Kit, and method for manufacturing third laminate using the kit

Abstract

Provided is a kit (1) including a first laminate (5) in which a first release film (151), a protective film forming film (13), and a second release film (152) are sequentially laminated, and a support sheet (10), the protective film forming film (13) having an elongation at break of greater than 700% at 23°C.

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. 2019-210862, 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 5 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 5 A) in the figure, the protective film 13 is formed by thermosetting or energy radiation curing to produce the protective film 13'. Figure 5 In section B), a support sheet 10 is stacked on the protective film 13'. Figure 5 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 5 E and Figure 5 F), picks up the semiconductor chip 7 with a protective film from the support sheet 10. Figure 5 (G in the text). Here, Figure 5 In section A, an apparatus for attaching a protective film 13 to the back side 8b of a semiconductor wafer 8, and... Figure 5 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 6 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 6 A), peeling back abrasion tape 17 ( Figure 6 In step B), the protective film 13 is formed by thermosetting or energy radiation curing to create the protective film 13'. Figure 6 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 6 E and Figure 6 F), picks up the semiconductor chip 7 with a protective film from the support sheet 10. Figure 6 (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 5In 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 5 A), and the protective film 13 is cured to form a protective film 13'. Figure 5 After B), attach the support sheet 10 to the protective film 13'. Figure 5 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 6 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] like Figure 7 As shown in A, the protective film formed by the film 13 that has been attached to the workpiece 14 sometimes protrudes from the workpiece 14.

[0019] In such a situation, such as Figure 7 As shown in B, when the second peeling film 152 of the protective film forming film 13 that has been attached to the workpiece 14 is peeled off, the protruding portion 90 of the protective film forming film 13 that protrudes from the workpiece 14 may be torn and attached to the second peeling film 152 and brought back by it.

[0020] Furthermore, in such cases, such as Figure 7 As shown in C, when the support sheet 10 is attached to the protective film forming film 13, the protruding part 90 of the protective film forming film 13 that protrudes from the workpiece 14 may break and scatter.

[0021] 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.

[0022] Technical means to solve technical problems

[0023] The present invention provides the following kit and a method for manufacturing a third laminate using the kit.

[0024] [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.

[0025] The protective film forms a film with an elongation at break of more than 700% at 23°C.

[0026] [2] According to the kit described in [1] above, the first stack is in the form of a roll.

[0027] [3] According to the kit described in [1] or [2] above, wherein the protective film forming film is thermosetting or energy-cured.

[0028] [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.

[0029] [5] The kit according to any one of [1] to [4] above, wherein the peel force between the protective film forming film and the second release film is greater than the peel force between the protective film forming film and the first release film.

[0030] The 180° peeling force between the protective film forming film and the second peeling film, measured at a peeling speed of 1 m / min and a temperature of 23°C, is 250 mN / 100 mm or less.

[0031] [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:

[0032] The process of peeling off the first release film from the first laminate;

[0033] The first lamination process of attaching the protective film to the workpiece to form the exposed surface of the film; and

[0034] In the second lamination process of attaching the support sheet to the side of the protective film forming film opposite to the exposed side,

[0035] 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.

[0036] [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:

[0037] The process of peeling off the first release film from the first laminate;

[0038] The first lamination process of attaching the protective film to the workpiece to form the exposed surface of the film; and

[0039] In the second lamination process of attaching the support sheet to the side of the protective film forming film opposite to the exposed side,

[0040] 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.

[0041] [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:

[0042] The process of peeling off the first release film from the first laminate;

[0043] The first lamination process of attaching the protective film to the workpiece to form the exposed surface of the film; and

[0044] In the second lamination process of attaching the support sheet to the side of the protective film forming film opposite to the exposed side,

[0045] 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.

[0046] [9] The manufacturing method of the third stack according to any one of [6] to [8] above, wherein the first stacking process is performed on a wafer table at a temperature of 80°C or above.

[0047]

[10] The method for manufacturing the third laminate according to any one of [6] to [9] 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.

[0048]

[11] In the manufacturing method of the third laminate described above

[10] , the backing tape is peeled off from the workpiece within 10 minutes of starting the attachment of the first lamination process.

[0049] Invention Effects

[0050] 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

[0051] Figure 1 A schematic cross-sectional view illustrating an example of the kit of this embodiment is shown for illustrative purposes.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] Figure 5 A in the diagram is a schematic cross-sectional view illustrating an example of a conventional method for manufacturing semiconductor chips with protective films.

[0063] Figure 5 B 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 5 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.

[0065] Figure 5 D 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 5 E 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 5F in the diagram is a schematic cross-sectional view illustrating an example of a conventional method for manufacturing semiconductor chips with protective films.

[0068] Figure 5 G in the diagram is a schematic cross-sectional view illustrating an example of a conventional method for manufacturing semiconductor chips with protective films.

[0069] Figure 6 A 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 6 B 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 6 C 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 6 D 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 6 E in the diagram is a schematic cross-sectional view illustrating another example of a conventional method for manufacturing semiconductor chips with protective films.

[0074] Figure 6 F in the diagram is a schematic cross-sectional view illustrating another example of a conventional method for manufacturing semiconductor chips with protective films.

[0075] Figure 6 G in the diagram is a schematic cross-sectional view illustrating another example of a conventional method for manufacturing semiconductor chips with protective films.

[0076] Figure 7 A in the diagram is a schematic cross-sectional view illustrating an example where the protrusion 90 of the protective film forming membrane is brought back by the peeling membrane, and an example where a crack occurs during the attachment of the support sheet.

[0077] Figure 7 B in the diagram is a schematic cross-sectional view illustrating an example where the protrusion 90 of the protective film forming membrane is brought back by the peeling membrane, and an example where a breakage occurs during the attachment of the support sheet.

[0078] Figure 7 C in the diagram is a schematic cross-sectional view illustrating an example where the protrusion 90 of the protective film is brought back by the peeling film and an example where a breakage occurs during the attachment of the support sheet.

[0079] Explanation of reference numerals in the attached figures

[0080] 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: Protective film forming film 13b: The 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. Detailed Implementation

[0081] 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.

[0082] <<Kit>>

[0083] 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.

[0084] 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.

[0085] 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.

[0086] <<Manufacturing Method of the Third Layer Using the Kit>>

[0087] 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 the following steps in sequence: peeling off the first release film 151 of the first laminate 5; 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 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).

[0088] 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.

[0089] 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).

[0090] 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.

[0091] 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 middle).

[0092] Next, the second release 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).

[0093] The first layer stacking process can be performed on a wafer worktable at a temperature above 80°C.

[0094] By performing the first layering process on a wafer worktable at a temperature of 80°C or higher, even if the first surface 13a of the protective film forming film 13 is a surface condition or material that makes it difficult for the workpiece 14 to achieve adhesion, it can still be fully adhered to the workpiece 14. As a result, the variety of workpieces to which the protective film forming film can be applied can be increased.

[0095] When the protective film forming composite sheet 3 is attached to the workpiece 14 on a wafer worktable at a temperature above 80°C, wrinkles are easily generated on the substrate 11 of the support sheet 10 because the support sheet 10 of the protective film forming composite sheet 3 is also heated together.

[0096] like Figure 7 As shown in Figure A, the protective film 13, which has been attached to the workpiece 14, sometimes protrudes from the wafer. For example... Figure 7 As shown in B, when the second peeling film 152 of the protective film forming film 13 that has been attached to the workpiece 14 is peeled off, the protruding portion 90 of the protective film forming film 13 that protrudes from the workpiece 14 may be torn and attached to the second peeling film 152 and brought back by it.

[0097] Preferably, the 180° peel force between the protective film forming film 13 and the second release film 152, measured at a peeling speed of 1 m / min and a temperature of 23°C, is 250 mN / 100 mm or less. Here, the peel force between the protective film forming film 13 and the second release film 152 is greater than the peel force between the protective film forming film 13 and the first release film 151.

[0098] The peel force between the protective film forming film 13 and the second release film 152 can be less than 250 mN / 100 mm, less than 220 mN / 100 mm, less than 200 mN / 100 mm, less than 180 mN / 100 mm, less than 160 mN / 100 mm, or less than 140 mN / 100 mm. By making the peel force between the protective film forming film 13 and the second release film 152 less than the above-mentioned upper limit value, it is possible to reduce the possibility that when the second release film 152 of the protective film forming film 13 already attached to the workpiece 14 is peeled off, the protruding portion 90 of the protective film forming film 13 protruding from the workpiece 14 will be torn and adhere to the second release film 152 and be brought back by it.

[0099] The peel force between the protective film forming film 13 and the second release film 152 can be 30 mN / 100 mm or more, or 50 mN / 100 mm or more. By making the peel force between the protective film forming film 13 and the second release film 152 at or above the aforementioned lower limit value, the operability of the first laminate 5 can be improved.

[0100] The 180° peel force between the protective film forming film 13 and the second peel film was measured in the following manner.

[0101] 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 test distance of 100 mm, a peeling speed of 1 m / min, and a temperature of 23°C.

[0102] 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° peeling force between the protective film forming film and the second peeling sheet".

[0103] The protective film forming film 13 of this embodiment has an elongation at break of greater than 700% at 23°C. By ensuring that the elongation at break of the protective film forming film 13 at 23°C is greater than 700%, the possibility of the protective film forming film 13 protruding from the workpiece 14 and scattering when the support sheet 10 is attached to the protective film forming film 13 can be reduced. Furthermore, the possibility of the protective film forming film 13 protruding from the workpiece 14 being torn when the second release film 152 is peeled off can also be reduced, thereby reducing the possibility of it adhering to the second release film 152 and being carried back by it.

[0104] The elongation at break of the protective film 13 at 23°C can be determined by the following method.

[0105] A protective film measuring 15 mm wide, 40 mm long, and 200 μm thick was formed as a test piece. This test piece was heated to 23°C and stretched at a tensile speed of 100 mm / min, starting with a clamping distance of 10 mm. The elongation at this point was measured. The elongation at break was calculated based on the elongation at which the test piece broke.

[0106] Here, elongation at break is the ratio of the increase in length (ΔL) of the specimen at the time of fracture in a tensile test according to JISK7161:2014 (ISO527-1:2012) to the original length (L).

[0107] In this embodiment, the workpiece 14 is a semiconductor wafer with a circuit surface 14a on one side, and a backing tape 17 can be attached to the circuit surface 14a of the workpiece 14.

[0108] Figure 3 E in 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.

[0109] 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)

[0110] exist Figure 3 E in 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 text)

[0111] 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.

[0112] The protective film forming film 13 of this embodiment has an elongation at break of more than 700% at 23°C.

[0113] like Figure 7 As shown in Figure A, the protective film 13, which has been attached to the workpiece 14, sometimes protrudes from the workpiece 14. For example... Figure 7 As shown in C, when the support sheet 10 is attached to the protective film forming film 13, the protruding part 90 of the protective film forming film 13 that protrudes from the workpiece 14 may break and scatter.

[0114] The elongation at break of the protective film 13 at 23°C can be greater than 700%, 800%, 1000%, 1200%, 1400%, 1900%, 3000%, 5000%, or 7000%.

[0115] By ensuring that the elongation at break of the protective film forming film 13 at 23°C is within the aforementioned range, the possibility of the protruding portion 90 of the protective film forming film 13 rupturing and scattering when the support sheet 10 is attached to the protective film forming film 13 can be reduced.

[0116] in the past, Figure 5In section A, an apparatus for attaching a protective film 13 to the back side 8b of a semiconductor wafer 8, and... Figure 5 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.

[0117] 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 3 E and Figure 3 The second stacking process is shown as F in the diagram. Therefore, compared to using separate devices for each process, it is possible to suppress accidental waste adhesion and improve production cycle time.

[0118] 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.

[0119] In this embodiment, it can be started from the beginning. Figure 3 The attachment location and completion point of the first lamination process shown in Figure B. 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 3The 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.

[0120] 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.

[0121] 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 3 The 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] In this embodiment, the second side 10b of the support sheet 10, which is opposite to the protective film forming film 13, can be adsorbed onto the suction table 80 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, and the backing adhesive tape 17 can be 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.

[0128] The manufacturing method of the third laminate of this embodiment, which uses the kit of this embodiment, utilizes the kit in an online process. In this embodiment, after the second lamination process, the process 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 it to be performed using an online process.

[0129] The manufacturing method of the third laminate in this embodiment enables the peeling of the backing tape from the workpiece to begin within 10 minutes of the attachment process at the start of the first lamination step. This reduces the risk of material transfer between the support sheet 10 and the protective film 13.

[0130] In this embodiment, as Figure 3Workpiece 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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] <First Layer>

[0136] 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.

[0137] 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.

[0138] 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.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] 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.

[0145] 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.

[0146] (Protective film forming composition)

[0147] 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.

[0148] 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.

[0149] 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.

[0150] (Polymer composition)

[0151] 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.

[0152] The weight-average molecular weight (Mw) of the polymer component is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,200,000, further preferably 200,000 to 1,000,000, and particularly preferably 300,000 to 900,000. If the weight-average molecular weight of the polymer component is above or below the aforementioned lower limit, the release film is easy to peel off, reducing the risk of poor peeling, also known as "tears." If the weight-average molecular weight of the polymer component is below the aforementioned upper limit, it prevents the protective film from failing to adhere to the workpiece due to reduced adhesion, and prevents the protective film from peeling off from the workpiece after application. Furthermore, by keeping the weight-average molecular weight (Mw) within the aforementioned range, a suitable elongation at break is easily achieved.

[0153] The molecular weight distribution (Mw / Mn) is preferably 4 or more, more preferably 4.2 or more, even more preferably 4.5 or more, particularly preferably 5.5 or more, and most preferably 7 or more. By making the molecular weight distribution at or above the above lower limit value, since molecules of various molecular weights are present in the polymer composition, the protective film forming film 13 can easily achieve a large elongation at break.

[0154] The molecular weight distribution (Mw / Mn) is preferably 14 or less, more preferably 12 or less, even more preferably 11 or less, and particularly preferably 10 or less. By making the molecular weight distribution below the above-mentioned upper limit value, the adhesion reliability between the workpiece 14 and the protective film 13 can be improved.

[0155] Here, Mn is the number-average molecular weight.

[0156] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) values ​​of each component are converted from standard polystyrene determined by gel permeation chromatography (GPC).

[0157] Acrylic resin is preferably used as the polymer component. The glass transition temperature (Tg) of the acrylic resin is preferably -60 to 50°C, more preferably -50 to 40°C, and even more preferably -40 to 30°C. For example, it can also be -30 to 20°C, -25 to 15°C, or -20 to 10°C.

[0158] 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 prevents the protective film from failing to adhere to the workpiece due to reduced adhesion, and prevents the protective film from peeling off the workpiece after application. Furthermore, it reduces the risk of cracks (fissures) forming when the protective film is bent during roll forming. Moreover, by keeping the glass transition temperature (Tg) within the above range, a suitable elongation at break is easily achieved.

[0159] From the perspective of adhesion and film-forming properties, relative to the total weight of the protective film (100g), the preferred content of the polymer component is 5-80 parts by mass, more preferably 8-70 parts by mass, and even more preferably 11-60 parts by mass. For example, it can also be 14-50 parts by mass, 17-45 parts by mass, or 20-40 parts by mass. By keeping the content of the polymer component within the above range, it is easy to achieve a suitable elongation at break.

[0160] The glass transition temperature (Tg) of the resin that constitutes the polymer component can be calculated using the Fox formula shown below.

[0161] 1 / Tg=(W1 / Tg1)+(W2 / Tg2)+……+(Wm / Tgm)

[0162] 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.

[0163] The glass transition temperatures of the homopolymers of the monomers in the Fox formula can be obtained using values ​​recorded in adhesive handbooks or polymer handbooks. For example, the glass transition temperatures of homopolymers are as follows: methyl acrylate 10°C, methyl methacrylate 105°C, 2-hydroxyethyl acrylate -15°C, n-butyl acrylate -54°C, and glycidyl methacrylate 41°C.

[0164] 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.

[0165] 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.

[0166] (Curing components)

[0167] 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.

[0168] 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.

[0169] By using energy-curable protective film formation, the protective film can be cured by energy rays in a short time.

[0170] Thermosetting components can be thermosetting resins and thermosetting agents. For example, epoxy resins are preferred as thermosetting resins.

[0171] 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.

[0172] 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 65 parts by mass, even more preferably 3 to 60 parts by mass, for example, 4 to 55 parts by mass, 5 to 50 parts by mass, or 6 to 45 parts by mass.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] 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.

[0177] 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.

[0178] 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.

[0179] 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.

[0180] 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.

[0181] 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.

[0182] 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.

[0183] 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.

[0184] (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.

[0185] 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.

[0186] 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.

[0187] 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.

[0188] 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.

[0189] For example, when curing an energy-curable protective film with energy rays, the preferred energy irradiation is 4–280 mW / cm². 2 Furthermore, the energy intensity of the radiation during curing is preferably 3–1000 mJ / cm². 2 .

[0190] In addition to the polymer and curing components mentioned above, the protective film may also contain the following components.

[0191] (Coloring agent)

[0192] 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.

[0193] Relative to 100 parts by mass of the total solids constituting the protective film, the amount of colorant incorporated is preferably 0.01 to 35 parts by mass, more preferably 0.02 to 15 parts by mass, and even more preferably 0.03 to 10 parts by mass. For example, it can also be 0.04 to 5 parts by mass, 0.05 to 1.5 parts by mass, or 0.06 to 1 part by mass. By keeping the amount of colorant incorporated at or below the above-mentioned upper limit, it is easy to confirm whether there is any lifting when it is attached to the workpiece 14. By keeping the amount of colorant incorporated at or below the above-mentioned lower limit, it is easy to confirm whether there is any cracking or carry-back phenomenon.

[0194] (Curing accelerator)

[0195] 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.

[0196] Preferred curing accelerators include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; organophosphorus compounds such as tributylphosphine, diphenylphosphine, and triphenylphosphine; and tetraphenylborates such as tetraphenylphosphine and triphenylphosphine tetraphenylborate. These curing agents can be used alone or in combination of two or more.

[0197] 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.

[0198] (Coupled agent)

[0199] 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.

[0200] 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.

[0201] The coupling agent is typically contained in a proportion of 0.03 to 20 parts by weight, preferably 0.05 to 10 parts by weight, and more preferably 0.1 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 0.03 parts by weight, the above-mentioned effect may not be obtained, and if it is greater than 20 parts by weight, degassing may occur.

[0202] (Filling material)

[0203] 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.

[0204] 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 powders, 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, for example, less than 80 parts by mass, or 1–70 parts by mass, or 2–65 parts by mass, or 3–60 parts by mass, or 5–55 parts by mass, or 10–50 parts by mass, or 15–45 parts by mass.

[0205] By keeping the content of inorganic filler material below the aforementioned upper limit, the risk of cracks (fissures) occurring when the protective film is bent during roll forming can be reduced; by keeping it above the aforementioned lower limit, the heat resistance of the protective film can be improved. By keeping the content of inorganic filler material within the aforementioned range, it is easy to achieve a suitable elongation at break and a suitable peel force for the heavy-face peel film 152.

[0206] (Photopolymerization initiator)

[0207] 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.

[0208] Specifically, 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-diethylthioxanone, α-hydroxycyclohexylphenyl ketone, benzyl phenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzoyl (benzil), dibenzoyl, diacetyl, 1,2-diphenylmethane, and 2-hydroxy-2-

[0209] Methyl-1-[4-(1-methylvinyl)phenyl]acetone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and β-chloroanthraquinone, etc. Photopolymerization initiators can be used alone or in combination of two or more.

[0210] 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.

[0211] (Cross-linking agent)

[0212] 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.

[0213] 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.

[0214] 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.

[0215] 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.

[0216] 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.

[0217] (General Additive)

[0218] 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.

[0219] (solvent)

[0220] The protective film forming composition preferably further contains a solvent. Protective film forming compositions containing solvents exhibit good processability.

[0221] 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.

[0222] 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.

[0223] 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.

[0224] 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.

[0225] 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.

[0226] 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.

[0227] <Supporting sheet>

[0228] 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.

[0229] 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.

[0230] 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.

[0231] 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.

[0232] (Substrate)

[0233] A resin film is preferred as the substrate constituting the support sheet.

[0234] 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.

[0235] 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.

[0236] 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.

[0237] These resin films can be cross-linked films.

[0238] 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 a thermoplastic resin into a sheet, a stretched resin film, or a resin film obtained by filming and curing a curable resin film using a prescribed method.

[0239] 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.

[0240] 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.

[0241] 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.

[0242] 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.

[0243] (Adhesive sheet)

[0244] 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.

[0245] 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.

[0246] 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.

[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 and a curing component. The polymer component has a weight-average molecular weight (Mw) of 10,000 to 2,000,000 and a molecular weight distribution (Mw / Mn) of 4 to 14. The polymer component includes an acrylic resin, and the glass transition temperature (Tg) of the acrylic resin is -6°C. At a temperature of 0–50°C, the polymer component content is 5–80 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 content of the curing component is 1–75 parts by mass relative to 100 parts of the total weight of the protective film forming film. The support sheet has a substrate, which contains a resin film. The 180° peel force between the protective film forming film and the second release film, measured at a peeling speed of 1 m / min and a temperature of 23°C, is less than 250 mN / 100 mm. The elongation at break of the protective film forming film at 23°C is greater than 700%.

[0254] 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 and a curing component. The weight-average molecular weight (Mw) of the polymer component is 10,000 to 2,000,000, and the molecular weight distribution (Mw / Mn) of the polymer component is 4 to 14. The polymer component includes an acrylic resin, and the glass transition temperature (Tg) of the acrylic resin is -60 to 50°C. For a total weight of 100 of the protective film forming film, the polymer component content is 5 to 80 parts by mass, the curing component contains a thermosetting resin, the thermosetting resin includes epoxy resin, and the content of the curing component is 1 to 75 parts by mass relative to the total weight of 100 of the protective film forming film. The support sheet has a substrate and an adhesive layer laminated on the substrate. The substrate contains a resin film. The 180° peel force between the protective film forming film and the second release film, measured at a peeling speed of 1 m / min and a temperature of 23°C, is less than 250 mN / 100 mm. The elongation at break of the protective film forming film at 23°C is greater than 700%.

[0255] Example

[0256] 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.

[0257] [Preparation of the protective film forming composition]

[0258] The following components are 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 various protective film forming compositions for forming protective film on semiconductor wafers.

[0259] (A-1): Polymer composition: 4 parts by weight of butyl acrylate, 82 parts by weight of methyl acrylate,

[0260] An acrylic polymer (weight average molecular weight: 350,000, molecular weight distribution (Mw / Mn): 4.4) is formed by copolymerizing 4 parts by weight of glycidyl methacrylate and 10 parts by weight of 2-hydroxyethyl acrylate. The glass transition temperature of this component is 5°C.

[0261] (A-2) An acrylic polymer (weight average molecular weight: 390,000, molecular weight distribution (Mw / Mn): 7.8) is prepared by copolymerizing 10 parts by mass of butyl acrylate, 80 parts by mass of methyl acrylate, 4 parts by mass of glycidyl methacrylate, and 6 parts by mass of 2-hydroxyethyl acrylate. The glass transition temperature of this component is 1°C.

[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: Dicyclopentadiene type epoxy resin: Manufactured by DIC Corporation, EPICLON HP-7200HH, epoxy equivalent 255~260g / eq

[0264] (B-3) Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, JER1055, epoxy equivalent 800-900 g / eq)

[0265] (C-1) Thermosetting agent: Thermoactive latent epoxy resin curing agent (dicyandiamide (manufactured by Mitsubishi Chemical Corporation, DICY7 active hydrogen content 21g / eq))

[0266] (D-1) Curing accelerator: 2-Phenyl-4,5-dihydroxymethylimidazol (manufactured by SHIKOKU CHEMICALSCORPORATION, CUREZOL (registered trademark) 2PHZ)

[0267] (E-1) Filler material: Silica filler (manufactured by Admatechs., SC105G-MMQ (average particle size 300nm))

[0268] (F-1) Colorant: Carbon black (manufactured by Mitsubishi Chemical Corporation, MA600)

[0269] (G-1) Silane Coupling Agent: Manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403

[0270] [Manufacturing of the first layer]

[0271] Using a doctor blade coater, the various protective film forming compositions described above were coated onto the release-treated side of a 50 μm thick polyethylene terephthalate (PET) film (equivalent to the second release film) that had undergone single-sided release treatment using silicone treatment, forming a coating layer. The protective film forming films of Examples 1 to 8, and Comparative Examples 1 and 2, with a thickness of 25 μm, were formed by drying them at 110°C for 2 minutes.

[0272] Furthermore, under conditions of 60℃±5℃, 0.4MPa, and 1m / min, the peeling treatment surface of a light-sided release film ("SP-PET381130" manufactured by Lintec Corporation, with a thickness of 38μm, equivalent to the first release film), which 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 release film), thus forming a laminate with release films stacked on both sides of the protective film forming film (i.e., the first laminate of Examples 1 to 8 and Comparative Examples 1 and 2).

[0273] (Adhesive composition)

[0274] The adhesive composition used in manufacturing the support sheet is a composition containing 100 parts by weight of polymer components (solid components) and 5 parts by weight of trifunctional dimethyl phthalate diisocyanate crosslinking agent ("TAKENATE D110N" manufactured by MITSUI CHEMICALS POLYURETHANES, INC.), and the concentration of the solid components is adjusted to 30% by weight by using a mixed solvent of methyl ethyl ketone, toluene and ethyl acetate.

[0275] In addition, the polymer composition is an acrylic copolymer with a weight average molecular weight of 500,000 obtained by copolymerizing 70 parts by weight of 2-ethylhexyl acrylate (hereinafter, sometimes referred to as "2EHA"), 20 parts by weight of methyl methacrylate (hereinafter, sometimes referred to as "MMA"), and 10 parts by weight of 2-hydroxyethyl acrylate (hereinafter, sometimes referred to as "HEA").

[0276] [Manufacturing of support sheets with release film]

[0277] The adhesive composition is applied to the release surface of a release film (SP-PET382150, manufactured by Lintec Corporation, 38 μm thick) using a doctor blade coater and dried at 110°C for 2 minutes to form an adhesive layer (10 μm thick after drying). Separately, a smooth polypropylene film (80 μm thick, manufactured by GUNZE LIMITED, with a surface roughness of 0.1 μm for the glossy side and 0.3 μm for the frosted side) is bonded to the exposed surface (the side 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.

[0278] 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 5 will be referred to as the kit of Embodiments 2 to 5, and 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.

[0279] [Composite (integrated) sheet for protective film formation]

[0280] The light-side release film of the first laminate of Comparative Example 2 (which is composed of a light-side release film / protective film forming film / heavy-side release film) was peeled off, and the adhesive layer exposed by peeling off the release film (SP-PET382150) of the support sheet was laminated on the exposed surface at 23°C, thus preparing a laminate sample of Comparative Example 2 composed of a substrate / adhesive layer / protective film forming film / heavy-side release film. All these operations were performed at 23°C.

[0281] <Wafer Attachment>

[0282] First, a silicon wafer (200 mm diameter, 350 μm thickness) with back-polishing tape (ADWILLE-8180HR manufactured by Lintec Corporation) and polished with #2000 was prepared. The light-side release film of the first laminate of Examples 1 to 8 and Comparative Example 1 (which is configured as a light-side release film / protective film forming film / heavy-side release film) was peeled off. Using an attachment device (the "RAD-3600F / 12" part of the connection device between "RAD(registered trademark)-3600F / 12" and "RAD-2700F / 12" manufactured by Lintec Corporation), the stage temperature was set to 23°C, 60°C, and 80°C, and the speed was set to 20 mm / s. The polished surface of the silicon wafer was then attached to the exposed surface. Next, a support sheet with the release film was pre-cut into a circular shape with a diameter of 203 mm, and the light-side release film was peeled off. Next, the heavy-side release film of the wafer / protective film forming film / heavy-side release film is peeled off. Using an attachment device (the "RAD-2700F / 12" part of the connecting device), set to 23°C and a speed of 20 mm / s, the exposed surface of the support sheet with the light-side release film pre-peeled is attached to the exposed surface. At this time, the support sheet is also attached to the 8-inch wafer ring frame. Next, the back-grinding tape is peeled off from the wafer / protective film forming film / support sheet. A series of processes, from peeling the light-side release film from the first laminate to peeling off the back-grinding tape, are performed in an in-line process.

[0283] 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.

[0284] 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".

[0285] 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.

[0286] 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.

[0287] 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.

[0288] 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.

[0289] 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.

[0290] The release film on the top surface of the laminate sample of Comparative Example 2 was peeled off. Using an attachment device (RAD-2700F / 12 manufactured by Lintec Corporation), the stage temperature was set to 23°C, 60°C, and 80°C, and the speed was set to 20 mm / s. The exposed surface of the protective film was attached to the polished surface of a silicon wafer (200 mm diameter, 350 μm thickness) polished with #2000. At this time, the laminate sample was also attached to an 8-inch wafer ring frame.

[0291] <Check if it floats>

[0292] Evaluation method: When the first laminate of Examples 1 to 8 and the laminate of Comparative Example 1 and Comparative Example 2 are attached to the silicon wafer in the manner described above, it is confirmed by visual inspection whether there is any floating between the protective film and the silicon wafer, or between the protective film and the support sheet. The results obtained by evaluation according to the following criteria are shown in Tables 1 and 2.

[0293] (Yes): It can be seen to float with the naked eye.

[0294] (None): No floating was observed with the naked eye.

[0295] <Check for wrinkles>

[0296] Evaluation method: When the first laminate of Examples 1 to 8 and the laminate of Comparative Example 1 and Comparative Example 2 were attached to the silicon wafer in the manner described above, it was confirmed by visual inspection whether there were wrinkles in the substrate. The results of the evaluation were shown in Tables 1 and 2.

[0297] (Yes): Wrinkles can be seen with the naked eye.

[0298] (None): No wrinkles were detected by the naked eye.

[0299] <Retraction phenomenon during peeling of the peeling film>

[0300] Evaluation method: When the first laminate (which is configured as a light-side release film / protective film forming film / heavy-side release film) of Examples 1 to 8 and Comparative Example 1 is attached to the silicon wafer in the manner described above, and the heavy-side release film is peeled off in the device, the protective film forming film is peeled off together with the heavy-side release film at the wafer end. The results obtained by the evaluation according to the following criteria are shown in Tables 1 and 2.

[0301] (Yes): It can be visually confirmed that the protective film is peeled off together with the surface stripping film at the wafer end.

[0302] (None): The protective film was not visually confirmed to be peeled off together with the surface stripping film at the wafer end.

[0303] <Cracking of the protective film during the attachment of the support sheet>

[0304] The protective film protrusion was visually inspected to determine whether it ruptured when the support sheet was attached to the first laminate of Examples 1 to 8 and Comparative Example 1.

[0305] Evaluation method: The protective film was visually inspected to determine whether the protrusion of the protective film was ruptured. The results of the evaluation according to the following criteria are shown in Tables 1 and 2.

[0306] (C): There are more than two locations where the protective film forming membrane is ruptured, as confirmed by the naked eye.

[0307] (B): The location where the protective film ruptures at the protrusion of the protective film is confirmed by visual inspection is 1.

[0308] (A): The rupture of the protective film protrusion was not visually confirmed.

[0309] <Determination of Elongation at Break>

[0310] A protective film measuring 15 mm wide and 40 mm long, and laminated to a thickness of 200 μm, was used as a test piece. This test piece was heated to 23°C, and the elongation was measured when stretched at a tensile speed of 100 mm / min and a clamping distance of 10 mm. The elongation at break was calculated based on the elongation at fracture.

[0311] <Determination of peel force of peel film>

[0312] The light-side release film of the light-side release film / protective film forming film / heavy-side release film structure is peeled off, and a 25μm layer of high-adhesion PET (manufactured by TOYOBO Co., Ltd., PET25A-4100) is attached to the exposed protective film forming film by hot lamination (70°C, 1m / min) to create a laminated sample. This is then cut to a 100mm width to prepare a sample for testing. Next, the back side of the heavy-side release film of the sample for testing is fixed to a support plate using double-sided tape.

[0313] Test method: Using a universal tensile testing machine (manufactured by Shimadzu Corporation, product name "AUTOGRAPH (registered trademark) AG-IS"), at 23°C, at a peel angle of 180° and a peel speed of 1 m / min, the laminate sample of protective film forming film / excellent adhesive PET was peeled from the heavy-side peel film, and the load at this time was taken as the peel force.

[0314] [Table 1]

[0315]

[0316] [Table 2]

[0317]

[0318] When the stage temperature is set to less than 80°C and the first laminate of Examples 1 to 8, Comparative Example 1, and Comparative Example 2 are attached to the wafer, floating is sometimes observed between the protective film and the wafer, and between the protective film and the support sheet. In contrast, when the stage temperature is set to 80°C and the first laminate of Examples 1 to 8, Comparative Example 1, and Comparative Example 2 are attached to the wafer, floating is not observed between the protective film and the wafer, or between the protective film and the support sheet.

[0319] Furthermore, when the stage temperature was set to 80°C and the first laminate of Examples 1 to 8, Comparative Example 1, and Comparative Example 2 were attached to the wafer, wrinkles were not observed in the substrates of Examples 1 to 8 and Comparative Example 1, but wrinkles were observed in the substrate of Comparative Example 2.

[0320] Because the 180° peel force between the protective film forming film and the second release film, measured at a peeling speed of 1 m / min and a temperature of 23°C, was less than 250 mN / 100 mm for the kits of Examples 1-4, Examples 6-8, and Comparative Example 1, the protective film forming film was not peeled off together with the second release film when peeling off the second release film from the protective film forming film. In contrast, because the 180° peel force of the kit of Example 5 was greater than 250 mN / 100 mm, the protective film forming film was peeled off together with the second release film.

[0321] Since the protective film forming film of the kits in Examples 1 to 6 and Example 8 has an elongation at break of more than 700% at 23°C, when the support sheet is attached to the wafer / protective film forming film, no cracking of the protruding part of the protective film forming film is visually detected.

[0322] Since the protective film forming film of the kit in Example 7 has an elongation at break of 730% at 23°C, when the support sheet is attached to the wafer / protective film forming film, the location where the protrusion of the protective film forming film breaks is visually confirmed to be 1.

[0323] Since the protective film forming film of Comparative Example 1 has an elongation at break of less than 700% at 23°C, when the support sheet is attached to the wafer / protective film forming film, more than two locations where the protrusion of the protective film forming film is ruptured can be visually confirmed.

[0324] These results indicate that the third-layer stack can be more appropriately manufactured using in-line processes by using the kits of Examples 1-8.

[0325] Industrial applicability

[0326] 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 and a support sheet, wherein a first release film, a thermosetting protective film forming film, and a second release film are sequentially laminated in the first laminate, and the support sheet is used to support a workpiece that is the object to be protected by the protective film forming film and the protective film forming film, wherein, The protective film is formed from a protective film forming composition comprising a polymer component, a curing component, and a filler material. The polymer component is an acrylic resin, the molecular weight distribution of the polymer component is 4 or higher and 14 or lower, the weight-average molecular weight of the polymer component is 100,000 to 1,200,000, and the glass transition temperature of the acrylic resin is in the range of -60°C to 50°C. The curing component comprises a thermosetting resin and a thermosetting agent. The thermosetting resin is an epoxy resin, and the thermosetting agent is a compound having two or more functional groups per molecule capable of reacting with epoxy groups. Relative to 100 parts by weight of the total weight of the protective film, the content of the polymer component is 5-80 parts by weight, the content of the thermosetting component is 1-75 parts by weight, and the content of the filler material is 2-65 parts by weight. The protective film forms a film with an elongation at break of more than 1900% at 23°C.

2. The kit according to claim 1, wherein, The first layer is rolled up.

3. The kit according to claim 1 or 2, wherein, The adhesive layer of the support sheet, which is attached to the protective film forming film, is stacked on the substrate.

4. The kit according to claim 1 or 2, wherein, The peel force between the protective film forming film and the second release film is greater than the peel force between the protective film forming film and the first release film. The peeling force at 180° between the protective film forming film and the second release film, measured at a peeling speed of 1 m / min and a temperature of 23°C, is less than 250 mN / 100 mm.

5. A method for manufacturing a third laminate, wherein the kit according to any one of claims 1 to 4 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: The process of peeling off the first release film from the first laminate; The first lamination process of attaching the protective film to the workpiece to form the exposed surface of the film; and In the second lamination process of attaching the support sheet to the side of the protective film opposite to the exposed side, 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, operations are performed from the start of the first lamination process to the end of the second lamination process, or between the first lamination process and the second lamination process, in which the second laminate, to which the protective film is attached, is conveyed piece by piece. 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.

6. A method for manufacturing a third laminate, wherein the kit according to any one of claims 1 to 4 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: The process of peeling off the first release film from the first laminate; The first lamination process of attaching the protective film to the workpiece to form the exposed surface of the film; and In the second lamination process of attaching the support sheet to the side of the protective film opposite to the exposed side, 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, operations are performed from the start of the first lamination process to the end of the second lamination process, or between the first lamination process and the second lamination process, in which the second laminate, to which the protective film is attached, is conveyed piece by piece. 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.

7. A method for manufacturing a third laminate, wherein the kit according to any one of claims 1 to 4 is used in an online process, and the third laminate comprises a workpiece, the protective film forming film, and the support sheet stacked sequentially, the manufacturing method comprising: The process of peeling off the first release film from the first laminate; The first lamination process of attaching the protective film to the workpiece to form the exposed surface of the film; and In the second lamination process of attaching the support sheet to the side of the protective film opposite to the exposed side, 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.

8. The method for manufacturing the third laminate according to any one of claims 5 to 7, wherein, The first layering process is performed on a wafer worktable at a temperature above 80°C.

9. The method for manufacturing the third laminate according to any one of claims 5 to 7, wherein, A backing abrasion tape is attached to the surface of the workpiece opposite to the exposed surface of the protective film to which it is attached. After the second lamination process, a process of peeling the backing abrasion tape off the workpiece is included.

10. The method for manufacturing the third laminate according to claim 9, wherein, Within 10 minutes of beginning the first lamination process, the backing tape is peeled off the workpiece.

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