏著性。Then, as shown in FIG. 6 , the protective film forming film 4 of the protective film forming composite sheet 10 pulled out is attached to the back surface of the wafer 6 (step 2 ). At this time, the outer peripheral portion of the protective film forming film 4 can be fixed by the ring frame 7 . In this embodiment, as shown in FIG. 6 , since the adhesive layer 5 for the jig is provided on the outer peripheral portion of the protective film forming film 4 , the adhesive layer 5 for the jig is attached to the ring frame 7 . Wafer 6 is attached to the surface of protective film forming film 4 opposite to the surface to which adhesive layer 3 is attached. When attaching the protective film-forming film 4 to the wafer 6 , the protective film-forming film 4 may be heated as necessary to exhibit adhesiveness.

然後，將所貼附的保護膜形成膜4製成保護膜從而形成保護膜(步驟3)，得到帶保護膜的晶圓6。當保護膜形成膜4為熱固性時，以規定溫度將保護膜形成膜4加熱適當的時間即可。此外，當保護膜形成膜4為能量射線固化性時，從支撐片1側射入能量射線即可。Then, the attached protective film-forming film 4 is made into a protective film to form a protective film (step 3), and a wafer 6 with a protective film is obtained. When the protective film forming film 4 is thermosetting, it is sufficient to heat the protective film forming film 4 at a predetermined temperature for an appropriate time. Moreover, what is necessary is just to inject an energy ray from the support sheet 1 side, when the protective film forming film 4 is energy-ray curable.

另外，保護膜形成膜4的固化可以在切割步驟後進行，也可以在從黏著片上拾取帶保護膜形成膜的晶片後使保護膜形成膜固化。In addition, the curing of the protective film forming film 4 may be performed after the dicing step, or the protective film forming film may be cured after picking up the wafer with the protective film forming film from the adhesive sheet.

接著，對保護膜進行雷射打標(步驟4)。另外，步驟4優選在步驟3之後進行，在本實施方案中，步驟4更優選在步驟5之前進行。Next, laser marking is performed on the protective film (step 4). In addition, step 4 is preferably performed after step 3, and in this embodiment, step 4 is more preferably performed before step 5.

對於雷射打標，可以藉由照射雷射而切削保護膜形成膜或保護膜的表面而進行打標，也可以藉由照射雷射使保護膜形成膜或保護膜的體積增加從而進行形成凸狀部的打標。使用公知的雷射打標裝置進行雷射打標即可。For laser marking, marking can be performed by cutting the surface of the protective film forming film or the protective film by irradiating laser light, or forming embossing by increasing the volume of the protective film forming film or protective film by irradiating laser light. The marking of the shape part. Laser marking may be performed using a known laser marking device.

對於支撐片的基材，由於藉由上述方式控制了未形成黏著劑層的主面的光澤度值及表面性狀，因此能夠進行清晰的打標，進而在觀察標記時能夠清晰地進行辨認。As for the base material of the support sheet, since the gloss value and surface properties of the main surface on which the adhesive layer is not formed are controlled in the above-mentioned manner, clear marking can be performed, and further, the marking can be clearly recognized when observed.

接著，利用公知的方法對帶保護膜的晶圓6進行切割，從而得到圖5所示的具有保護膜40的晶片(帶保護膜的晶片70)(步驟5)。即，保護膜形成用複合片的支撐片能夠發揮切割片的功能。Next, the wafer with a protective film 6 is diced by a known method to obtain a wafer having a protective film 40 (a wafer with a protective film 70 ) shown in FIG. 5 (step 5). That is, the support sheet of the composite sheet for protective film formation can function as a dicing sheet.

(10. 變形例) 在上述的實施方案中，對將支撐片與保護膜形成膜一體化的保護膜形成用複合片進行了說明，但支撐片與保護膜形成膜也可以不進行一體化。即，由上述的支撐片與用於貼附於支撐片的黏著劑層的表面的保護膜形成膜構成的套件也包括在本發明內。該套件能夠藉由首先將保護膜形成膜與工件貼合，然後再將支撐片的黏著劑層與保護膜形成膜貼合而使用。 (10. Variations) In the above-mentioned embodiments, the composite sheet for protective film formation in which the support sheet and the protective film forming film are integrated has been described, but the support sheet and the protective film forming film may not be integrated. That is, the set which consists of the said support sheet and the protective film forming film for sticking to the surface of the adhesive layer of a support sheet is also included in this invention. This kit can be used by first bonding the protective film forming film to the workpiece, and then bonding the adhesive layer of the support sheet to the protective film forming film.

保護膜形成用複合片也可以具有圖7所示的構成。圖7所示的保護膜形成用複合片11藉由具備支撐片1與層疊於支撐片1的黏著劑層3側的保護膜形成膜4而構成，所述支撐片1藉由在基材2的一個面上層疊黏著劑層3而成。保護膜形成膜4以俯視時與工件大致相同或稍大於工件的方式形成，且以小於支撐片1的方式形成。黏著劑層3的未層疊保護膜形成膜4的部分可貼附於環形框架等夾具。The composite sheet for protective film formation may have the structure shown in FIG. 7. The composite sheet 11 for forming a protective film shown in FIG. It is formed by laminating an adhesive layer 3 on one side of the The protective film forming film 4 is formed so as to be substantially the same as or slightly larger than the workpiece in plan view, and is formed so as to be smaller than the support sheet 1 . The portion of the adhesive layer 3 where the protective film forming film 4 is not laminated can be attached to a jig such as a ring frame.

以上，對本發明的實施方案進行了說明，但本發明不受上述實施方案的任何限定，可以在本發明的範圍內以各種形式進行變更。 實施例 As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment at all, It can change in various forms within the scope of this invention. Example

以下，利用實施例對本發明進行更詳細的說明，但本發明並不限定於這些實施例。Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these Examples.

(實施例1) (支撐片的製作) 首先，利用以下方法製作構成支撐片的基材。 (Example 1) (manufacturing of support sheet) First, the base material constituting the support sheet was produced by the following method.

作為構成基材的材質，用混煉機熔融混煉聚丙烯膜(拉伸模量為MD方向320MPa/CD方向290MPa、熔點156℃)，得到擠出用原料。As a material constituting the base material, a polypropylene film (tensile modulus 320 MPa in MD direction/290 MPa in CD direction, melting point 156° C.) was melted and kneaded by a kneader to obtain a raw material for extrusion.

使用小型T模擠出機(Toyo Seiki Seisaku-sho, Ltd.製造，產品名稱“Labo Plastomill (注冊商標)”)在220℃下將所得到的擠出用原料擠出成型，用實施了印花加工(磨石研磨、濕噴射(液體珩磨)處理、乾噴射(噴砂)處理)的金屬輥(40℃)對剛完成成型後的片進行冷卻，由此得到調整了與金屬輥相接觸的面的表面粗糙度的厚度為80μm的基材。Using a small T-die extruder (manufactured by Toyo Seiki Seisaku-sho, Ltd., product name "Labo Plastomill (registered trademark)"), the obtained extrusion material was extruded at 220° C., and printed. (grindstone grinding, wet spray (liquid honing) treatment, dry spray (sandblasting) treatment) metal roll (40°C) cools the sheet immediately after forming, thereby obtaining a surface that is in contact with the metal roll The thickness of the surface roughness is 80 μm for the substrate.

然後，利用以下方法製作構成支撐片的黏著劑層。Then, the adhesive layer constituting the support sheet was produced by the following method.

向100質量份(固體成分換算)的丙烯酸酯類共聚物(重均分子量：80萬)中添加15質量份的3官能度苯二亞甲基二異氰酸酯交聯劑(MITSUI TAKEDA CHEMICALS, INC.製造、商品名稱“TAKENATE 110N”)，用甲基乙基酮稀釋至固體成分濃度為25質量%，從而製備包含黏著劑層用組合物的塗佈劑，所述丙烯酸酯類共聚物藉由使80質量份的丙烯酸2-乙基己酯(2EHA)、20質量份的丙烯酸2-羥基乙酯(HEA)共聚而得到。15 parts by mass of a trifunctional xylylene diisocyanate crosslinking agent (manufactured by MITSUI TAKEDA CHEMICALS, INC. , trade name "TAKENATE 110N"), diluted with methyl ethyl ketone to a solid content concentration of 25% by mass to prepare a coating agent containing a composition for an adhesive layer. The acrylate copolymer was prepared by making 80 It is obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) and 20 parts by mass of 2-hydroxyethyl acrylate (HEA).

將上述的黏著劑層用組合物的塗佈劑塗佈於剝離膜(LINTEC Corporation製造，商品名稱“SP-PET381031”，進行了矽酮剝離處理的聚對苯二甲酸乙二醇酯(PET)膜、厚度：38μm)的實施了剝離處理的面上，將其乾燥，從而製作具有厚度為5μm的黏著劑層的帶黏著劑層的剝離膜。Apply the above-mentioned coating agent for the adhesive layer composition to a release film (manufactured by LINTEC Corporation, trade name "SP-PET381031", polyethylene terephthalate (PET) that has undergone a silicone release treatment. Film, thickness: 38 μm) The peeling-treated surface was dried to produce a peeling film with an adhesive layer having an adhesive layer with a thickness of 5 μm.

將帶黏著劑層的剝離膜的黏著劑層的表面與基材的未調整表面粗糙度的面(未與金屬輥接觸的面)貼合，從而製作支撐片。該支撐片為長條狀，將其捲繞而形成片卷。The surface of the adhesive layer of the peeling film with an adhesive layer was bonded to the surface of the substrate on which the surface roughness was not adjusted (the surface not in contact with the metal roller) to produce a support sheet. The support sheet is long and wound to form a sheet roll.

(1)包含保護膜形成膜的第一層疊體的製作 將下述的(a)~(g)成分混合，用甲基乙基酮稀釋至固體成分濃度為50質量%，從而製備保護膜形成膜用塗佈劑。 (a)黏結劑聚合物：150質量份(固體成分換算，以下相同)的(甲基)丙烯酸酯共聚物(使10質量份的丙烯酸正丁酯、70質量份的丙烯酸甲酯、5質量份的甲基丙烯酸縮水甘油酯及15質量份的丙烯酸2-羥基乙酯共聚而得到的丙烯酸類共聚物，重均分子量：80萬，玻璃化轉變溫度：-1℃) (b-1)熱固性成分：60質量份的雙酚A型環氧樹脂(Mitsubishi Chemical Corporation製造，產品名稱“jER828”，環氧當量184~194g/eq) (b-2)熱固性成分：10質量份的雙酚A型環氧樹脂(Mitsubishi Chemical Corporation製造，產品名稱“jER1055”，環氧當量800~900g/eq) (b-3)熱固性成分：30質量份的雙環戊二烯型環氧樹脂(DAINIPPON INK AND CHEMICALS,INC.製造，產品名稱“EPICLON HP-7200HH”，環氧當量255~260g/eq) (c)熱活性潛伏性環氧樹脂固化劑：2質量份的二氰二胺(ADEKA CORPORATION製造：ADEKA HARDENER EH-3636AS，活性氫量21g/eq) (d)固化促進劑：2質量份的2-苯基-4,5-二羥基甲基咪唑(SHIKOKU CHEMICALS CORPORATION製造，產品名稱“CUREZOL 2PHZ”) (e)填料：320質量份的二氧化矽填料(Admatechs公司製造，產品名稱“SC2050MA”，平均粒徑：0.5μm) (f)著色劑：1.2質量份的炭黑(Mitsubishi Chemical Corporation製造，產品名稱“#MA650”，平均粒徑：28nm) (g)矽烷偶聯劑：2質量份(Shin-Etsu Chemical Co., Ltd.製造，產品名稱“KBM-403”) (1) Preparation of the first laminate including the protective film forming film The following components (a) to (g) were mixed and diluted with methyl ethyl ketone to a solid content concentration of 50% by mass to prepare a coating agent for forming a protective film. (a) Binder polymer: 150 parts by mass (in terms of solid content, the same below) of (meth)acrylate copolymer (10 parts by mass of n-butyl acrylate, 70 parts by mass of methyl acrylate, 5 parts by mass of Acrylic copolymer obtained by copolymerization of glycidyl methacrylate and 15 parts by mass of 2-hydroxyethyl acrylate, weight average molecular weight: 800,000, glass transition temperature: -1°C) (b-1) Thermosetting component: 60 parts by mass of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER828", epoxy equivalent 184~194g/eq) (b-2) Thermosetting component: 10 parts by mass of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER1055", epoxy equivalent 800~900g/eq) (b-3) Thermosetting component: 30 parts by mass of dicyclopentadiene-type epoxy resin (manufactured by DAINIPPON INK AND CHEMICALS, INC., product name "EPICLON HP-7200HH", epoxy equivalent 255~260g/eq) (c) Thermally active latent epoxy resin curing agent: 2 parts by mass of dicyandiamide (manufactured by ADEKA CORPORATION: ADEKA HARDENER EH-3636AS, active hydrogen content 21g/eq) (d) Curing accelerator: 2 parts by mass of 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by SHIKOKU CHEMICALS CORPORATION, product name "CUREZOL 2PHZ") (e) Filler: 320 parts by mass of silica filler (manufactured by Admatechs, product name "SC2050MA", average particle diameter: 0.5 μm) (f) Colorant: 1.2 parts by mass of carbon black (manufactured by Mitsubishi Chemical Corporation, product name "#MA650", average particle diameter: 28 nm) (g) Silane coupling agent: 2 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-403")

準備厚度為38μm的在聚對苯二甲酸乙二醇酯(PET)膜的一個面上形成矽酮類的剝離劑層而成的第一剝離膜(LINTEC Corporation製造，產品名稱“SP-PET381031”)與厚度為38μm的在PET膜的一個面上形成矽酮類的剝離劑層而成的第二剝離膜(LINTEC Corporation製造，產品名稱“SP-PET381130”)。Prepare a first release film (manufactured by LINTEC Corporation, product name "SP-PET381031" by forming a silicone-based release agent layer on one side of a polyethylene terephthalate (PET) film with a thickness of 38 μm. ) and a second release film (manufactured by LINTEC Corporation, product name "SP-PET381130") having a thickness of 38 μm and a silicone-based release agent layer formed on one surface of the PET film.

首先，利用刮刀塗佈機在第一剝離膜的剝離面上塗佈上述保護膜形成膜用塗佈劑，並將其乾燥，從而形成厚度為25μm的保護膜形成膜。然後，在保護膜形成膜上重疊第二剝離膜的剝離面而將兩者貼合，從而得到由第一剝離膜、保護膜形成膜(厚度：25μm)及第二剝離膜構成的第一層疊體。該層疊體為長條狀，將其捲繞而形成片卷。First, the above coating agent for protective film-forming film was applied on the peeling surface of the first peeling film with a knife coater, and dried to form a protective film-forming film having a thickness of 25 μm. Then, the release surface of the second release film was superimposed on the protective film forming film and the two were bonded to obtain a first laminate consisting of the first releasing film, the protective film forming film (thickness: 25 μm) and the second releasing film. body. This laminated body is long, and it winds up and becomes a sheet roll.

(2)包含夾具用黏著劑層的第二層疊體的製作 將下述的(j)及(k)成分混合，用甲苯稀釋至固體成分濃度為15質量%，從而製備夾具用黏著劑層用塗佈劑。 (j)黏著主劑：100質量份的(甲基)丙烯酸酯共聚物(使69.5質量份的丙烯酸丁酯、30質量份的丙烯酸甲酯、0.5質量份的丙烯酸2-羥基乙酯共聚而得到的共聚物，重均分子量：50萬) (k)交聯劑：5質量份的甲苯二異氰酸酯類交聯劑(TOYOCHEM CO., LTD.製造，產品名稱“BHS8515”) (2) Preparation of the second laminate including the adhesive layer for jigs The following components (j) and (k) were mixed and diluted with toluene to a solid content concentration of 15% by mass to prepare a coating agent for an adhesive layer for jigs. (j) Adhesive main agent: 100 parts by mass of (meth)acrylate copolymer (obtained by copolymerizing 69.5 parts by mass of butyl acrylate, 30 parts by mass of methyl acrylate, and 0.5 parts by mass of 2-hydroxyethyl acrylate) Copolymer, weight average molecular weight: 500,000) (k) Crosslinking agent: 5 parts by mass of toluene diisocyanate crosslinking agent (manufactured by TOYOCHEM CO., LTD., product name "BHS8515")

準備厚度為38μm的在PET膜的一個面上形成矽酮類的剝離劑層而成的第一及第二剝離膜(LINTEC Corporation製造，產品名稱“SP-PET381031”)與作為芯材的聚氯乙烯膜(Okamoto Industries,Inc.製造，厚度：50μm)。First and second release films (manufactured by LINTEC Corporation, product name "SP-PET381031") with a thickness of 38 μm formed by forming a silicone-based release agent layer on one side of the PET film and polychloride as a core material were prepared. Vinyl film (manufactured by Okamoto Industries, Inc., thickness: 50 μm).

首先，利用刮刀塗佈機在第一剝離膜的剝離面上塗佈上述的夾具用黏著劑層用塗佈劑，並將其乾燥，從而形成厚度為5μm的第一夾具用黏著劑層。然後，將上述芯材與第一夾具用黏著劑層貼合，從而得到由芯材、第一夾具用黏著劑層及第一剝離膜構成的層疊體A。該層疊體A為長條狀，將其捲繞而形成片卷。First, the above-mentioned coating agent for the adhesive layer for jigs was applied on the release surface of the first release film by a knife coater, and dried to form a first adhesive layer for jigs with a thickness of 5 μm. Then, the said core material and the adhesive agent layer for 1st jigs were bonded together, and the laminated body A which consists of a core material, the adhesive agent layer for 1st jigs, and a 1st release film was obtained. This laminated body A is long, and it winds up and forms a sheet roll.

然後，利用刮刀塗佈機在第二剝離膜的剝離面上塗佈上述的夾具用黏著劑層用塗佈劑，並將其乾燥，從而形成厚度為5μm的第二夾具用黏著劑層。然後，將上述層疊體A中的芯材的露出面與第二夾具用黏著劑層貼合，從而得到由第一剝離膜/第一夾具用黏著劑層/芯材/第二夾具用黏著劑層/第二剝離膜構成的第二層疊體(以下，有時將“第一夾具用黏著劑層/芯材/第二夾具用黏著劑層”這一結構稱為“夾具用黏著劑層”)。該層疊體為長條狀，將其捲繞而形成片卷。Then, the above-mentioned coating agent for the adhesive layer for jigs was applied on the peeling surface of the second release film with a knife coater, and dried to form a second adhesive layer for jigs with a thickness of 5 μm. Then, the exposed surface of the core material in the above-mentioned laminated body A is bonded to the adhesive layer for the second jig, thereby obtaining a composition consisting of the first release film/adhesive layer for the first jig/core material/adhesive for the second jig. layer/second release film (hereinafter, the structure of "adhesive layer for first jig/core material/adhesive layer for second jig" may be referred to as "adhesive layer for jig" ). This laminated body is long, and it winds up and becomes a sheet roll.

(3)第三層疊體的製作 從在上述(1)中得到的第一層疊體中剝離第二剝離膜，從而露出保護膜形成膜。另一方面，從在上述得到的支撐片上剝離剝離膜，從而露出黏著劑層。以上述保護膜形成膜與該黏著劑層相接觸的方式將第一層疊體與支撐片貼合，從而得到層疊支撐片、保護膜形成膜及第一剝離膜而成的第三層疊體，其中，支撐片由基材及黏著劑層構成。 (3) Fabrication of the third laminate The second release film is peeled off from the first laminate obtained in the above (1) to expose the protective film forming film. On the other hand, the release film was peeled off from the support sheet obtained above to expose the adhesive layer. The first laminate is bonded to the support sheet in such a manner that the above-mentioned protective film-forming film is in contact with the adhesive layer to obtain a third laminate in which the support sheet, the protective film-forming film, and the first release film are stacked, wherein , the supporting sheet is composed of a base material and an adhesive layer.

(4)保護膜形成用複合片的製作 從在上述(2)中得到的第二層疊體中剝離第二剝離膜，保留第一剝離膜而對夾具用黏著劑層的內周邊進行半切，去除內側的圓形部分。此時，將夾具用黏著劑層的內周邊的直徑設為220mm。 (4) Production of composite sheet for protective film formation The second release film was peeled off from the second laminate obtained in the above (2), and the inner periphery of the adhesive layer for jigs was cut in half while leaving the first release film, and the inner circular portion was removed. At this time, the diameter of the inner periphery of the adhesive layer for jigs was set to 220 mm.

從在上述(3)中得到的第三層疊體中剝離第一剝離膜，將所露出的保護膜形成膜與第二層疊體中露出的夾具用黏著劑層重合並壓接。然後，保留第二層疊體中的第一剝離膜而對保護膜形成用複合片的外周邊進行半切，去除外側的部分。此時，將保護膜形成用複合片的外周邊的直徑設為270mm。The first release film was peeled off from the third laminate obtained in the above (3), and the exposed protective film-forming film and the adhesive layer for jigs exposed in the second laminate were laminated and pressure-bonded. Then, the outer periphery of the composite sheet for protective film formation was half-cut, leaving the 1st release film in a 2nd laminated body, and the outer part was removed. At this time, the diameter of the outer periphery of the composite sheet for protective film formation was set to 270 mm.

由此，得到由在基材上層疊黏著劑層(厚度：5μm)而成的支撐片、層疊於支撐片的黏著劑層側的保護膜形成膜、層疊於保護膜形成膜的與支撐片相反一側的周邊部的環狀的夾具用黏著劑層、及層疊於夾具用黏著劑層的與保護膜形成膜相反一側的剝離膜構成的保護膜形成用複合片。該保護膜形成用複合片為長條狀，將其捲繞而形成片卷。Thus, a support sheet formed by laminating an adhesive layer (thickness: 5 μm) on a substrate, a protective film-forming film laminated on the adhesive layer side of the support sheet, and a support sheet opposite to the protective film-forming film were obtained. A protective film-forming composite sheet composed of an annular adhesive layer for jigs on one peripheral portion, and a release film laminated on the side of the adhesive layer for jigs opposite to the protective film-forming film. This composite sheet for protective film formation is long, and this is wound up to form a sheet roll.

(實施例2~4及比較例1~3) 對磨石研磨、濕噴射處理、乾噴射處理進行組合，從而改變相對較大的凹凸與平滑的面的存在狀態，由此將實施例1的用於製作基材的金屬輥變更為具有規定的印花形狀的金屬輥，從而變更與金屬輥相接觸的面的表面粗糙度，除此以外，用與實施例1相同的方法製作保護膜形成用複合片。 (Examples 2~4 and Comparative Examples 1~3) Combining grindstone grinding, wet blasting, and dry blasting to change the presence of relatively large irregularities and smooth surfaces, the metal roller used to produce the base material in Example 1 was changed to have a specified A composite sheet for forming a protective film was produced in the same manner as in Example 1, except that the surface roughness of the surface in contact with the metal roll was changed by using a stamped metal roll.

使用在實施例1~4及比較例1~3中得到的支撐片或保護膜形成用複合片，進行下述測定及評價。Using the support sheet or the composite sheet for protective film formation obtained in Examples 1-4 and Comparative Examples 1-3, the following measurement and evaluation were performed.

(基材的露出表面的光澤性) 從各個實施例及比較例的支撐片上剝離剝離膜並貼附於無色透明的鈉鈣玻璃，從而製成測定用試驗樣本。針對測定用試驗樣本，使用光澤度計(NIPPON DENSHOKU INDUSTRIES Co.,Ltd.製造的光澤度計(Glossmeter)“VG 2000”)，依據JIS Z 8741從基材的未形成黏著劑層的一面側射入光，從而測定基材的未形成黏著劑層的一側的表面(露出表面)的60°鏡面光澤度，將該測定值作為基材的表面的光澤度值。將結果示於表1。 (glossiness of the exposed surface of the substrate) The peeling film was peeled off from the support sheet of each Example and the comparative example, and it stuck to the colorless transparent soda-lime glass, and the test sample for measurement was produced. For the test sample for measurement, use a gloss meter (Glossmeter (Glossmeter) "VG 2000" manufactured by NIPPON DENSHOKU INDUSTRIES Co., Ltd.), according to JIS Z 8741, from the side where the adhesive layer is not formed on the substrate. The 60° specular gloss of the surface (exposed surface) on the side where the adhesive layer is not formed of the base material was measured by entering light, and the measured value was taken as the gloss value of the surface of the base material. The results are shown in Table 1.

(基材的露出表面的表面粗糙度Sa1及Sa2) 使用Hitachi High-Tech Science Corporation製造的掃描型白光干涉顯微鏡VS-1550對各個實施例及比較例的支撐片的基材的露出表面進行觀察，按照以下方法計算出Sa1及Sa2。 (Surface roughness Sa1 and Sa2 of the exposed surface of the substrate) The exposed surface of the base material of the support sheet of each Example and the comparative example was observed using the scanning white light interference microscope VS-1550 manufactured by Hitachi High-Tech Science Corporation, and Sa1 and Sa2 were calculated by the following method.

將觀察倍率設為50倍並以多視野模式進行觀察。在觀察視野中，設定X軸方向上的長度0.36mm×Y軸方向上的長度0.27mm的區域，將X軸方向分為15列、Y軸方向分為20行而進行觀察，對合計300個格子進行觀察。The observation magnification was set to 50 times and observation was performed in the multi-view mode. In the observation field of view, an area with a length of 0.36 mm in the X-axis direction and a length of 0.27 mm in the Y-axis direction is set, and the X-axis direction is divided into 15 columns and the Y-axis direction is divided into 20 rows for observation. A total of 300 grid for observation.

對300個格子進行圖像合成，形成1張4.91mm×4.90mm的圖像。在所合成的1張圖像的整個區域測定Sa，並將其設為Sa1。將結果示於表1。Image synthesis is performed on 300 grids to form an image of 4.91mm×4.90mm. Sa is measured over the entire area of one composited image, and this is set as Sa1. The results are shown in Table 1.

然後，不合成300個格子的圖像，對各個格子測定Sa，從而得到300個Sa資料。在300個Sa資料中，提取出最小值至第20小的Sa的資料。將所提取的20個Sa的資料的平均值設為Sa2。將結果示於表1。Then, without synthesizing images of 300 grids, Sa was measured for each grid to obtain 300 Sa data. Among the 300 Sa data, the data from the smallest value to the 20th smallest Sa are extracted. Let the average value of the 20 extracted data of Sa be Sa2. The results are shown in Table 1.

(雷射打標的辨認性) 從各個實施例及比較例的保護膜形成用複合片上去除剝離膜，使用貼附裝置(LINTEC Corporation製造的“RAD-2700F/12”)、於70℃的溫度下、在厚度為350μm、外徑為8英寸的矽晶圓上貼附保護膜形成用複合片及環形框架。然後，在130℃、2小時的條件下對保護膜形成膜進行加熱使其固化從而形成保護膜。接著，使用列印裝置(EO公司製造，CSM300M，波長532nm)，隔著支撐片對保護膜照射雷射，並按照以下兩個圖案(圖案1及圖案2)進行打標。 圖案1：文字大小為0.5mm×0.5mm、文字間隔為0.05mm、文字個數為20個文字 圖案2：文字大小為0.15mm×0.25mm、文字間隔為0.05mm、文字個數為20個文字 (Recognizability of laser marking) The peeling film was removed from the protective film-forming composite sheet of each Example and Comparative Example, and the thickness was 350 μm at a temperature of 70° C. A composite sheet for forming a protective film and a ring frame are attached to an 8-inch silicon wafer. Then, the protective film forming film was heated and cured under the conditions of 130° C. for 2 hours to form a protective film. Next, using a printing device (manufactured by EO Corporation, CSM300M, wavelength 532nm), the protective film was irradiated with laser light through the support sheet, and the following two patterns (pattern 1 and pattern 2) were marked. Pattern 1: The character size is 0.5mm×0.5mm, the character interval is 0.05mm, and the number of characters is 20 characters Pattern 2: The text size is 0.15mm×0.25mm, the text interval is 0.05mm, and the text number is 20 characters

按照以下所示的標準，對隔著支撐片觀察和不隔著支撐片觀察(去除支撐片而觀察)藉由上述雷射打標形成在保護膜上的文字的兩種情況進行評價。將結果示於表1。 A：能夠毫無問題地讀取圖案1及2中的所有文字。 B：讀取圖案2時存在不清晰的部分，但能夠毫無問題地讀取圖案1中的所有文字。 C：讀取圖案1及2時均有不清晰的部分。 According to the criteria shown below, two cases of observation through the support sheet and observation without the support sheet (observation without the support sheet) were evaluated by the above-mentioned laser marking formed on the protective film. The results are shown in Table 1. A: All the characters in Patterns 1 and 2 can be read without any problem. B: There are unclear parts when pattern 2 is read, but all the characters in pattern 1 can be read without any problem. C: There are unclear parts when both patterns 1 and 2 are read.

(保護膜形成用複合片的安裝(mount)拉出性) 將各個實施例及比較例的保護膜形成用複合片捲繞從而形成片卷。將片卷在室溫(23℃)下保存三天。從保存後的片卷中拉出保護膜形成用複合片，並在剝離剝離膜後，使用貼附裝置(LINTEC Corporation製造，RAD-2700)，將所拉出的保護膜形成用複合片貼附於矽晶圓(厚度為350μm，外徑為8英寸)及環形框架，按照以下3個等級對此時的與拉出不良相關的操作性進行評價。將拉出不良設為：拉出保護膜形成用複合片時，在黏著劑層與保護膜形成用膜之間發生部分剝離，支撐片轉印到剝離膜上的情況；或無法進行拉出保護膜形成用複合片這一操作的情況。將結果示於表1。 A：貼附50片，1片以下存在拉出不良 B：貼附50片，2片以上且5片以下存在拉出不良 C：貼附50片，6片以上存在拉出不良 (Mount pull-out property of composite sheet for protective film formation) The composite sheet for protective film formation of each Example and the comparative example was wound up and the sheet roll was formed. The rolls were stored at room temperature (23°C) for three days. Pull out the composite sheet for protective film formation from the sheet roll after storage, and after peeling off the release film, use an attaching device (manufactured by LINTEC Corporation, RAD-2700) to attach the drawn composite sheet for protective film formation On the silicon wafer (thickness: 350μm, outer diameter: 8 inches) and the ring frame, the operability related to the pull-out failure at this time was evaluated according to the following three levels. Defective drawing is defined as: when pulling out the composite sheet for forming a protective film, partial peeling occurs between the adhesive layer and the film for forming a protective film, and the support sheet is transferred to the release film; or when the protective film cannot be pulled out The case of the operation of the composite sheet for film formation. The results are shown in Table 1. A: 50 pieces are attached, and less than 1 piece has poor pull-out B: 50 sheets are attached, and there is a pull-out failure of more than 2 sheets and less than 5 sheets C: 50 sheets are attached, and there is failure to pull out more than 6 sheets

[表1] 　 基材 評價 光澤性 表面粗糙度 激光打標的辨認性 固定拉出性 60º光澤度 Sa1 Sa2 Sa1/Sa2 隔著支撐片 觀察 不隔著支撐片觀察 [-] [μm] [μm] 實施例1 58 0.89 0.20 4.45 A A A 實施例2 43 0.58 0.24 2.42 B A A 實施例3 27 0.80 0.31 2.58 B B A 實施例4 21 0.71 0.40 1.78 B B A 比較例1 2 0.94 0.85 1.11 C C A 比較例2 12 0.51 0.44 1.16 C B A 比較例3 150 0.03 0.01 3.00 A A C [Table 1] Substrate Evaluation Glossiness Surface roughness Recognizability of laser marking fixed pull-out 60º Gloss Sa1 Sa2 Sa1/Sa2 Observation through the support sheet Observing without a support [-] [μm] [μm] Example 1 58 0.89 0.20 4.45 A A A Example 2 43 0.58 0.24 2.42 B A A Example 3 27 0.80 0.31 2.58 B B A Example 4 twenty one 0.71 0.40 1.78 B B A Comparative example 1 2 0.94 0.85 1.11 C C A Comparative example 2 12 0.51 0.44 1.16 C B A Comparative example 3 150 0.03 0.01 3.00 A A C

根據表1確認到，以上述方式控制支撐片的基材的未形成黏著劑層的主面的光澤度值與表面性狀時，能夠兼顧拉出性與雷射打標的辨認性。From Table 1, it was confirmed that when the glossiness value and surface properties of the main surface of the base material of the support sheet on which the adhesive layer is not formed are controlled in the above-mentioned manner, both pull-out properties and laser marking visibility can be achieved.

1:支撐片 2:基材 2a,2b,4a:主面 3:黏著劑層 4:保護膜形成膜 5:夾具用黏著劑層 6:晶圓 6a:晶片 6b:凸狀電極 7:環形框架 10:保護膜形成用複合片 11:複合片 40:保護膜 50:大區域 60,60a,60b,60c,60d,60e,60f,60g,60h,60i:小區域 70:帶保護膜的晶片 IV:部分 OA:重疊區域 1: support sheet 2: Substrate 2a, 2b, 4a: main surface 3: Adhesive layer 4: Protective film forming film 5: Adhesive layer for fixture 6: Wafer 6a: Wafer 6b: Convex electrode 7: Ring frame 10: Composite sheet for protective film formation 11: Composite sheet 40: Protective film 50: large area 60,60a,60b,60c,60d,60e,60f,60g,60h,60i: small area 70:Wafer with protective film IV: part OA: overlapping area

圖1為本實施方案的支撐片的一個實例的剖面示意圖。 圖2為本實施方案的保護膜形成用複合片的一個實例的剖面示意圖。 圖3為用於說明本實施方案的支撐片的基材的未形成黏著劑層的主面的表面性狀的示意圖。 圖4為圖3中的IV部分的放大示意圖。 圖5為具有將保護膜形成膜製成保護膜而得到的保護膜的晶片的一個實例的剖面示意圖。 圖6為用於說明將本實施方案的保護膜形成用複合片貼附於晶圓的步驟的剖面示意圖。 圖7為本實施方案的保護膜形成用複合片的其他實例的剖面示意圖。 FIG. 1 is a schematic cross-sectional view of an example of a support sheet of the present embodiment. Fig. 2 is a schematic cross-sectional view of an example of the composite sheet for forming a protective film according to this embodiment. FIG. 3 is a schematic view for explaining the surface texture of the main surface of the base material of the support sheet according to the present embodiment, on which no adhesive layer is formed. FIG. 4 is an enlarged schematic view of part IV in FIG. 3 . 5 is a schematic cross-sectional view of an example of a wafer having a protective film obtained by forming a protective film forming film as a protective film. FIG. 6 is a schematic cross-sectional view illustrating a step of attaching the protective film-forming composite sheet of the present embodiment to a wafer. Fig. 7 is a schematic cross-sectional view of another example of the composite sheet for forming a protective film according to this embodiment.

1:支撐片 1: support piece

2:基材 2: Substrate

2a:主面 2a: main surface

2b:主面 2b: main surface

3:黏著劑層 3: Adhesive layer

3a:表面 3a: Surface

Claims (8)

一種支撐片，其具有基材與形成在所述基材的一個主面上的黏著劑層， 所述基材的未形成黏著劑層的主面上的4.91mm×4.90mm的四邊形區域的算數平均高度Sa1大於0.50μm， 所述未形成黏著劑層的主面在入射角為60°時的光澤度值為20以上。 A support sheet having a base material and an adhesive layer formed on one main surface of the base material, The arithmetic average height Sa1 of the 4.91mm×4.90mm quadrilateral region on the main surface of the base material on which no adhesive layer is formed is greater than 0.50 μm, The main surface on which the adhesive layer is not formed has a gloss value of 20 or more at an incident angle of 60°. 根據請求項1所述的支撐片，其中， 所述未形成黏著劑層的主面上的4.91mm×4.90mm的四邊形區域是由300個作為0.36mm×0.27mm的四邊形區域的小區域合成而得到的大區域， 將各個小區域的算數平均高度中的最小算數平均高度至第20小的算數平均高度的平均值設為Sa2時，Sa2為0.43μm以下。 The supporting sheet according to claim 1, wherein, The quadrangular area of 4.91 mm x 4.90 mm on the main surface where the adhesive layer is not formed is a large area obtained by synthesizing 300 small areas which are quadrangular areas of 0.36 mm x 0.27 mm, When the average value from the smallest arithmetic mean height to the 20th smallest arithmetic mean height among the arithmetic mean heights of each small region is Sa2, Sa2 is 0.43 micrometers or less. 根據請求項1或2所述的支撐片，其中， 作為Sa1相對於Sa2之比的Sa1/Sa2為1.40以上。 The supporting sheet according to claim 1 or 2, wherein, Sa1/Sa2 which is the ratio of Sa1 to Sa2 is 1.40 or more. 根據請求項1~3中任一項所述的支撐片，其中， 不在所述未形成黏著劑層的主面上形成其他層。 The support sheet according to any one of claims 1 to 3, wherein, No other layer is formed on the main surface on which the adhesive layer is not formed. 一種保護膜形成用複合片，其具有請求項1~4中任一項所述的支撐片與形成在所述支撐片的黏著劑層上的保護膜形成膜。A composite sheet for forming a protective film comprising the support sheet according to any one of claims 1 to 4 and a protective film forming film formed on an adhesive layer of the support sheet. 一種套件，其具有請求項1~4中任一項所述的支撐片與用於貼附於所述支撐片的黏著劑層的表面的保護膜形成膜。A kit comprising the support sheet according to any one of claims 1 to 4 and a protective film forming film to be attached to the surface of the adhesive layer of the support sheet. 一種裝置的製造方法，其具有： 將捲繞成卷狀的請求項1~4中任一項所述的支撐片放卷並拉出的步驟， 將所拉出的支撐片貼附於工件的步驟， 對所述工件進行雷射打標的步驟，及 加工所述工件從而得到所述工件的加工物的步驟。 A method of manufacturing a device, comprising: The step of unwinding and pulling out the support sheet according to any one of claim items 1 to 4 wound into a roll, a step of attaching the pulled out supporting sheet to the workpiece, the step of laser marking the workpiece, and A step of processing the workpiece to obtain a processed product of the workpiece. 一種裝置的製造方法，其具有： 將捲繞成卷狀的請求項5所述的保護膜形成用複合片放卷並拉出的步驟， 將所拉出的保護膜形成用複合片的保護膜形成膜貼附於工件背面的步驟， 將所貼附的保護膜形成膜製成保護膜的步驟， 對所述保護膜或所述保護膜形成膜進行雷射打標的步驟，及 將背面具有保護膜或保護膜形成膜的所述工件單顆化，從而得到多個帶保護膜或保護膜形成膜的工件的加工物的步驟。 A method of manufacturing a device, comprising: A step of unwinding and pulling out the composite sheet for forming a protective film described in claim 5 wound into a roll, a step of attaching the drawn protective film forming film of the protective film forming composite sheet to the back surface of the workpiece, the step of making the attached protective film forming film into a protective film, a step of laser marking the protective film or the protective film forming film, and A step of singulating the workpiece having a protective film or a protective film-forming film on its back surface to obtain a plurality of workpieces having a protective film or a protective film-forming film.
TW111108503A 2021-03-17 2022-03-09 Support sheet, composite sheet for forming protective film, and manufacturing method of device wherein the support sheet is capable of taking into account of both poor drawing out of the sheet and identifiability of laser marking when viewed through a substrate TW202238699A (en)

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