Kit, and method for manufacturing third laminate using the kit

Abstract

The present application provides a kit (1) having a first laminate (5) and a support sheet (10), the first laminate (5) having a first release film (151), a protective film forming film (13), and a second release film (152) sequentially laminated, the protective film forming film (13) being attached to a mirror surface of a mirror-finished silicon wafer using a laminating roller at 70°C, the 180° peel adhesion between the protective film forming film (13) and the silicon wafer after the attachment is completed for 5 minutes, measured at a peel rate of 100 mm / min and a temperature of 23°C, being 900 mN / 25 mm or more.

Description

Technical Field

[0001] This invention relates to a kit and a method for manufacturing a third laminate using the kit. This application claims priority based on Japanese Patent Application No. 2019-210863, filed on November 21, 2019, the contents of which are incorporated herein by reference.

[0002] In detail, the present invention relates to a kit and a method for manufacturing a third stack using the kit in an in-line process. The kit comprises a first stack having a first release film, a protective film forming film and a second release film stacked sequentially, and a support sheet for supporting a workpiece such as a semiconductor wafer that is the object of protection of the protective film forming film and the protective film forming film. The third stack has the workpiece, the protective film forming film and the support sheet stacked sequentially.

[0003] Here, "online process" refers to "a process performed within a device that connects multiple devices that perform one or more processes, or within the same device, including multiple processes and the transfer of processes between them, where workpieces are transferred piece by piece between processes". Background Technology

[0004] In recent years, semiconductor devices using a mounting method known as flip-chip have been manufactured. In flip-chip technology, a semiconductor chip with electrodes such as bumps on its circuit surface is used, and these electrodes are bonded to a substrate. Therefore, the back side of the semiconductor chip, opposite to the circuit surface, is sometimes exposed.

[0005] A resin film containing organic material is formed on the back side of the exposed semiconductor chip as a protective film, and it is sometimes assembled into a semiconductor device as a semiconductor chip with a protective film. The protective film is used to prevent cracks from forming on the semiconductor chip after the dicing process or packaging (e.g., Patent Documents 1-4).

[0006] Such semiconductor chips with protective films can undergo, for example... Figure 7 The process shown is used to manufacture the wafer. Specifically, a method is known in which a protective film 13 is formed by stacking a protective film on the back side 8b of a semiconductor wafer 8 having a circuit surface. Figure 7 A) in the figure, the protective film 13 is formed by thermosetting or energy radiation curing to produce the protective film 13'. Figure 7 In section B), a support sheet 10 is stacked on the protective film 13'. Figure 7 In step D), the semiconductor wafer 8 and the protective film 13' are cut to form a semiconductor chip 7 with a protective film. Figure 7 E and Figure 7 F), picks up the semiconductor chip 7 with a protective film from the support sheet 10. Figure 7 (G in the text). Here, Figure 7 In section A, an apparatus for attaching a protective film 13 to the back side 8b of a semiconductor wafer 8, and... Figure 7 The device in D that attaches the support sheet 10 to the protective film 13' will operate using separate devices.

[0007] Furthermore, a protective film forming composite sheet, which is integrally formed of the protective film forming film 13 and the support sheet 10, is used in the manufacture of semiconductor chips with protective films (e.g., Patent Documents 2, 3, and 4).

[0008] The manufacturing method of a semiconductor chip with a protective film using a composite wafer for forming a protective film, for example, through... Figure 8 The process shown. That is, a method is known in which a protective film forming composite sheet 3 for forming a protective film is attached to the back side 8b of a semiconductor wafer 8 having a circuit surface, wherein a protective film forming film 13 is formed by stacking a protective film forming film 13 and a support sheet 10. Figure 8 A), peeling back abrasion tape 17 ( Figure 8 In step B), the protective film 13 is formed by thermosetting or energy radiation curing to create the protective film 13'. Figure 8 In step C), the semiconductor wafer 8 and the protective film 13' are cut to form a semiconductor chip 7 with a protective film. Figure 8 E and Figure 8 F), picks up the semiconductor chip 7 with a protective film from the support sheet 10. Figure 8 (G in the middle).

[0009] Existing technical documents

[0010] Patent documents

[0011] Patent Document 1: Japanese Patent No. 4271597

[0012] Patent Document 2: International Publication No. 2014 / 157426

[0013] Patent Document 3: Japanese Patent No. 5363662

[0014] Patent Document 4: Japanese Patent Application Publication No. 2016-225496 Summary of the Invention

[0015] The technical problem to be solved by the present invention

[0016] exist Figure 7In the conventional method for manufacturing a semiconductor chip with a protective film shown, the workpiece (i.e., the semiconductor wafer 8) that is to be protected by the protective film forming film 13 is a workpiece whose back-abrasion tape has been peeled off. Because the protective film forming film 13 is stacked on the back side 8b of the semiconductor wafer 8... Figure 7 A), and the protective film 13 is cured to form a protective film 13'. Figure 7 After B), attach the support sheet 10 to the protective film 13'. Figure 7 Therefore, for the apparatus for attaching a protective film to form a film 13 on the back side 8b of the semiconductor wafer 8 and the apparatus for attaching a support sheet 10 on the protective film 13', separate apparatuses would be used, making it difficult to set these processes as in-line processes.

[0017] Figure 8 In conventional methods for manufacturing semiconductor chips with protective films, the protective film forming composite sheet 3, which integrates the protective film forming film 13 and the support sheet 10, allows the steps of attaching the protective film forming film 13 to the workpiece (i.e., the semiconductor wafer 8) to be protected by the protective film forming film 13 and attaching the support sheet 10 to be combined into a single step. However, when using the protective film forming composite sheet 3, it is necessary to combine the characteristics of the protective film forming film 13 and the support sheet 10 according to their properties. In order to achieve the purpose of manufacturing semiconductor chips with protective films, multiple protective film forming composite sheets 3 must be prepared. Furthermore, the manufacturing costs of punching and other processes become a problem when preparing the protective film forming composite sheet 3. Moreover, when using the protective film forming composite sheet 3, during the placement process, the tape may meander within the placement machine after the tape roll is set, posing a risk that the placement position or tension of the first few wafers may not meet the settings.

[0018] use Figure 7 In the conventional method for manufacturing semiconductor chips with protective films, the protective film forming film 13 and the support sheet 10 used in the process of attaching the protective film forming film 13 to the back surface 8b of the semiconductor wafer 8 with the backing tape 17 attached, and attaching the support sheet 10 to the protective film forming film 13, the backing tape 17 may be peeled off before the adhesion between the back surface 8b of the semiconductor wafer 8 and the protective film forming film 13 is sufficient, which may result in peeling between the protective film forming film 13 and the semiconductor wafer 8.

[0019] The present invention addresses the above-mentioned situation by providing a kit suitable for manufacturing a third laminate using an in-line process, and a method for manufacturing the third laminate using the kit in an in-line process. The third laminate comprises, in sequence, a semiconductor wafer or other workpiece, a protective film forming film, and a support sheet. The protective film forming film forms a protective film that protects the back side of the workpiece and improves its appearance. The support sheet supports the protective film forming film. The kit includes the protective film forming film and the support sheet.

[0020] Technical means to solve technical problems

[0021] The present invention provides the following kit and a method for manufacturing a third laminate using the kit.

[0022] [1] A kit comprising a first laminate and a support sheet, wherein a first release film, a protective film forming film and a second release film are sequentially laminated in the first laminate, and the support sheet is used to support the workpiece that is the object to be protected by the protective film forming film and the protective film forming film.

[0023] Using a laminator roller at 70°C, the protective film is applied to the mirror surface of a mirror-finished silicon wafer. After 5 minutes of application, at a peeling speed of 100 mm / min and a temperature of 23°C, the 180° peel adhesion between the protective film and the silicon wafer is measured to be 900 mN / 25 mm or more.

[0024] [2] According to the kit described in [1] above, the first stack is in the form of a roll.

[0025] [3] According to the kit described in [1] or [2] above, wherein the protective film forming film is thermosetting or energy-cured.

[0026] [4] The kit according to any one of [1] to [3] above, wherein the adhesive layer of the support sheet attached to the protective film forming film is stacked on the substrate.

[0027] [5] According to any one of the above [1] to [4], wherein the support sheet is attached to the protective film forming film using a laminating roller at 23°C, and the 180° peel adhesion between the protective film forming film and the support sheet is 100mN / 25mm or more, measured at a peeling speed of 100mm / min and a temperature of 23°C 3 minutes after the attachment is completed.

[0028] [6] A method for manufacturing a third laminate, wherein the kit described in any one of [1] to [5] above is used in an online process, and the third laminate contains a workpiece, the protective film forming film and the support sheet stacked sequentially, the manufacturing method comprising:

[0029] The process of peeling off the first release film from the first laminate;

[0030] The first lamination process of attaching the protective film to the workpiece to form the exposed surface of the film; and

[0031] In the second lamination process of attaching the support sheet to the side of the protective film opposite to the exposed side,

[0032] The transport distance of the workpiece from the point where the first lamination process begins to the point where the second lamination process is completed is less than 7000 mm.

[0033] [7] A method for manufacturing a third laminate, wherein the kit described in any one of [1] to [5] above is used in an online process, and the third laminate contains a workpiece, the protective film forming film and the support sheet stacked sequentially, the manufacturing method comprising:

[0034] The process of peeling off the first release film from the first laminate;

[0035] The first lamination process of attaching the protective film to the workpiece to form the exposed surface of the film; and

[0036] In the second lamination process of attaching the support sheet to the side of the protective film opposite to the exposed side,

[0037] The time for transporting the workpiece from the start of the first lamination process to the completion of the second lamination process is less than 400 seconds.

[0038] [8] A method for manufacturing a third laminate, wherein the kit described in any one of [1] to [5] above is used in an online process, and the third laminate contains a workpiece, the protective film forming film and the support sheet stacked sequentially, the manufacturing method comprising:

[0039] The process of peeling off the first release film from the first laminate;

[0040] The first lamination process of attaching the protective film to the workpiece to form the exposed surface of the film; and

[0041] In the second lamination process of attaching the support sheet to the side of the protective film opposite to the exposed side,

[0042] Between the first lamination process and the second lamination process, the second laminate, on which the protective film is attached to the workpiece, is transferred piece by piece.

[0043] [9] The method for manufacturing the third laminate according to any one of [6] to [8] above, wherein a backing tape is attached to the surface of the workpiece opposite to the exposed surface of the protective film to which the protective film is attached, and a step of peeling the backing tape off the workpiece is included after the second lamination step.

[0044]

[10] In the manufacturing method of the third laminate described above [9], the backing tape is peeled off from the workpiece within 10 minutes of starting the attachment of the first lamination process.

[0045] Invention Effects

[0046] According to the present invention, a kit suitable for manufacturing a third laminate using an online process and a method for manufacturing the third laminate using the kit in an online process are provided, wherein the third laminate comprises a workpiece such as a semiconductor wafer, a protective film forming film and a support sheet stacked sequentially, the protective film forming film being capable of forming a protective film, the protective film being used to protect the back side of the workpiece and simultaneously improve its appearance, the support sheet being used to support the protective film forming film, and the kit comprising the protective film forming film and the support sheet. Attached Figure Description

[0047] Figure 1 A schematic cross-sectional view illustrating an example of the kit of this embodiment is shown for illustrative purposes.

[0048] Figure 2 A in the diagram is a schematic cross-sectional view illustrating an example of the step of peeling off the first release film of the first laminate in the manufacturing method of the third laminate of this embodiment.

[0049] Figure 2 B in the diagram is a schematic cross-sectional view illustrating an example of the step of peeling off the first release film of the first laminate in the manufacturing method of the third laminate of this embodiment.

[0050] Figure 2 C in the diagram is a schematic cross-sectional view illustrating an example of the step of peeling off the first release film of the first laminate in the manufacturing method of the third laminate of this embodiment.

[0051] Figure 3 In the diagram, A is a schematic cross-sectional view illustrating an example of the first lamination process and an example of the second lamination process in the manufacturing method of the third laminate of this embodiment.

[0052] Figure 3 B in the diagram is a schematic cross-sectional view illustrating an example of the first lamination process and an example of the second lamination process in the manufacturing method of the third laminate of this embodiment.

[0053] Figure 3 C in the diagram is a schematic cross-sectional view illustrating an example of the first lamination process and an example of the second lamination process in the manufacturing method of the third laminate of this embodiment.

[0054] Figure 3 In the diagram, D is a schematic cross-sectional view illustrating an example of the first lamination process and an example of the second lamination process in the manufacturing method of the third laminate of this embodiment.

[0055] Figure 3 E in the diagram is a schematic cross-sectional view illustrating an example of the first lamination process and an example of the second lamination process in the manufacturing method of the third laminate of this embodiment.

[0056] Figure 3 F in the diagram is a schematic cross-sectional view illustrating an example of the first lamination process and an example of the second lamination process in the manufacturing method of the third laminate of this embodiment.

[0057] Figure 4 A cross-sectional view is shown to illustrate an example of how the backing tape can be normally peeled off from the third laminate.

[0058] Figure 5 This is a cross-sectional view illustrating an example of a defect that occurs when the back-grinding tape is peeled off from the third laminate, resulting in peeling between the protective film and the workpiece.

[0059] Figure 6 This is a cross-sectional view illustrating an example of a defect that occurs when the backing tape is peeled off from the third laminate, resulting in peeling between the protective film and the support sheet.

[0060] Figure 7 A in the diagram is a schematic cross-sectional view illustrating an example of a conventional method for manufacturing a semiconductor chip with a protective film.

[0061] Figure 7 B in the diagram is a schematic cross-sectional view illustrating an example of a conventional method for manufacturing semiconductor chips with protective films.

[0062] Figure 7 C in the diagram is a schematic cross-sectional view illustrating an example of a conventional method for manufacturing a semiconductor chip with a protective film.

[0063] Figure 7D in the diagram is a schematic cross-sectional view illustrating an example of a conventional method for manufacturing semiconductor chips with protective films.

[0064] Figure 7 E in the diagram is a schematic cross-sectional view illustrating an example of a conventional method for manufacturing semiconductor chips with protective films.

[0065] Figure 7 F in the diagram is a schematic cross-sectional view illustrating an example of a conventional method for manufacturing semiconductor chips with protective films.

[0066] Figure 7 G in the diagram is a schematic cross-sectional view illustrating an example of a conventional method for manufacturing semiconductor chips with protective films.

[0067] Figure 8 A in the diagram is a schematic cross-sectional view illustrating another example of a conventional method for manufacturing semiconductor chips with protective films.

[0068] Figure 8 B in the diagram is a schematic cross-sectional view illustrating another example of a conventional method for manufacturing semiconductor chips with protective films.

[0069] Figure 8 C in the diagram is a schematic cross-sectional view illustrating another example of a conventional method for manufacturing semiconductor chips with protective films.

[0070] Figure 8 D in the diagram is a schematic cross-sectional view illustrating another example of a conventional method for manufacturing semiconductor chips with protective films.

[0071] Figure 8 E in the diagram is a schematic cross-sectional view illustrating another example of a conventional method for manufacturing semiconductor chips with protective films.

[0072] Figure 8 F in the diagram is a schematic cross-sectional view illustrating another example of a conventional method for manufacturing semiconductor chips with protective films.

[0073] Figure 8 G in the diagram is a schematic cross-sectional view illustrating another example of a conventional method for manufacturing semiconductor chips with protective films.

[0074] Explanation of reference numerals in the attached figures

[0075] 1: Kit; 3: Composite sheet for protective film formation; 5: First laminate; 6: Second laminate; 7: Semiconductor chip with protective film; 8: Semiconductor wafer; 8b: Back side of semiconductor wafer; 9: Semiconductor chip; 10: Support sheet; 10a: First side of support sheet; 11: Substrate; 11a: First side of substrate; 12: Adhesive layer; 12a: First side of adhesive layer; 13: Protective film forming film; 13': Protective film; 13a: First side of protective film forming film 13b: Second side of the protective film forming film; 14: Workpiece; 14a: Circuit side of the workpiece; 14b: Back side of the workpiece; 151: First release film (light-side release film); 152: Second release film (heavy-side release film); 16: Adhesive layer for fixture; 17: Backing tape; 18: Fixing fixture; 19: Third laminate; 19': Fourth laminate; 20: Semiconductor device; 21: Semiconductor device with protective film; 70: Punching blade; 80: Suction table. Detailed Implementation

[0076] The following describes in detail a kit as an example of an embodiment of the present invention, and a method for manufacturing a third laminate using the kit. Additionally, in the figures used in the following description, for ease of understanding, feature portions may sometimes be enlarged, and the dimensional ratios of the constituent elements may not be the same as in reality.

[0077] <<Kit>>

[0078] Figure 1 A schematic cross-sectional view is shown to illustrate an example of the kit of this embodiment. The kit of this embodiment includes a first laminate 5 and a support sheet 10. A first release film 151, a protective film forming film 13 and a second release film 152 are sequentially laminated in the first laminate 5. The support sheet 10 is used to support the workpiece and the protective film forming film 13, which are the objects to be protected by the protective film forming film 13.

[0079] In this embodiment, a laminating roller at 70°C is used to attach the protective film forming film 13 to the mirror surface of a mirror-finished silicon wafer. After 5 minutes of attachment, at a peeling speed of 100 mm / min and a temperature of 23°C, the 180° peel adhesion between the protective film forming film 13 and the silicon wafer is measured to be 900 mN / 25 mm or more.

[0080] Preferably, either the first release film 151 or the second release film 152 is a light-sided release film, and the other is a heavy-sided release film. In this embodiment, the first release film 151 is a light-sided release film, and the second release film 152 is a heavy-sided release film.

[0081] As a support sheet 10, examples include a sheet consisting only of a substrate 11, or an adhesive sheet having an adhesive layer 12 on the substrate 11. In this embodiment, the support sheet 10 has an adhesive layer 12 laminated on the substrate 11 and is used in such a way that after the second release film 152 of the protective film forming film 13 is peeled off, the adhesive layer 12 of the support sheet 10 is attached to the second surface 13b on the side of the second release film 152.

[0082] <<Manufacturing Method of the Third Layer Using the Kit>>

[0083] The manufacturing method of the third laminate in this embodiment is a method of using the kit to manufacture the third laminate in an online process. The third laminate contains a workpiece, a protective film forming film 13, and a support sheet 10 stacked in sequence. The manufacturing method includes, in sequence: a step of peeling off the first release film 151 of the first laminate 5; a first lamination step of attaching the exposed surface of the protective film forming film 13 (i.e., the first surface 13a of the protective film forming film 13) to the workpiece; and a second lamination step of attaching the support sheet 10 to the surface of the protective film forming film opposite to the exposed surface (i.e., the second surface 13b of the protective film forming film).

[0084] Figure 2 This is an example of the use of the first laminate 5, which is a cross-sectional schematic diagram illustrating an example of the step of peeling off the first release film of the first laminate in the manufacturing method of the third laminate of this embodiment.

[0085] For the first layer 5 ( Figure 2 In A), for example, a circular punching blade 70 is inserted from the side of the first peeling film 151, which serves as a light-surface peeling film. Figure 2 (B) and peel off the first peeling film 151. Figure 2 (C in the middle).

[0086] Figure 3 A in Figure 3 D in the diagram is a schematic cross-sectional view illustrating an example of the first lamination process in the manufacturing method of the third laminate of this embodiment.

[0087] In the first lamination process, the exposed surface of the protective film forming film 13 (i.e., the first surface 13a of the protective film forming film 13) formed by peeling off the first release film 151 of the first laminate 5 is attached to the workpiece 14, which is the object to be protected. Figure 3 A in ( Figure 3 B and Figure 3 (C in the text). Next, the second peeling film 152 is peeled off, exposing the side of the protective film forming film 13 opposite to the exposed side (i.e., the second side 13b of the protective film forming film). Figure 3 (D in the middle).

[0088] In this embodiment, the workpiece 14 is a semiconductor wafer with a circuit surface 14a on one side, and a backing tape 17 is attached to the circuit surface 14a of the workpiece 14.

[0089] Figure 3 E and Figure 3 F in the diagram represents an example of the use of the support sheet 10, and is a cross-sectional schematic diagram illustrating an example of the second lamination process in the manufacturing method of the third laminate of this embodiment.

[0090] In the second lamination process, a second laminate 6, on which a protective film 13 is attached to the workpiece 14, is formed by attaching a protective film to the workpiece 14. Figure 3 A support sheet 10 is attached to the side of the protective film forming membrane opposite to the exposed surface (i.e., the second surface 13b of the protective film forming membrane) in (D). Figure 3 E and Figure 3 (F in the text)

[0091] exist Figure 3 E and Figure 3 In the second lamination process shown in F, a support sheet 10 is attached to the second surface 13b of the protective film forming film 13 laminated on the back surface 14b of the workpiece 14. The support sheet 10 is, for example, a circular polypropylene film with a thickness of 80 μm, and has a clamping adhesive layer 16 on its outer periphery. In this embodiment, the workpiece 14 and the protective film forming film 13 are fixed together to a fixing clamp 18 (e.g., an annular frame). Furthermore, the support sheet 10 is attached to the second surface 13b of the protective film forming film 13, and simultaneously fixed to the fixing clamp 18 (e.g., an annular frame) by the clamping adhesive layer 16. Figure 3 (E in the middle).

[0092] If the support plate 10 itself has sufficient adhesion to the fixing clamp 18, it is not necessary to have an adhesive layer 16 for the clamp.

[0093] in the past, Figure 7 In section A, an apparatus for attaching a protective film 13 to the back side 8b of a semiconductor wafer 8, and... Figure 8 In the middle D, the device that attaches the support sheet 10 to the protective film 13' operates using separate devices. For each laminate, multiple laminates are stored in a cassette and transported to the next device.

[0094] However, in this embodiment, at least within an apparatus that connects the apparatus for performing the first lamination process and the apparatus for performing the second lamination process, or within the same apparatus, the process from... Figure 3 A in Figure 3 The first stacking process, indicated by D in the diagram, begins from... Figure 3 E and Figure 3 The operation up to the second lamination process shown in F in the diagram allows for the transfer of the second laminate 6, with the protective film forming film 13 attached to the workpiece 14, piece by piece, between the first and second lamination processes. That is, the protective film forming film 13 and the second laminate 6 of the workpiece 14 can be transferred without being stored in a box, within an apparatus that connects the apparatus for performing the first lamination process and the apparatus for performing the second lamination process, or within the same apparatus. Figure 4 The second stacking process is shown. Therefore, compared to using separate devices for each process, it is possible to suppress accidental waste adhesion and improve production cycle time.

[0095] In this embodiment, after the first lamination process, the process of peeling the second release film 152 from the second surface 13b side of the protective film forming film 13 is also performed in the apparatus that connects the apparatus for performing the first lamination process and the apparatus for performing the second lamination process, or in the same apparatus. Before the first lamination process, it is preferable that the process of peeling the first release film 151 from the first surface 13a side of the protective film forming film 13 of the first laminate 5 is also performed in the apparatus that connects the apparatus for performing the first lamination process and the apparatus for performing the second lamination process, or in the same apparatus.

[0096] In this embodiment, it can be started from the beginning. Figure 3 The location of attachment for the first layering process shown in Figure B, up to completion. Figure 3 The transport distance of workpiece 14 between the attachment points in the second lamination process shown in Figure F is set to less than 7000 mm, thereby reducing the equipment space. From the start... Figure 3 The attachment location and completion point of the first lamination process shown in Figure B. Figure 3 The conveying distance of the workpiece 14 between the attachment points in the second stacking process shown in F can be less than 6500mm, less than 6000mm, less than 4500mm, or less than 3000mm.

[0097] By ensuring that the transport distance of the workpiece 14 from the point where the first lamination process begins to the point where the second lamination process is completed is within the aforementioned range, the risk of accidental airborne debris adhering to the protective film forming film can be reduced.

[0098] In this embodiment, starting from the beginning Figure 3 The first lamination process shown in Figure B, from attachment to completion Figure 3 The transfer time of workpiece 14 during the second lamination process shown in Figure F can be less than 400 seconds, thereby shortening the process time. From the start... Figure 3The first lamination process shown in Figure B, from attachment to completion Figure 3 The transfer time of workpiece 14 between the attachment times in the second layering process shown in F can be less than 350s, less than 300s, less than 250s, less than 200s, or less than 150s.

[0099] By keeping the transport time of workpiece 14 from the start of the first lamination process to the completion of the second lamination process below the aforementioned upper limit, the risk of accidental airborne debris adhering to the protective film forming film can be reduced.

[0100] The time for transporting workpiece 14 from the start of the first layering process to the completion of the second layering process can be more than 50 seconds, more than 100 seconds, more than 150 seconds, or more than 200 seconds.

[0101] By ensuring that the transport time of workpiece 14 from the start of the first lamination process to the completion of the second lamination process is greater than the aforementioned lower limit, the transport speed is prevented from being too fast. Therefore, during the workpiece transport process, when the workpiece is moved while being held by the robotic arm, the workpiece can be properly held and prevented from falling. Furthermore, wear on the moving parts of the device can be reduced.

[0102] In the first lamination process, the speed at which the exposed surface of the protective film forming film 13 is attached to the workpiece 14, and in the second lamination process, the speed at which the support sheet 10 is attached to the surface of the protective film forming film 13 opposite to the exposed surface, can be 100 mm / s or less, or 80 mm / s or less, or 60 mm / s or less, or 40 mm / s or less. By keeping the attachment speed in the first lamination process and the attachment speed in the second lamination process at or below the aforementioned upper limits, the adhesion between the workpiece 14 and the protective film forming film 13, and the adhesion between the protective film forming film 13 and the support sheet 10, can be improved.

[0103] The attachment speed in the first and second lamination processes can be 2 mm / s or more, 5 mm / s or more, or 10 mm / s or more. By setting the attachment speed in the first and second lamination processes to the lower limit or above, the production efficiency of the third laminate 19 can be improved, and the transport time of the workpiece 14 from the start of the attachment in the first lamination process to the completion of the attachment in the second lamination process can be reduced to 400 seconds or less.

[0104] In this embodiment, next, in an apparatus that connects the apparatus for performing the first lamination process and the apparatus for performing the second lamination process, or in the same apparatus, the second surface 10b of the support sheet 10, which is opposite to the protective film forming film 13, is adsorbed onto the suction table 80, and the backing adhesive tape 17 is peeled off from the third laminate 19. Figure 4 A cross-sectional view is shown to illustrate an example of the backing tape being properly peeled off from the third laminate 19.

[0105] In this embodiment, a laminating roller at 70°C is used to attach the protective film forming film 13 to the mirror surface of a mirror-finished silicon wafer. After 5 minutes of attachment, at a peeling speed of 100 mm / min and a temperature of 23°C, the 180° peel adhesion between the protective film forming film 13 and the silicon wafer is measured to be 900 mN / 25 mm or more.

[0106] By ensuring that the 180° peel adhesion between the protective film forming film 13 and the silicon wafer is greater than 900mN / 25mm after 5 minutes of application, the likelihood of peeling between the protective film forming film 13 and the workpiece 14 is reduced when the back-grinding tape 17 is peeled off. Figure 5 A cross-sectional view illustrating an example of a defect that occurs when the back-grinding tape 17 is peeled off from the third laminate 19, between the protective film forming film 13 and the workpiece 14.

[0107] The manufacturing method of the third laminate of this embodiment, using the kit of this embodiment, utilizes the kit in an online process. In this embodiment, after the second lamination process, the step of peeling the backing tape from the workpiece is also performed in an apparatus that connects the apparatus for performing the first lamination process and the apparatus for performing the second lamination process, or in the same apparatus, thereby enabling online processing. The manufacturing method of the third laminate of this embodiment can begin peeling the backing tape from the workpiece within 10 minutes of the attachment process starting in the first lamination process. This reduces the risk of material transfer between the support sheet 10 and the protective film forming film 13.

[0108] Will Figure 7When the conventional protective film forming film 13 used in the manufacturing method of the semiconductor chip with protective film shown is applied in the manufacturing method of the third laminate of this embodiment, since the manufacturing method of the third laminate of this embodiment uses an in-line process to perform a first lamination step of attaching the protective film forming film 13 to the workpiece 14 and a second lamination step of attaching the support sheet 10 to the protective film forming film 13, the backing tape 17 may be peeled off before the adhesion between the workpiece 14 and the protective film forming film 13 has become strong. Therefore, when the backing tape 17 is peeled off from the third laminate 19, peeling may occur between the workpiece 14 and the protective film forming film 13.

[0109] As described above, for the kit of this embodiment, the protective film forming film 13 is attached to the mirror surface of the mirror-finished silicon wafer using a laminating roller at 70°C. After 5 minutes of attachment, the 180° peel adhesion between the protective film forming film 13 and the silicon wafer is 900mN / 25mm or more. Since the 180° peel adhesion between the protective film forming film 13 and the silicon wafer becomes stronger in a short time after attachment, the possibility of peeling between the protective film forming film 13 and the workpiece 14 is reduced when the back-grinding tape 17 is peeled off.

[0110] After 5 minutes of application, the 180° peel adhesion between the protective film 13 and the silicon wafer is preferably 950 mN / 25 mm or more, more preferably 1050 mN / 25 mm or more, and particularly preferably 1150 mN / 25 mm or more.

[0111] From the perspective of preventing accidental peeling during processes such as handling after peeling off the backing tape, the 180° peel adhesion between the protective film 13 formed after 30 minutes of application and the silicon wafer is preferably 1100mN / 25mm or more, more preferably 1150mN / 25mm or more, and particularly preferably 1200mN / 25mm or more.

[0112] In this embodiment, the support sheet 10 is attached to the protective film forming film 13 using a laminating roller at 23°C. After 3 minutes of attachment, the 180° peel adhesion between the protective film forming film 13 and the support sheet 10, measured at a peeling speed of 100 mm / min and a temperature of 23°C, is preferably 100 mN / 25 mm or more.

[0113] By ensuring that the 180° peel adhesion between the protective film forming film 13 and the support sheet 10 after 3 minutes of application is 100mN / 25mm or more, the likelihood of peeling between the protective film forming film 13 and the support sheet 10 is reduced when the backing tape 17 is peeled off. Figure 6A cross-sectional view illustrating an example of a defect that occurs when the backing tape 17 is peeled off from the third laminate 19, between the protective film forming film 13 and the support sheet 10.

[0114] After 3 minutes of application, the 180° peel adhesion between the protective film 13 and the support sheet 10 can be 110mN / 25mm or more, or 120mN / 25mm or more, or 130mN / 25mm or more, or 180mN / 25mm or more, or 230mN / 25mm or more.

[0115] From the perspective of preventing accidental peeling during the process after peeling off the backing tape, the 180° peel adhesion between the protective film 13 formed after 30 minutes of application and the support sheet is preferably 120mN / 25mm or more, more preferably 200mN / 25mm or more, and particularly preferably 220mN / 25mm or more.

[0116] In this embodiment, as Figure 3 Workpiece 14, shown as A, uses a semiconductor wafer. One side of the semiconductor wafer is a circuit surface 14a, and bumps are formed thereon. Furthermore, to prevent the circuit surface 14a and bumps of the semiconductor wafer from breaking or developing dents or cracks on the back side of the wafer during grinding, the circuit surface 14a and bumps are protected with circuit surface protective tape. The circuit surface protective tape is a back-grinding tape 17, and the back side of the semiconductor wafer (i.e., the back side 14b of the workpiece) is the ground surface.

[0117] As for workpiece 14, there is no limitation as long as it has a circuit surface 14a on one side and the other side can be referred to as the back side. Examples of workpiece 14 include a semiconductor wafer with a circuit surface on one side, or a semiconductor device panel composed of an assembly of semiconductor devices with terminals formed by sealing resin and individual electronic components that have been singulated and sealed with sealing resin, and having a terminal forming surface (in other words, a circuit surface) of a semiconductor device with terminals on one side.

[0118] As the back-abrasion tape 17, for example, a surface protection sheet disclosed in Japanese Patent Application Publication No. 2016-192488 and Japanese Patent Application Publication No. 2009-141265 can be used. The back-abrasion tape 17 has an adhesive layer with moderate re-peelability. The adhesive layer can be formed from a common weak-adhesion adhesive such as rubber resin, acrylic resin, silicone resin, polyurethane resin, or polyvinyl ether. Furthermore, the adhesive layer can be an energy-cured adhesive that is cured by energy irradiation to become re-peelable. The back-abrasion tape 17 is in the shape of a double-sided tape, and the outer side of the back-abrasion tape 17 can be fixed to a rigid support, or the workpiece 14 can be fixed to the rigid support.

[0119] In this specification, "energy rays" refers to rays containing energy quanta within electromagnetic waves or beams of charged particles. Examples of energy rays include ultraviolet light, radiation, and electron beams. For instance, ultraviolet light can be irradiated using a high-pressure mercury lamp, fusion lamp, xenon lamp, black light, or LED light as a source. As for electron beams, electron beams generated by electron beam accelerators or similar devices can be used.

[0120] Furthermore, in this specification, "energy-ray curing property" refers to the property of curing by irradiation with energy rays, and "non-energy-ray curing property" refers to the property of not curing even when irradiated with energy rays.

[0121] <First Layer>

[0122] The first laminate 5 can be manufactured, for example, as follows: A protective film forming composition containing solvent is coated onto the release surface of a second release film 152 with a thickness of 38 μm using a doctor blade coater. The coated surface is then dried in an oven at 120°C for 2 minutes to form a protective film forming film. Next, the release surface of a first release film 151 with a thickness of 38 μm is superimposed on the protective film forming film, and the two are bonded together to obtain the first laminate 5 composed of the first release film 151, the protective film forming film (thickness: 25 μm), and the second release film 152. Such a first laminate 5 is suitable for storage, for example, in roll form.

[0123] The first laminate 5 can be manufactured by setting the release surface of the first release film 151 to a rough surface with a surface roughness Ra of, for example, 200 nm, and setting the release surface of the second release film 152 to a smooth surface with a surface roughness Ra of, for example, 30 nm, which is smoother than the rough surface.

[0124] Alternatively, even if the surface roughness Ra of the peeling surface of the first peeling film 151 is the same as the surface roughness of the peeling surface of the second peeling film 152, the first laminate 5 can be manufactured in, for example, the following manner.

[0125] Specifically, a protective film forming composition containing solvent is coated onto the release surface of the second release film 152 with a surface roughness Ra of 30 nm using a doctor blade coater, and then dried in an oven at 120°C for 2 minutes to form a protective film forming film. Next, a first release film 151 with a surface roughness Ra of 30 nm and a thickness of 38 μm is superimposed on the protective film forming film, and the two are bonded together under conditions such as 23°C and 0.4 MPa to obtain a protective film forming film composed of the first release film 151, the protective film forming film 13 (thickness: 25 μm), and the second release film 152. Thus, the first surface 13a of the protective film forming film 13 and the first release film 151 form a light release surface, while the second surface 13b of the protective film forming film 13 and the second release film 152 form a heavy release surface with a greater release strength than the light release surface. This first laminate 5 is also suitable for storage in, for example, a roll form.

[0126] The surface roughness of the first release film 151 side of the protective film forming film can be adjusted according to the temperature and pressure conditions of the release surface of the first release film 151 adhered to the protective film forming film. If the temperature and pressure conditions of the release surface of the first release film 151 adhered to the protective film forming film are increased, the surface roughness of the first release film 151 side of the protective film forming film will be faithful to the surface roughness of the release surface of the first release film 151.

[0127] The surface roughness Ra of the rough surface of the protective film formed by the protective film adhered to the back side of the workpiece can be 32-1200 nm, preferably 32-1000 nm, more preferably 32-900 nm, and particularly preferably 32-800 nm.

[0128] The greater the surface roughness Ra of the rough side of the protective film forming membrane, the smaller the area in substantial contact with the release film. Therefore, by making the surface roughness Ra of the rough side of the protective film forming membrane above the lower limit value, it is easier to peel off preferentially when the rough side of the protective film forming membrane is peeled off.

[0129] Therefore, when peeling off the light-side peeling film, the risk of the protective film forming film not being properly peeled off from the light-side peeling film, resulting in a portion of the protective film forming film remaining on the light-side peeling film, also known as poor peeling, or "tears of separation," can be reduced.

[0130] The surface roughness Ra of the smooth surface of the protective film formed on the side attached to the support sheet is preferably 20-80 nm, preferably 24-50 nm, and preferably 28-32 nm.

[0131] The ratio of the surface roughness Ra of the rough surface of the protective film to the surface roughness Ra of the smooth surface of the protective film (surface roughness Ra of the rough surface / surface roughness Ra of the smooth surface) can be 1.1 to 50, 1.2 to 45, 1.3 to 35, 1.4 to 30, or 1.5 to 24.

[0132] Protective film forming films can be formed using a protective film forming composition containing its constituent materials. For example, a protective film forming film can be formed by coating a protective film forming composition onto its forming surface (e.g., a release film) and drying it as needed. The content ratio of the components that do not vaporize at room temperature in the protective film forming composition is generally the same as the content ratio of the components in the protective film forming film. In this specification, "room temperature" means a temperature without special cooling or heating, i.e., a normal temperature, such as temperatures of 15 to 25°C.

[0133] (Protective film forming composition)

[0134] In applications where strong protective performance is not required, a protective film forming composition without curing agents can be used as a component of the protective film forming composition. This is convenient as it eliminates the need for a curing process. However, due to the brittleness of the chip, sufficient adhesion and protective performance may not be achieved. Preferably, the protective film forming composition contains both polymer and curing agents.

[0135] Polymer components are sometimes also curable components. In this specification, when a protective film forming composition contains components that are both polymeric and curable components, it is considered that the protective film forming composition contains both polymeric and curable components.

[0136] (Polymer composition)

[0137] To impart sufficient adhesion and film-forming properties (sheet-forming properties) to the protective film, polymer components can be used. Acrylic resins, polyester resins, polyurethane resins, silicone resins, etc., can be used as polymer components.

[0138] The weight-average molecular weight (Mw) of the polymer component is preferably between 10,000 and 2,000,000, more preferably between 100,000 and 1,200,000. If the weight-average molecular weight of the polymer component is above the lower limit mentioned above, the release film is easy to peel off, reducing the risk of poor peeling, also known as "tear peeling". If the weight-average molecular weight of the polymer component is below the upper limit mentioned above, it can prevent the protective film from failing to adhere to the workpiece due to reduced adhesion, and can prevent the protective film from peeling off from the workpiece after application.

[0139] Acrylic resin is preferably used as the polymer component. The glass transition temperature (Tg) of the acrylic resin is preferably in the range of -60 to 50°C, more preferably in the range of -50 to 40°C, and particularly preferably in the range of -40 to 30°C.

[0140] If the glass transition temperature of the acrylic resin is above the lower limit mentioned above, the release film is easy to peel off, reducing the risk of poor peeling, also known as "tears". If the glass transition temperature of the acrylic resin is below the upper limit mentioned above, it can prevent the protective film from failing to adhere to the workpiece due to reduced adhesion, and can prevent the protective film from peeling off the workpiece after application. In addition, it can reduce the risk of cracks (fissures) occurring when the protective film is bent during roll forming.

[0141] From the perspective of adhesion, bonding and film-forming properties, the preferred content of polymer components relative to the total weight of the protective film formed (100 parts) is 5-50 parts by mass, 10-45 parts by mass, 14-40 parts by mass, and 18-35 parts by mass.

[0142] The glass transition temperature (Tg) of the resin that constitutes the polymer component can be calculated using the Fox formula shown below.

[0143] 1 / Tg=(W1 / Tg1)+(W2 / Tg2)+……+(Wm / Tgm)

[0144] In the formula, Tg is the glass transition temperature of the resin constituting the polymer component, Tg1, Tg2, ..., Tgm are the glass transition temperatures of the homopolymers of each monomer used as a raw material for the resin constituting the polymer component, and W1, W2, ..., Wm are the mass fractions of each monomer. Wherein, W1 + W2 + ... + Wm = 1.

[0145] The glass transition temperatures of the homopolymers of the monomers in the Fox formula can be obtained using values ​​recorded in polymer datasheets, adhesive handbooks, or polymer handbooks. For example, the glass transition temperatures of homopolymers are as follows: methyl acrylate is 10°C, methyl methacrylate is 105°C, 2-hydroxyethyl acrylate is -15°C, n-butyl acrylate is -54°C, and glycidyl methacrylate is 41°C.

[0146] As monomers constituting the aforementioned acrylic resins, examples include (meth)acrylate monomers or their derivatives. For instance, alkyl (meth)acrylates with 1 to 18 carbon atoms in the alkyl group can be listed, specifically including methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Furthermore, (meth)acrylates having a cyclic skeleton can be listed, specifically including cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and (meth)acrylate imide. Further, as monomers having functional groups, examples include hydroxyl-containing (meth)acrylate methyl methacrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate; in addition, glycidyl (meth)acrylate having epoxy groups can also be listed. For acrylic resins, acrylic resins containing monomers with hydroxyl groups are preferred because they have good compatibility with the curing components described later. Furthermore, the aforementioned acrylic resins can be copolymerized with acrylic acid, methacrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, etc.

[0147] Furthermore, as a polymer component, a thermoplastic resin for maintaining the flexibility of the cured protective film can be incorporated. Preferably, the thermoplastic resin has a weight-average molecular weight of 1,000 to 100,000, and more preferably, a thermoplastic resin with a weight-average molecular weight of 3,000 to 80,000. Preferably, the glass transition temperature of the thermoplastic resin is -30 to 120°C, and more preferably -20 to 120°C. Examples of thermoplastic resins include polyester resins, polyurethane resins, phenoxy resins, polybutene, polybutadiene, and polystyrene. These thermoplastic resins can be used alone or in combination of two or more. By including the above-mentioned thermoplastic resins, the protective film forming film follows the transfer surface of the protective film forming film, thus suppressing the formation of voids.

[0148] (Curing components)

[0149] The curing component can be a thermosetting component and / or an energy-curable component. This allows the protective film to be thermosetting and / or energy-curable.

[0150] By using a thermosetting protective film to form a film, even if the protective film is thick, it can be easily heat-cured, thus making it possible to form a thick protective film with good protective performance. Multiple workpieces can be cured simultaneously during the heat curing process.

[0151] By using energy-curable protective film formation, the protective film can be cured by energy rays in a short time.

[0152] Thermosetting components can be thermosetting resins and thermosetting agents. For example, epoxy resins are preferred as thermosetting resins.

[0153] As epoxy resins, conventionally known epoxy resins can be used. Specifically, examples of epoxy resins include multifunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether or its hydride, o-cresin phenolic varnish epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and phenylene skeleton type epoxy resins, etc., all epoxy compounds having more than one level of functionality in their molecules. These epoxy resins can be used alone or in combination of two or more.

[0154] Relative to the total weight of the protective film forming film 100, the preferred content of the thermosetting component is 1 to 75 parts by mass, more preferably 2 to 60 parts by mass, even more preferably 3 to 50 parts by mass, for example, 4 to 40 parts by mass, 5 to 35 parts by mass, or 6 to 30 parts by mass.

[0155] If the content of thermosetting resin is above the lower limit mentioned above, sufficient adhesion between the protective film and the workpiece can be obtained, and the protective film has excellent performance in protecting the workpiece. If it is below the upper limit mentioned above, the preservation stability is excellent when stored in roll form.

[0156] Thermosetting agents function as curing agents for thermosetting resins, especially epoxy resins. Preferred thermosetting agents include compounds having two or more functional groups per molecule capable of reacting with epoxy groups. Examples of such functional groups include phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, and acid anhydrides. Phenolic hydroxyl groups, amino groups, and acid anhydrides are preferred examples, with phenolic hydroxyl groups and amino groups being even more preferred.

[0157] Specific examples of phenolic curing agents include polyfunctional phenolic resins, biphenyl, phenolic varnish-type phenolic resins, dicyclopentadiene phenolic resins, Zylock-type phenolic resins, and arylalkylphenol resins. Specific examples of amine curing agents include DICY (dicyandiamide). These curing agents can be used alone or in combination of two or more.

[0158] The content of the thermosetting agent is preferably 0.1 to 500 parts by weight, more preferably 1 to 200 parts by weight, relative to 100 parts by weight of the thermosetting resin. If the content of the thermosetting agent is above the lower limit mentioned above, sufficient curing can achieve adhesion; if it is below the upper limit mentioned above, the moisture absorption rate of the protective film is suppressed, and the adhesion reliability between the workpiece and the protective film is improved.

[0159] As an energy-ray curing component, a low-molecular-weight compound (energy-ray polymerizable compound) containing energy-ray polymerizable groups and which polymerizes and cures upon exposure to energy rays such as ultraviolet light or electron beams can be used. Specifically, examples of such energy-ray curable components include trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxy pentaacrylate, dipentaerythritol hexaacrylate, or acrylates such as 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, low-polyester acrylates, urethane acrylate oligomers, epoxy-modified acrylates, polyether acrylates, and itaconic acid oligomers. Such compounds have at least one polymerizable double bond within their molecules and typically have a weight-average molecular weight of 100–30,000, preferably around 300–10,000. Relative to the total weight of the protective film forming film 100, the preferred content of the energy-curable component is 1 to 80 parts by mass, more preferably 2 to 70 parts by mass, and even more preferably 3 to 60 parts by mass, for example, 4 to 50 parts by mass or 5 to 40 parts by mass.

[0160] Furthermore, as an energy-ray curing component, an energy-ray curable polymer can be formed by bonding energy-ray polymerizable groups to the main chain or side chain of the polymer component. Such an energy-ray curable polymer combines the functions of both a polymer component and a curing component.

[0161] The main skeleton of energy ray-cured polymers is not particularly limited and can be acrylic resin, which is commonly used as a polymer component. In addition, it can also be polyester, polyether, etc. However, since the synthesis and physical properties are relatively easy to control, acrylic resin is particularly preferred as the main skeleton.

[0162] The energy-polymerizable groups bonded to the main chain or side chains of the energy-curable polymer are, for example, groups containing carbon-carbon double bonds that are energy-polymerizable, such as (meth)acryloyl groups. The energy-polymerizable groups can be bonded to the energy-curable polymer via alkylene groups, alkoxy groups, or polyalkoxy groups.

[0163] The weight-average molecular weight (Mw) of the energy-curable polymer bonded with energy-ray polymerizable groups is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000. Furthermore, the glass transition temperature (Tg) of the energy-ray curable polymer is preferably in the range of -60 to 50°C, further preferably in the range of -50 to 40°C, and particularly preferably in the range of -40 to 30°C.

[0164] Energy-curable polymers can be obtained, for example, by reacting an acrylic resin containing functional groups such as hydroxyl, carboxyl, amino, substituted amino, or epoxy groups with a polymerizable group containing polymerizable groups, such as 1 to 5 substituents that react with the functional group and energy-ray polymerizable carbon-carbon double bonds per molecule. Examples of substituents that react with the functional group include isocyanate groups, glycidyl groups, and carboxyl groups.

[0165] Examples of compounds containing polymerizable groups include (meth)acryloyloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, (meth)acryloyl isocyanate, allyl isocyanate, glycidyl (meth)acrylate, and (meth)acrylic acid.

[0166] The acrylic resin is preferably a copolymer formed from (meth)acrylic acid monomers or their derivatives having functional groups such as hydroxyl, carboxyl, amino, substituted amino, and epoxy groups, and other (meth)acrylic acid ester monomers or their derivatives that can be copolymerized with them.

[0167] (Meth)acrylic acid monomers or their derivatives having functional groups such as hydroxyl, carboxyl, amino, substituted amino, and epoxy groups include, for example, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate with hydroxyl groups; acrylic acid, methacrylic acid, and itaconic acid with carboxyl groups; and glycidyl methacrylate and glycidyl acrylate with epoxy groups.

[0168] Other (meth)acrylate monomers or their derivatives that can be copolymerized with the above-mentioned monomers include, for example, alkyl (meth)acrylates with alkyl groups having 1 to 18 carbon atoms, specifically methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.; and (meth)acrylates having a cyclic skeleton, specifically cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, acrylateimide, etc. Furthermore, vinyl acetate, acrylonitrile, styrene, etc., can be copolymerized into the above-mentioned acrylic resins.

[0169] Even when using energy-curable polymers, the aforementioned energy-curable polymeric compound can be used simultaneously, as can the polymer component. Regarding the relationship between the proportions of these three components in the protective film forming film of the present invention, the energy-curable polymeric compound is preferably included in the amount of 1 to 1500 parts by mass, more preferably in the amount of 100 parts by mass of the sum of the energy-curable polymer and the polymer component, and particularly preferably in the amount of 20 to 200 parts by mass.

[0170] As mentioned above, the curing conditions for forming a protective film by thermosetting the protective film are not particularly limited as long as the degree of curing allows the protective film to fully perform its function. It is only necessary to make appropriate selections based on the type of thermosetting protective film.

[0171] The curing conditions for forming a protective film that can be cured by energy rays are not particularly limited as long as the degree of curing is sufficient to allow the protective film to fully perform its function. It is only necessary to make appropriate selections based on the type of protective film that can be cured by energy rays.

[0172] For example, when curing an energy-curable protective film with energy rays, the preferred energy irradiation is 4–280 mW / cm². 2 Furthermore, the intensity of the energy rays during curing is preferably 3–1000 mJ / cm². 2 .

[0173] In addition to the polymer and curing components mentioned above, the protective film may also contain the following components.

[0174] (Coloring agent)

[0175] The protective film forming film preferably contains a colorant. By incorporating a colorant into the protective film forming film, infrared radiation and other harmful substances generated from surrounding devices can be blocked when assembling a semiconductor device into a machine, preventing malfunctions of the semiconductor device caused by these sources. Furthermore, the visibility of text such as product serial numbers printed on the protective film obtained after curing the protective film forming film is improved. Specifically, in semiconductor devices or semiconductor chips with a protective film, product serial numbers and other information are typically printed on the surface of the protective film using laser marking (a method of printing text by using a laser to remove the surface of the protective film). By containing a colorant in the protective film, the contrast difference between the laser-removed portion and the unremoved portion of the protective film can be fully obtained, thus improving visibility. Organic or inorganic pigments and dyes can be used as colorants. Pigments are preferred from the perspective of heat resistance, etc. Carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, etc., can be used as pigments, but are not limited to these. Among these, carbon black is particularly preferred from the perspective of operability and dispersibility. Colorants can be used alone or in combination of two or more.

[0176] The amount of colorant incorporated is preferably 0.1 to 35 parts by mass relative to 100 parts by mass of the total solids that constitute the protective film, more preferably 0.5 to 25 parts by mass, and particularly preferably 1 to 15 parts by mass.

[0177] (Curing accelerator)

[0178] Curing accelerators are used to regulate the curing speed of the protective film. It is particularly preferred to use a curing accelerator when both epoxy resin and a thermosetting agent are used in the curing component.

[0179] Preferred curing accelerators include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-

[0180] Imidazoles such as methyl-5-hydroxymethylimidazolium; organophosphorus compounds such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenylborates such as tetraphenylphosphine and triphenylphosphine tetraphenyl borate. These curing agents can be used alone or in combination of two or more.

[0181] The curing accelerator is preferably included in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 1 part by weight, relative to 100 parts by weight of the curing component. By including the curing accelerator in the above range, excellent adhesion properties are achieved even when exposed to high temperature and high humidity, and high adhesion reliability is achieved even when exposed to harsh reflow soldering conditions.

[0182] (Coupled agent)

[0183] Coupling agents can be used to improve the adhesion reliability of the protective film to the workpiece. Furthermore, by using coupling agents, the water resistance of the protective film obtained through curing is improved without compromising its heat resistance.

[0184] As a coupling agent, compounds having functional groups that can react with polymer components, curing components, etc., are preferred. Silane coupling agents are ideally chosen as coupling agents. Examples of such coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-(methacryloyloxypropyl)trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)-γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureapropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazole silane, etc. These coupling agents can be used alone or in combination of two or more.

[0185] The coupling agent is typically included in a proportion of 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, and more preferably 0.3 to 5 parts by weight, relative to 100 parts by weight of the total polymer and curing components. If the content of the coupling agent is less than 0.1 parts by weight, the above-mentioned effect may not be obtained, and if it is greater than 20 parts by weight, degassing may occur. By keeping the content of the coupling agent within the above range, it is easy to adjust the adhesion between the protective film forming film and the support sheet after 3 minutes, and the adhesion between the protective film forming film and the silicon wafer after 5 minutes.

[0186] (Filling material)

[0187] By incorporating filler materials into the protective film, the coefficient of thermal expansion in the cured protective film can be adjusted. Optimizing the coefficient of thermal expansion of the cured protective film for semiconductor chips can improve the adhesion reliability between the workpiece and the protective film. Inorganic filler materials are preferred. Furthermore, the moisture absorption rate of the cured protective film can be reduced.

[0188] Preferred inorganic filler materials include powders such as silica, alumina, talc, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, and boron nitride, as well as beads formed by spherizing these materials, single-crystal fibers, and glass fibers. Silica and alumina fillers are preferred. One or more of the above inorganic filler materials can be used alone or in combination. The content of the inorganic filler material relative to 100 parts by mass of the total solids constituting the protective film can be 1–85 parts by mass, 5–80 parts by mass, 10–75 parts by mass, 20–70 parts by mass, or 30–66 parts by mass.

[0189] By keeping the content of inorganic filler material below the aforementioned upper limit, the risk of cracks (fissures) occurring when bending the protective film during roll forming can be reduced; by keeping it above the aforementioned lower limit, the heat resistance of the protective film can be improved. Furthermore, by keeping the content of inorganic filler within the aforementioned range, it is easier to adjust the adhesion between the protective film and the support sheet after 3 minutes, and the adhesion between the protective film and the silicon wafer after 5 minutes.

[0190] (Photopolymerization initiator)

[0191] When the protective film forming film contains an energy-curing component as the aforementioned curing component, it is cured by irradiating it with energy rays such as ultraviolet light during use. In this case, by including a photopolymerization initiator in the composition, the polymerization curing time and the amount of light irradiation can be reduced.

[0192] Examples of photopolymerization initiators include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoate, benzoin dimethyl ketal, 2,4-diethylthioxanthone, α-hydroxycyclohexylphenyl ketone, benzyl phenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzoyl (benzil), dibenzoyl, diacetyl, 1,2-diphenylmethane, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and β-chloroanthraquinone. One photopolymerization initiator can be used alone or in combination of two or more.

[0193] As for the blending ratio of the photopolymerization initiator, it is preferable to include 0.1 to 10 parts by mass of the photopolymerization initiator relative to 100 parts by mass of the energy-curable component, and more preferably 1 to 5 parts by mass of the photopolymerization initiator. If the ratio is above or below the lower limit, sufficient protective performance can be obtained through photopolymerization, and if the ratio is below the upper limit, the generation of residues that do not contribute to photopolymerization can be suppressed, thereby ensuring sufficient curing of the protective film.

[0194] (Cross-linking agent)

[0195] To adjust the adhesion and cohesiveness between the protective film and the workpiece, crosslinking agents can be added. Examples of crosslinking agents include organic polyisocyanate compounds and organic polyimide compounds.

[0196] Examples of the aforementioned organic polyisocyanate compounds include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, trimers of their organic polyisocyanate compounds, and terminal isocyanate carbamate prepolymers obtained by reacting these organic polyisocyanate compounds with polyol compounds.

[0197] Examples of organic polyisocyanate compounds include, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-phenylenedimethylene diisocyanate; 1,4-phenylenedimethylene diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylolpropane adduct toluene diisocyanate; and lysine isocyanate.

[0198] Examples of the aforementioned organic polyimide compounds include N,N'-diphenylmethane-4,4'-bis(1-aziridinylcarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, and N,N'-toluene-2,4-bis(1-aziridinylcarboxamide)triethylene melamine.

[0199] The crosslinking agent is typically used at a ratio of 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the polymer components and the energy-curable polymer.

[0200] (General Additive)

[0201] In addition to the above, various additives can be incorporated into the protective film as needed. Examples of such additives include adhesion promoters, leveling agents, plasticizers, antistatic agents, antioxidants, ion trapping agents, gettering agents, and chain transfer agents.

[0202] (solvent)

[0203] The protective film forming composition preferably further contains a solvent. Protective film forming compositions containing solvents exhibit good processability.

[0204] The solvent is not particularly limited, but preferred solvents include, for example, hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds with amide bonds) such as dimethylformamide and N-methylpyrrolidone.

[0205] The protective film forming composition may contain only one solvent or two or more solvents. When there are two or more solvents, their combination and ratio can be arbitrarily selected.

[0206] From the perspective of enabling more uniform mixing of the components in the adhesive composition, the solvent contained in the protective film forming composition is preferably methyl ethyl ketone or the like.

[0207] The protective film formed by coating and drying the protective film forming composition composed of the components described above has adhesiveness and curability. In its uncured state, it is bonded to a workpiece (such as a semiconductor wafer or chip) by pressing it onto the workpiece. The protective film forming film can be heated during pressing. After curing, a protective film with high impact resistance and excellent adhesive strength is finally provided, maintaining sufficient protective function even under harsh high temperature and high humidity conditions. Furthermore, the protective film forming film can be a single-layer structure, or a multi-layer structure as long as it contains one or more layers containing the above-described components.

[0208] The thickness of the protective film is not particularly limited; it can be 3–300 μm, 3–200 μm, 5–100 μm, 7–80 μm, 10–70 μm, 12–60 μm, 15–50 μm, 18–40 μm, or 20–30 μm.

[0209] If the thickness of the protective film is above the lower limit mentioned above, the protective performance of the protective film can be sufficient. If it is below the upper limit mentioned above, the cost can be reduced and the energy rays can reach the interior of the protective film formed by the energy rays curing.

[0210] <Supporting sheet>

[0211] As one embodiment of the present invention, the support sheet used can be exemplified by a sheet consisting solely of a substrate or an adhesive sheet having an adhesive layer laminated on the substrate.

[0212] The support plate serves as: a release plate to prevent dust and other contaminants from adhering to the surface of the protective film forming film; or a conveying plate that is attached to a fixing fixture such as a ring frame and a workpiece with a protective film forming film, and can maintain the fixing fixture and carry out the conveying without the robotic arm directly contacting the workpiece with the protective film forming film.

[0213] The thickness of the support sheet can be appropriately selected according to the application. From the perspective of ensuring good adhesion to the workpiece with the protective film and the fixing fixture, it is preferably 10 to 500 μm, more preferably 20 to 350 μm, and even more preferably 30 to 200 μm.

[0214] In addition, the thickness of the aforementioned support sheet includes not only the thickness of the substrate constituting the support sheet, but also the thickness of these layers or films when an adhesive layer is present, excluding the release film and the like that not attached to the protective film forming film.

[0215] (Substrate)

[0216] A resin film is preferred as the substrate constituting the support sheet.

[0217] Examples of such resin films include low-density polyethylene (LDPE) films or linear low-density polyethylene (LLDPE) films, polyethylene films, ethylene-propylene copolymer films, polypropylene films, polybutene films, polybutadiene films, polymethylpentene films, polyvinyl chloride films, vinyl chloride copolymer films, polyethylene terephthalate films, polyethylene naphthalate films, polybutylene terephthalate films, polyurethane films, ethylene-vinyl acetate copolymer films, ionomer resin films, ethylene-(meth)acrylic acid copolymer films, ethylene-(meth)acrylic acid copolymer films, polystyrene films, polycarbonate films, polyimide films, fluoropolymer films, etc.

[0218] In one embodiment of the present invention, the substrate used may be a single-layer film formed of a resin film, or a laminated film consisting of two or more resin films.

[0219] Furthermore, in one aspect of the present invention, a sheet on which the surface of the aforementioned resin film or other substrate has undergone surface treatment can be used as a support sheet.

[0220] These resin films can be cross-linked films.

[0221] Furthermore, resin films obtained by coloring these resin films or by printing them can also be used. Moreover, the resin film can be a resin film obtained by extruding thermoplastic resin into sheets, a stretched resin film, or a resin film obtained by filming and curing a curable resin film using a prescribed method.

[0222] Among these resin films, a substrate comprising a polypropylene film is preferred from the perspective of having excellent heat resistance, moderate flexibility for spreadability, and easy maintenance of pick-up adaptability.

[0223] Furthermore, the composition of the substrate containing the polypropylene film can be a single-layer structure formed solely of the polypropylene film, or a multi-layer structure formed by the polypropylene film and other resin films.

[0224] When the protective film is thermosetting, by making the resin film constituting the substrate heat-resistant, damage to the substrate caused by heat can be suppressed, and adverse conditions in the manufacturing process of semiconductor devices can be suppressed.

[0225] The thickness of the substrate constituting the support sheet is preferably 10 to 500 μm, more preferably 15 to 300 μm, and even more preferably 20 to 200 μm.

[0226] (Adhesive sheet)

[0227] As an adhesive sheet used as the support sheet 10 in one aspect of the present invention, an adhesive sheet having an adhesive layer 12 formed of an adhesive on the substrate 11 such as the resin film can be cited as an example. By having an adhesive layer 12, the 180° peel adhesion between the protective film forming film and the support sheet can be easily adjusted.

[0228] Adhesives used as forming materials for adhesive layers include adhesive compositions comprising adhesive resins, which may further contain general additives such as the aforementioned crosslinking agents or adhesive imparting agents.

[0229] When considering the structure of such an adhesive resin, examples include acrylic resin, polyurethane resin, rubber resin, silicone resin, and polyethylene ether. When considering the function of such a resin, examples include energy ray curable adhesives.

[0230] The 180° peel adhesion (β2) between the protective film formed by the protective film forming film and the support sheet is preferably 0.03 to 4.0 N / 25 mm, more preferably 0.05 to 2.5 N / 25 mm, even more preferably 0.10 to 2.0 N / 25 mm, and even more preferably 0.15 to 1.5 N / 25 mm.

[0231] In one aspect of the invention, from the perspective of adjusting the adhesion (β2) between the protective film and the support sheet within the above-mentioned range and from the perspective of achieving good pick-up, it is preferable to use an adhesive sheet with an adhesive layer having energy-ray curable properties formed from an adhesive composition containing an energy-ray curable resin, or an adhesive sheet with a micro-adhesive adhesive layer.

[0232] As an energy ray curable resin, any resin having polymerizable groups such as (meth)acryloyl or vinyl groups is acceptable, and an adhesive resin having polymerizable groups is preferred.

[0233] Furthermore, from the perspective of adjusting the 180° peel adhesion and adhesion (β2) between the protective film forming film and the support sheet to the range described above, an adhesive containing acrylic resin is preferred.

[0234] As the acrylic resin, an acrylic polymer having a structural unit (x1) derived from an alkyl methacrylate is preferred, and an acrylic copolymer having a structural unit (x1) and a structural unit (x2) derived from a monomer containing a functional group is more preferred.

[0235] The number of carbon atoms in the alkyl group of the above-mentioned (meth)acrylate is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8.

[0236] As the alkyl methacrylate, examples of alkyl methacrylates that are the same as those constituting the above-described structural unit (a1) can be listed.

[0237] In addition, alkyl (meth)acrylates can be used alone or in combination with two or more.

[0238] The content of structural unit (x1) is typically 50 to 100% by mass relative to the total structural units (100% by mass) of the acrylic polymer, preferably 50 to 99.9% by mass, more preferably 60 to 99% by mass, and even more preferably 70 to 95% by mass.

[0239] As examples of the aforementioned functional group-containing monomers, hydroxyl-containing monomers, carboxyl-containing monomers, epoxy-containing monomers, etc., can be listed. As specific examples of each monomer, monomers that are the same as those exemplified as the monomers constituting structural unit (a2) can be listed.

[0240] In addition, these monomers can be used individually or in combination with more than one.

[0241] The content of structural units (x2) relative to the total structural units (100% by mass) of the acrylic polymer is typically 0 to 40% by mass, preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass, and even more preferably 5 to 20% by mass.

[0242] Furthermore, as an acrylic resin used in one aspect of the present invention, it can be an energy-curable acrylic resin obtained by further reacting an acrylic copolymer having the above-described structural units (x1) and (x2) with a compound having energy-ray polymerizable groups.

[0243] As a compound with a polymerizable group that can generate energy rays, it is acceptable as long as it is a compound with a polymerizable group such as (meth)acryloyl or vinyl.

[0244] When using an adhesive containing acrylic resin, it is preferable to contain a crosslinking agent while containing acrylic resin, from the perspective of adjusting the 180° peel adhesion and adhesion (β2) between the protective film forming film and the support sheet within the above-mentioned range.

[0245] Examples of crosslinking agents include isocyanate crosslinking agents, imine crosslinking agents, epoxy crosslinking agents, oxazoline crosslinking agents, and carbodiimide crosslinking agents. From the perspective of adjusting the 180° peel adhesion and adhesion (β2) between the protective film forming film and the support sheet within the above-mentioned range, isocyanate crosslinking agents are preferred.

[0246] The content of crosslinking agent is preferably 0.01 to 20 parts by mass relative to the total mass (100 parts by mass) of acrylic resin contained in the adhesive, more preferably 0.1 to 15 parts by mass, even more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 8 parts by mass.

[0247] The support sheet 10 can be composed of a single layer or multiple layers. When the support sheet is composed of multiple layers, the constituent materials and thicknesses of these multiple layers can be the same or different from each other. As long as the effect of the present invention is not impaired, there is no particular limitation on the combination of these multiple layers.

[0248] In addition, in this specification, not only in the case of support sheets, "multiple layers may be the same or different from each other" means "all layers may be the same, all layers may be different, or only some layers may be the same". Furthermore, "multiple layers may be different from each other" means "at least one of the constituent materials and thicknesses of each layer is different from each other".

[0249] The support sheet can be transparent or opaque, and can be colored according to the purpose.

[0250] For example, when the protective film forming film has energy ray curing properties, a support sheet is preferred to allow energy rays to pass through.

[0251] For example, in order to perform optical inspection of the protective film formed through the support sheet, the support sheet is preferably transparent.

[0252] From the perspective of ensuring good operability, the support sheet can have a release film before it is attached to the protective film to form a film.

[0253] As one embodiment of the kit, for example, a kit having a first laminate and a support sheet can be provided. The first laminate contains a first release film, a protective film forming film, and a second release film stacked sequentially. The support sheet supports the workpiece to be protected by the protective film forming film and the protective film forming film. The protective film forming film contains a polymer component, a curing component, and a filler material. The polymer component has a weight-average molecular weight (Mw) of 10,000 to 2,000,000 and includes an acrylic resin with a glass transition temperature (Tg) of -60 to 50°C. The polymer component content is 5 to 50 parts by mass relative to 100 parts of the total weight of the protective film forming film. The curing component contains a thermosetting resin, which includes an epoxy resin. The curing component content is 1 to 75 parts by mass relative to 100 parts of the total weight of the protective film forming film. The filler material contains silica filler, and the content of the filler material is 1 to 85 parts by weight relative to 100 parts by weight of the total solids constituting the protective film. The support sheet has a substrate comprising a resin film. Using a laminating roller at 70°C, the protective film is attached to the mirror surface of a mirror-finished silicon wafer. After 5 minutes of attachment, at a peel speed of 100 mm / min and a temperature of 23°C, the 180° peel adhesion between the protective film and the silicon wafer is measured to be 900 mN / 25 mm or more. Using a laminating roller at 23°C, the support sheet is attached to the protective film. After 3 minutes of attachment, at a peel speed of 100 mm / min and a temperature of 23°C, the 180° peel adhesion between the protective film and the support sheet is measured to be 100 mN / 25 mm.

[0254] The 180° peel adhesion between the protective film formed by the protective film and the support sheet is 0.03 to 4.0 N / 25 mm.

[0255] As one embodiment of the kit, for example, a kit having a first laminate and a support sheet can be provided. The first laminate contains a first release film, a protective film forming film, and a second release film stacked sequentially. The support sheet supports the workpiece, which is the object to be protected by the protective film forming film, and the protective film forming film. The protective film forming film contains a polymer component, a curing component, and a filler material. The weight-average molecular weight (Mw) of the polymer component is 10,000 to 2,000,000. The polymer component includes acrylic resin, and the glass transition temperature (Tg) of the acrylic resin is -60 to 50°C. The content of the polymer component is 5 to 50 parts by mass relative to 100 parts of the total weight of the protective film forming film. The curing component contains a thermosetting resin, and the thermosetting resin includes epoxy resin. The content of the curing component is 1 to 75 parts by mass relative to 100 parts of the total weight of the protective film forming film. The filler material contains silica filler, and the content of the filler material is [not specified] relative to 100 parts by mass of the total solid components constituting the protective film forming film. The support sheet comprises 1 to 85 parts by weight, a substrate comprising a resin film, an adhesive layer of the support sheet adhered to the protective film forming film is laminated on the substrate, the adhesive layer comprising acrylic resin, and the protective film forming film is adhered to the mirror surface of a mirror-finished silicon wafer using a lamination roller at 70°C. After 5 minutes of adhesion, the distance between the protective film forming film and the silicon wafer is measured at a peeling speed of 100 mm / min and a temperature of 23°C. The 80° peel adhesion is 900mN / 25mm or more. Using a laminating roller at 23°C, the support sheet is attached to the protective film forming film. After 3 minutes of attachment, the 180° peel adhesion between the protective film forming film and the support sheet is measured at a peeling speed of 100mm / min and a temperature of 23°C. The 180° peel adhesion between the protective film formed by the protective film forming film and the support sheet is 0.03 to 4.0 N / 25mm.

[0256] Example

[0257] The present invention will now be described in more detail through specific embodiments. However, the present invention is not limited to any of the embodiments shown below.

[0258] [Preparation of the protective film forming composition]

[0259] The following components were mixed at their respective mixing ratios (converted to solid components) as shown in Tables 1 and 2, and diluted with methyl ethyl ketone to a solid component concentration of 50% by mass relative to the total mass of the protective film forming composition, to prepare the protective film forming compositions of Examples 1 to 4 and Comparative Example 1 for forming a protective film forming film for semiconductor wafers.

[0260] (A-1): Polymer composition: (meth)acrylic acid copolymer (weight average molecular weight: 400,000) obtained by copolymerizing 90 parts by mass of methyl acrylate and 10 parts by mass of 2-hydroxyethyl acrylate. The glass transition temperature of this composition is 7°C.

[0261] (A-2): Polymer composition: An acrylic polymer (weight average molecular weight: 800,000) obtained by copolymerizing 55 parts by weight of n-butyl acrylate, 10 parts by weight of methyl acrylate, 20 parts by weight of glycidyl methacrylate, and 15 parts by weight of 2-hydroxyethyl acrylate. The glass transition temperature of this composition is -28℃.

[0262] (B-1) Thermosetting resin: Bisphenol A type epoxy resin: Manufactured by Mitsubishi Chemical Corporation, JER828, epoxy equivalent 184~194g / eq

[0263] (B-2) Thermosetting resin: Bisphenol A type epoxy resin: Manufactured by Mitsubishi Chemical Corporation, JER1055, epoxy equivalent 800-900 g / eq

[0264] (B-3) Thermosetting resin: Dicyclopentadiene type epoxy resin: Manufactured by DIC Corporation, EPICLON HP-7200HH, epoxy equivalent 255~260g / eq

[0265] (B-4) Thermosetting resin: Dicyclopentadiene type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., XD-1000, epoxy equivalent 248g / eq)

[0266] (B-5) Thermosetting resin: Bisphenol A type epoxy resin with 20 parts of methyl methacrylate particles added (manufactured by NIPPONSHOKUBAI CO.,LTD., BPA328, epoxy equivalent 235g / eq)

[0267] (C-1) Thermosetting agent: Thermoactive latent epoxy resin curing agent (dicyandiamide (manufactured by Mitsubishi Chemical Corporation, DICY7 active hydrogen content 21g / eq))

[0268] (D-1) Curing accelerator: 2-Phenyl-4,5-dihydroxymethylimidazol (manufactured by SHIKOKU CHEMICALSCORPORATION, CUREZOL 2PHZ)

[0269] (E-1) Filler material: Silica filler (manufactured by Admatechs., SC205G-MMQ (average particle size 0.3μm))

[0270] (E-2) Filler material: Silica filler (manufactured by TATSUMORI, SV-10, average particle size 8.0 μm)

[0271] (E-3) Filler material: Silica filler (manufactured by Admatechs., SC2050MA, average particle size 0.5μm)

[0272] (F-1) Colorant: Three-color mixed pigment (manufactured by Sanyo Color Works, LTD., D1201M, 30% solids concentration).

[0273] (F-2) Colorant: Carbon black (manufactured by Mitsubishi Chemical Corporation, MA600B)

[0274] (G-1) Silane coupling agent: Manufactured by Shin-Etsu Chemical Co., Ltd., X-41-1056

[0275] (G-2) Silane coupling agent: MSEP-2, an epoxy-containing oligomer, manufactured by Mitsubishi Chemical Corporation.

[0276] [Creating the first layer of the stack]

[0277] The protective film forming compositions of Examples 1 to 4 and Comparative Example 1 obtained above were coated on the peeling surface of a single-sided peeling film ("SP-PET501031" manufactured by Lintec Corporation, with a thickness of 50 μm, equivalent to the second peeling film) made of polyethylene terephthalate (PET) film that had undergone single-sided peeling treatment using silicone treatment, and dried at 100°C for 3 minutes, thereby forming a protective film forming film of Examples 1 to 4 and Comparative Example 1 with a thickness of 25 μm.

[0278] Furthermore, under conditions of a temperature of 23±5℃, a pressure of 0.4MPa, and a speed of 1m / min, the peeling treatment side of a light-sided peeling film ("SP-PET381031" manufactured by Lintec Corporation, with a thickness of 38μm, equivalent to the first peeling film) that has been separately treated with silicone to peel off one side of polyethylene terephthalate (PET) film was attached to the exposed surface of the protective film forming film (the surface opposite to the side with the peeling film), thus forming a laminate with peeling films stacked on both sides of the protective film forming film (i.e., the first laminate of Examples 1 to 4 and Comparative Example 1).

[0279] (Adhesive composition)

[0280] The adhesive composition used in manufacturing the support sheet is a composition containing 100 parts by weight of (meth)acrylate alkyl ester copolymer (solid component) and 45 parts by weight of trifunctional dimethyl phthalate diisocyanate crosslinking agent (MITSUI CHEMICALSPOLYURETHANES, INC. "TAKENATE D110N"), and the concentration of the solid component is adjusted to 30% by weight by using a mixed solvent of methyl ethyl ketone, toluene and ethyl acetate.

[0281] In addition, the (meth)acrylate alkyl ester copolymer is an acrylic copolymer with a weight average molecular weight of 700,000 obtained by copolymerizing 50 parts by weight of 2-ethylhexyl acrylate (hereinafter, sometimes abbreviated as "2EHA"), 35 parts by weight of methyl methacrylate (hereinafter, sometimes abbreviated as "MMA"), and 15 parts by weight of 2-hydroxyethyl acrylate (hereinafter, sometimes abbreviated as "HEA").

[0282] [Manufacturing of the support sheet]

[0283] The adhesive composition is applied to the release treatment surface of a release film (SP-PET381031, manufactured by Lintec Corporation, 38 μm thick) and dried at 100°C for 3 minutes to form an adhesive layer (10 μm thick after drying). A polypropylene film (80 μm thick, manufactured by GUNZE LIMITED.) is then bonded to the exposed surface (the surface opposite to the side with the release film) to obtain a support sheet with a release film consisting of a substrate, an adhesive layer, and a release film.

[0284] Hereinafter, the kit having the first laminate and the support sheet of Embodiment 1 will be referred to as the kit of Embodiment 1. Similarly, the kit having the first laminate and the support sheet of Embodiments 2 to 4 will be referred to as the kit of Embodiments 2 to 4, respectively. The kit having the first laminate and the support sheet of Comparative Example 1 will be referred to as the kit of Comparative Example 1.

[0285] <Adhesion strength between the protective film and the silicon wafer after 5 minutes>

[0286] The light-side release film of the first laminate (comprising a light-side release film / protective film forming film / heavy-side release film) of Examples 1 to 4 and Comparative Example 1 was peeled off. Adhesive tape (product name PET50PL SHIN: acrylic adhesive layer / 50μm PET substrate) manufactured by Lintec Corporation was laminated onto the exposed surface at 23°C to prepare laminate samples of Examples 1 to 4 and Comparative Example 1, composed of a PET substrate / acrylic adhesive layer / protective film forming film / heavy-side release film. The laminate samples were cut into short strips 25mm wide and 250mm long. All these operations were performed at 23°C.

[0287] Separately from the actual process evaluation, prepare a 600μm thick silicon wafer with mirror finish.

[0288] The release film of the laminated samples of Examples 1 to 4 and Comparative Example 1 was peeled off, and the exposed side of the protective film was attached to the mirror surface of a 600 μm thick silicon wafer with a pressure of 0.3 MPa using a laminator that heats the rollers to 70°C.

[0289] At 23°C, without heating, the adhesive was left to stand for 5 minutes (±0.5 minutes) after the initial application. Then, the adhesive was peeled off at 180° using the following method.

[0290] Test method: The test was conducted using a universal tensile testing machine (manufactured by Shimadzu Corporation, product name "AUTOGRAPH AG-IS"), according to JIS Z0237:2009, at a peeling speed of 100 mm / min and a temperature of 23°C, for a test distance of 100 mm.

[0291] Furthermore, the average of the measured values ​​between the initial 10 mm and the last 10 mm of the measurement distance (80 mm) is taken as the "180° peel adhesion between the protective film and the silicon wafer".

[0292] <Adhesion strength of the protective film between the film and the silicon wafer after 30 minutes>

[0293] Using a sealing machine that heats the rollers to 70°C and applies a pressure of 0.3 MPa, the aforementioned exposed surfaces of the protective film formed in Examples 1 to 4 and Comparative Example 1 are attached to the mirror surface of a 600 μm thick silicon wafer that has undergone mirror finishing.

[0294] At 23°C, the film was left to stand without heating. After 30 minutes (±0.5 minutes) from the completion of the bonding, the protective film was peeled off from the silicon wafer at 180° and the adhesion was measured.

[0295] <Adhesion strength between the protective film and the support sheet after 3 minutes>

[0296] Apply double-sided adhesive tape (adhesive layer / PET film / adhesive layer) to the SUS board to prepare the object to be bonded, which consists of "adhesive layer / PET / adhesive layer / SUS board".

[0297] Peel off the light-side release film of the first laminate (which is configured as a light-side release film / protective film forming film / heavy-side release film) of Examples 1 to 4 and Comparative Example 1, and attach the exposed side of the protective film forming film to the adhesive layer of the object to be adhered, thereby obtaining a laminate composed of SUS board / adhesive layer / PET film / adhesive layer / protective film forming film / heavy-side release film.

[0298] The support sheet was cut into short strips 25 mm wide and 250 mm long. Furthermore, the release liner of the laminate consisting of SUS sheet / adhesive layer / PET film / adhesive layer / protective film forming film / reel-off film was peeled off to produce laminates of Examples 1 to 4 and Comparative Example 1, consisting of SUS sheet / adhesive layer / PET film / adhesive layer / protective film forming film. All these operations were performed at 23°C.

[0299] Using a sealing machine (roller temperature 23°C) and a pressure of 0.3 MPa, the adhesive layer of the short strip-shaped support sheet is attached to the exposed surface of the protective film forming film of the laminate of Examples 1 to 4 and Comparative Example 1, which are composed of SUS board / adhesive layer / PET film / adhesive layer / protective film forming film.

[0300] At 23°C, the surface is left to stand without heating. After 3 minutes (±0.5 minutes) from the time of application, 180° peeling is performed and the adhesion is measured using the following method.

[0301] Test method: The test was conducted using a universal tensile testing machine (manufactured by Shimadzu Corporation, product name "AUTOGRAPH AG-IS"), according to JIS Z0237:2009, at a peeling speed of 100 mm / min and a temperature of 23°C, for a test distance of 100 mm.

[0302] Furthermore, the average of the measured values ​​between the initial 10 mm and the last 10 mm of the measurement distance (80 mm) is taken as the "180° peel adhesion between the protective film forming film and the support sheet".

[0303] <Adhesion strength between the protective film and the support sheet after 30 minutes>

[0304] Similarly, using a sealing machine (roller temperature 23°C) and a pressure of 0.3 MPa, the adhesive layer of the short strip-shaped support sheet was attached to the exposed surface of the protective film forming film of Examples 1 to 4 and Comparative Example 1.

[0305] At 23°C, the film was left to stand without heating. After 30 minutes (±0.5 minutes) from the time of application, the protective film was peeled off from the support sheet at 180° and the adhesion was measured.

[0306] [Creating the Third Layer]

[0307] As the workpiece used for actual process peeling evaluation, a 12-inch silicon wafer (40μm thick) with back-abrasion tape (Adwill E-8180HR manufactured by Lintec Corporation) with back-abrasion tape and mirror finish was used.

[0308] To create a third-layer stack for actual process evaluation, the attachment device ("RAD-3600F / 12" manufactured by Lintec Corporation) and the attachment device ("RAD-2700F / 12" manufactured by Lintec Corporation) are connected and assembled in an online manner that allows the workpiece of a 12-inch silicon wafer with backing matting tape to be transported by a robotic arm.

[0309] The first release film is peeled off from the laminate (i.e., the first laminate of Examples 1 to 4 and Comparative Example 1) in which the second release film, the protective film forming film, and the first release film are sequentially stacked. Using an attachment apparatus ("RAD-3600F / 12" manufactured by Lintec Corporation), the exposed side of the protective film forming film is attached to the mirror-finished back side of the 12-inch silicon wafer (40 μm thick) with back-abrasion tape under the conditions of lamination roller temperature of 70°C, attachment speed of 50 mm / s, and pressure of 0.3 MPa, to obtain the second laminate of Examples 1 to 4 and Comparative Example 1 in which the second release film, the protective film forming film, the silicon wafer, and the back-abrasion tape are sequentially stacked.

[0310] Next, the second release film was peeled off from the second laminate of Examples 1 to 4 and Comparative Example 1, and the release film of the support sheet with the release film was peeled off as well. Using an attachment apparatus ("RAD-2700F / 12" manufactured by Lintec Corporation), under the conditions of a lamination roller temperature of 23°C, an attachment speed of 20 mm / s, and a pressure of 0.3 MPa, the exposed surface of the adhesive layer of the support sheet was bonded to the exposed surface of the protective film forming film, thus obtaining the third laminate of Examples 1 to 4 and Comparative Example 1, which consisted of a substrate, an adhesive layer, a protective film forming film, a silicon wafer, and a back-grinding tape, stacked sequentially. At this time, the support sheet was attached to a 12-inch wafer annular frame.

[0311] Next, the backing bonding tape is peeled off from the wafer / protective film / support sheet. This process involves a series of steps, from peeling the light-side release film from the first laminate to peeling off the backing bonding tape, performed in an online process.

[0312] The transport distance of the silicon wafer from the point where the silicon wafer is first attached to the protective film to the point where the support sheet is attached to the protective film is completed is 5000 mm.

[0313] The silicon wafer transport time from the start of attaching the silicon wafer to the protective film to the completion of attaching the support sheet to the protective film is 300 seconds. In this specification, this transport time is sometimes simply referred to as "transport time".

[0314] The time from the start of attaching the silicon wafer to the protective film to the start of peeling the backing tape off the silicon wafer is 7 minutes.

[0315] When the wafer and support sheet attachment operations are repeated 30 times on the first laminate of Example 1 in the manner described above under the condition of a transport time of 300s, the number of silicon wafers with protective film forming film can be correctly maintained and transported 30 times.

[0316] When the wafer and support sheet attachment operations are repeated 30 times on the first stack of Example 1 in the manner described above under the condition of a transport time of 170s, the number of silicon wafers with protective film forming film can be correctly maintained and transported 30 times.

[0317] When the wafer and support sheet attachment operations are repeated 30 times on the first stack of Example 1 in the manner described above under the condition of a transport time of 120s, the number of silicon wafers with protective film forming film that can be correctly held and transported is 29.

[0318] When the wafer and support sheet attachment operations are repeated 30 times on the first stack of Example 1 in the manner described above under the condition of a transport time of 60 seconds, the number of silicon wafers with protective film forming film that can be correctly held and transported is 28.

[0319] <Actual Process Peeling Evaluation Test>

[0320] As an evaluation of actual process peeling, peeling tests of the back-abrasion tape were carried out using RAD-2700F / 12 with the suction table temperature set to 23°C for 10 sheets of each of Examples 1 to 4 and Comparative Example 1.

[0321] (The protective film forms a separation between the film and the silicon wafer)

[0322] In a test of 10 wafers, the number of wafers that peeled off between the protective film and the silicon wafer was counted. The results, evaluated according to the following criteria, are shown in Tables 1 and 2.

[0323] A (Pass): In the test of 10 wafers, there was no peeling between the protective film and the silicon wafer.

[0324] B (Pass): In the test of 10 wafers, 1 or 2 silicon wafers experienced peeling between the protective film and the silicon wafer.

[0325] C (Failure): In the test of 10 wafers, more than 3 silicon wafers experienced peeling between the protective film and the silicon wafer.

[0326] (The protective film forms a separation between the film and the support sheet)

[0327] In the above experiments, the number of wafers that peeled off between the protective film and the support sheet was counted. The experimental results are shown in Tables 1 and 2.

[0328] (Delamination between the protective film and the silicon wafer, and between the protective film and the support sheet)

[0329] In the above tests, the number of wafers that peeled off between the protective film and the silicon wafer, and between the protective film and the support sheet, was counted. The results, evaluated according to the following criteria, are shown in Table 1.

[0330] A (Pass): In the test of 10 wafers, no peeling occurred at all between the protective film and the silicon wafer, or between the protective film and the support sheet.

[0331] B (Pass): In the test of 10 wafers, one or two silicon wafers experienced peeling in either the protective film forming film between the silicon wafer and the protective film forming film or between the protective film forming film and the support sheet.

[0332] C (Pass): In the test of 10 wafers, more than 3 silicon wafers experienced peeling in either the protective film between the silicon wafer and the protective film or between the protective film and the support sheet.

[0333] D (Failure): In a test of 10 wafers, more than 5 silicon wafers experienced peeling between the protective film and the silicon wafer, or between the protective film and the support sheet.

[0334] [Table 1]

[0335]

[0336] [Table 2]

[0337]

[0338] Using the kits from Examples 1 to 4, which employ lamination rollers at 70°C to attach the protective film to the mirror surface of a mirror-finished silicon wafer, and where, after 5 minutes of attachment, the 180° peel adhesion between the protective film and the silicon wafer is 900 mN / 25 mm or higher, a third laminate was manufactured using an in-line process. When the back-grinding tape was peeled off, no peeling occurred between the protective film and the workpiece, or the possibility of peeling between the protective film and the workpiece was reduced. By using the kits from Examples 1 to 4, a third laminate can be manufactured using an in-line process. Manufacturing the third laminate using an in-line process can suppress accidental contamination and improve production cycle time.

[0339] Using the kits of Examples 1-4, which employ lamination rollers at 23°C to attach the support sheet to the protective film forming film, and after 3 minutes of attachment, exhibiting a 180° peel adhesion of 100 mN / 25 mm or higher between the protective film forming film and the support sheet, a third laminate was manufactured using an in-line process. When the backing tape was peeled off, no peeling occurred between the protective film forming film and the support sheet. By using the kits of Examples 1-4, the in-line process can be more suitable for manufacturing the third laminate.

[0340] Furthermore, compared to conventional protective film forming composite sheets, the kits of Examples 1 to 4 have the advantage of being inexpensive to manufacture. Also, compared to using conventional protective film forming composite sheets, the possibility of tape serpentinizing within the pick-and-place machine and causing adhesion failure is low, and the adhesion position or adhesion tension is easy to set.

[0341] For the third laminate obtained by using the kit of Comparative Example 1, which had a 180° peel adhesion force of less than 900mN / 25mm between the protective film forming film and the silicon wafer after 5 minutes of application, a large number of wafers peeled off between the protective film forming film and the workpiece or between the protective film forming film and the support sheet when the back-grinding tape was peeled off. The kit of Comparative Example 1 is not suitable for use in in-line processes.

[0342] Industrial applicability

[0343] The kit of the present invention can be used in the manufacturing method of a third laminate, which can be used in the manufacture of a semiconductor device with a protective film.

Claims

1. A kit comprising a first laminate in which a first release film, a protective film forming film which is thermosetting and non-energy ray-curable, and a second release film are sequentially laminated, and a support sheet for supporting a workpiece which is an object of protection by the protective film forming film and the protective film forming film, wherein 180° peel adhesion between the protective film forming film and a mirror-finished silicon wafer is 900 mN / 25 mm or more, which is measured at a temperature of 23°C at a peel rate of 100 mm / min after the protective film forming film is attached to a mirror surface of the mirror-finished silicon wafer using a laminating roll at 70°C for 5 minutes, wherein the protective film forming film is formed from a protective film forming composition comprising a polymer component, a curable component, a filler, and a silane coupling agent, wherein the polymer component is an acrylic resin having a glass transition temperature in the range of -60 to 50°C and a weight average molecular weight of 100,000 to 1,200,000, wherein the curable component comprises a thermosetting resin which is an epoxy resin and a thermosetting agent which is a compound having two or more functional groups capable of reacting with an epoxy group in one molecule, wherein the filler is a silica filler, and wherein the content of the polymer component is 5 to 50 parts by mass, the content of the curable component is 1 to 75 parts by mass, and the content of the filler is 20 to 70 parts by mass, with respect to 100 parts by mass of the total weight of the protective film forming film.

2. The kit according to claim 1, wherein the first laminate is in a roll shape.

3. The kit according to claim 1 or 2, wherein an adhesive layer of the support sheet is laminated on a base material.

4. The kit according to any one of claims 1 to 3, wherein 180° peel adhesion between the protective film forming film and the support sheet is 100 mN / 25 mm or more, which is measured at a temperature of 23°C at a peel rate of 100 mm / min after the support sheet is attached to the protective film forming film using a laminating roll at 23°C for 3 minutes.

5. A method for manufacturing a third laminate in which a workpiece, the protective film forming film, and the support sheet are sequentially laminated, using the kit according to any one of claims 1 to 4 in an in-line process, the method comprising, in sequence: a process of peeling the first release film of the first laminate; a first laminating process of attaching an exposed surface of the protective film forming film to the workpiece; and a second laminating process of attaching the support sheet to a surface of the protective film forming film opposite to the exposed surface, wherein the operation from the first laminating process to the second laminating process is performed in a device in which a device for performing the first laminating process and a device for performing the second laminating process are connected, or in the same device, or the second laminate in which the protective film forming film is attached to the workpiece is conveyed piece by piece between the first laminating process and the second laminating process.

6. The method according to claim 5, wherein the first laminating process and the second laminating process are performed in the same device. ​ 2. The kit of claim 1, wherein, ​ 3. The kit of claim 1 or 2, wherein, ​ 4. The kit of claim 1 or 2, wherein, ​ ​ ​ ​ ​ ​ ​ The conveyance distance of the workpiece from the point at which the first layering process is started to the point at which the second layering process is completed is 7000 mm or less.

6. A method for manufacturing a third laminate, which uses the set described in any one of claims 1 to 4 in an in-line process, and in which a workpiece, the protective film forming film, and the support sheet are sequentially layered, the method comprising, in sequence: a process of peeling the first peel film of the first laminate; a first layering process of attaching an exposed surface of the protective film forming film to the workpiece; and a second layering process of attaching the support sheet to a surface of the protective film forming film opposite the exposed surface, the operations from the start of the first layering process to the completion of the second layering process are performed in a device in which a device that performs the first layering process and a device that performs the second layering process are connected, or in the same device, or the second laminate in which the protective film forming film is attached to the workpiece is conveyed piece by piece between the first layering process and the second layering process, the conveyance time of the workpiece from the start of the attachment of the first layering process to the completion of the attachment of the second layering process is 400 seconds or less.

7. A method for manufacturing a third laminate, which uses the set described in any one of claims 1 to 4 in an in-line process, and in which a workpiece, the protective film forming film, and the support sheet are sequentially layered, the method comprising, in sequence: a process of peeling the first peel film of the first laminate; a first layering process of attaching an exposed surface of the protective film forming film to the workpiece; and a second layering process of attaching the support sheet to a surface of the protective film forming film opposite the exposed surface, the second laminate in which the protective film forming film is attached to the workpiece is conveyed piece by piece between the first layering process and the second layering process.

8. The method for manufacturing a third laminate according to any one of claims 5 to 7, wherein A back grinding tape is attached to a surface of the workpiece opposite the side on which the exposed surface of the protective film forming film is attached, and a process of peeling the back grinding tape from the workpiece is included after the second layering process.

9. The method for manufacturing a third laminate according to claim 8, wherein The peeling of the back grinding tape from the workpiece is started within 10 minutes from the start of the attachment of the first layering process.

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