TWI839508B - Method for manufacturing a third laminate, method for manufacturing a fourth laminate, method for manufacturing a semiconductor device with an inner surface protective film, and method for manufacturing a third laminate - Google Patents

Abstract

The present invention relates to a method for manufacturing a third laminate (19), wherein one side of a workpiece (14) is a conductive surface (14a), and the other side is an inner side (14b); one side of a film (13) for forming an inner surface protective film is a smooth surface (13b), and the other side is a rough surface (13a) that is rougher than the smooth surface (13b). The method for manufacturing the third laminate (19) sequentially comprises: a first lamination step, in which the rough surface (13a) of the film (13) for forming an inner surface protective film is adhered to the inner side (14b) of the workpiece (14) in a facing manner; and a second lamination step, in which a support sheet (10) is adhered to the smooth surface (13b) of the film (13) for forming an inner surface protective film.

Description

A method for manufacturing a third laminate, a method for manufacturing a fourth laminate, a method for manufacturing a semiconductor device with an inner surface protective film, and a third laminate

The present invention relates to a method for manufacturing a third laminate, a method for manufacturing a fourth laminate, a method for manufacturing a semiconductor device with an inner surface protective film, and a third laminate. Specifically, the present invention relates to: a method for manufacturing a third laminate, wherein the third laminate is formed by laminating a workpiece such as a semiconductor wafer, a film for forming an inner surface protective film, and a support sheet in sequence; a method for manufacturing a fourth laminate, wherein the fourth laminate is formed by laminating a workpiece such as a semiconductor wafer, an inner surface protective film, and a support sheet in sequence; a method for manufacturing a semiconductor device with an inner surface protective film, wherein the method for manufacturing a third laminate and the method for manufacturing a fourth laminate are used; and a third laminate is formed by laminating a workpiece such as a semiconductor wafer, a film for forming an inner surface protective film, and a support sheet in sequence. This application claims priority based on Japanese Patent Application No. 2019-086298 filed in Japan on April 26, 2019, and the contents of that application are incorporated herein by reference.

In recent years, a so-called flip-chip (face down) packaging method has been applied to manufacture semiconductor devices. In the flip-chip method, a semiconductor chip having electrodes such as bumps on a conductive surface is used, and the aforementioned electrodes are bonded to a substrate. Therefore, the inner surface of the semiconductor chip opposite to the conductive surface is sometimes exposed.

On the inner surface of the exposed semiconductor chip, a resin film containing an organic material is sometimes formed as an inner surface protective film, and the semiconductor chip with the inner surface protective film is assembled into a semiconductor device. The inner surface protective film is used to prevent cracks from occurring in the semiconductor chip after the dicing step or packaging (e.g., Patent Document 1, Patent Document 2).

Such a semiconductor chip with an inner surface protective film is manufactured, for example, through the steps shown in Fig. 9. That is, the following method is known: a film 13 for forming an inner surface protective film is laminated on the inner surface 8b of a semiconductor wafer 8 having a conductive surface (Fig. 9(A)), the film 13 for forming an inner surface protective film is thermally cured or energy-beam-cured to form an inner surface protective film 13' (Fig. 9(B)), the inner surface protective film 13' is laser-marked (Fig. 9(C)), a supporting sheet 10 is laminated on the inner surface protective film 13' (Fig. 9(D)), the semiconductor wafer 8 and the inner surface protective film 13' are cut to form a semiconductor chip 7 with an inner surface protective film (Fig. 9(E) and Fig. 9(F)), and the semiconductor chip 7 with an inner surface protective film is picked up from the supporting sheet 10. The order of the curing step and the laser marking step is arbitrary, and the inner surface protective film forming film 13 may be laminated on the inner surface 8b of the semiconductor wafer 8 having the electric path surface (FIG. 9(A)), and after the inner surface protective film forming film 13 is laser marked, the inner surface protective film forming film 13 is thermally cured or energy-ray cured to form the inner surface protective film 13', and then the steps of FIG. 9(D) to FIG. 9(G) are performed. Here, the device for laminating the inner surface protective film forming film 13 on the inner surface 8b of the semiconductor wafer 8 in FIG. 9(A) and the device for laminating the support sheet 10 on the inner surface protective film 13' in FIG. 9(D) are performed by different devices. These methods are not only used for cutting a semiconductor wafer to produce a semiconductor device as a singulated semiconductor chip, but are also used for producing the following semiconductor devices: a semiconductor device panel composed of an assembly of semiconductor devices in which at least one electronic component is sealed with a sealing resin is similarly cut to produce a semiconductor device in which at least one electronic component is sealed with a sealing resin.

In addition, a composite sheet for forming a protective film in which the inner surface protective film forming film 13 and the supporting sheet 10 are integrated is also used for the production of a semiconductor chip with an inner surface protective film (for example, Patent Document 2).

The method for manufacturing a semiconductor chip with an inner surface protective film using a protective film forming composite sheet is, for example, through the steps shown in FIG10. That is, the following method is known: the inner surface protective film forming film 13 (FIG. 10(A')) of the protective film forming composite sheet 1 formed by laminating the inner surface protective film forming film 13 and the support sheet 10 is attached to the inner surface 8b of the semiconductor wafer 8 having an electric path surface, the electric path protection tape 17 (FIG. 10(B')) is peeled off, and the inner surface protective film forming film 13 is subjected to heat curing or energy beam curing. The inner surface protective film 13' is hardened to form a inner surface protective film 13' (FIG. 10(C')), the inner surface protective film 13' is laser marked from the side of the support sheet 10 (FIG. 10(D')), the semiconductor wafer 8 and the inner surface protective film 13' are cut to form a semiconductor chip 7 with an inner surface protective film (FIG. 10(E') and FIG. 10(F')), and the semiconductor chip 7 with an inner surface protective film is picked up from the support sheet 10. In this case, the order of the hardening step and the laser marking step is also arbitrary. These methods are not only used for manufacturing semiconductor devices as semiconductor chips, but also for manufacturing the following semiconductor devices: from a semiconductor device panel composed of an assembly of semiconductor devices in which at least one electronic component is sealed with a sealing resin, cutting is performed in the same manner to manufacture a semiconductor device in which at least one electronic component is sealed with a sealing resin. [Prior art document] [Patent document]

[Patent Document 1] Japanese Patent No. 4271597. [Patent Document 2] Japanese Patent No. 5363662.

[The problem that the invention wants to solve]

In the method for manufacturing a semiconductor device in which an inner surface protective film forming film 13 is laminated on the inner surface 8b of a semiconductor wafer 8 as shown in FIG9, the exposed inner surface protective film forming film 13 or the inner surface protective film 13' can be directly laser marked. However, in the method for manufacturing a semiconductor device in which an inner surface protective film forming film 13 is attached to the inner surface 8b of a semiconductor wafer 8 as shown in FIG10, laser marking is performed by irradiating laser light through the support sheet 10 from the side of the support sheet 10, but the outline of the text or mark printed at the interface between the inner surface protective film forming film 13 and the support sheet 10 is blurred, and the visibility after printing is deteriorated.

Therefore, the purpose of the present invention is to provide a method for manufacturing a third laminate, wherein the third laminate is formed by laminating a workpiece such as a semiconductor wafer, a film for forming an inner surface protective film, and a support sheet in sequence, and the inner surface protective film can be laser-marked through the support sheet, and the laser marking has good visibility. In addition, the purpose of the present invention is to provide a method for manufacturing a fourth laminate, wherein the fourth laminate is formed by laminating a workpiece such as a semiconductor wafer, an inner surface protective film, and a support sheet in sequence, and the inner surface protective film can be laser-marked through the support sheet, and the laser marking has good visibility. Furthermore, the purpose of the present invention is to provide a method for manufacturing a semiconductor device with an inner surface protective film using these manufacturing methods. [Means for Solving the Problem]

The present invention provides the following methods for manufacturing a third laminate, a method for manufacturing a fourth laminate, a method for manufacturing a semiconductor device with an inner surface protective film, and a third laminate.

[1] A method for manufacturing a third laminate, wherein the third laminate is formed by laminating a workpiece, a film for forming an inner surface protective film, and a support sheet in sequence; one side of the workpiece is a conductive surface, and the other side is an inner surface; one side of the film for forming an inner surface protective film is a smooth surface, and the other side is a rough surface that is rougher than the smooth surface; the method for manufacturing the third laminate comprises: a first lamination step of laminating the rough surface of the film for forming an inner surface protective film on the inner surface of the workpiece in a facing relationship; and a second lamination step of laminating the support sheet on the smooth surface of the film for forming an inner surface protective film.

[2] The method for manufacturing a third laminate as described in [1] above, wherein at least the process from the first lamination step to the second lamination step is performed by connecting a device for attaching a film for forming an inner surface protective film to a device for attaching a support sheet, or by performing the process in the same device. [3] The method for manufacturing a third laminate as described in [1] or [2] above, wherein between the first lamination step and the second lamination step, the second laminate having the film for forming an inner surface protective film attached to the workpiece is conveyed piece by piece. [4] The method for manufacturing a third laminate as described in any one of the above [1] to [3], wherein the distance of transporting the workpiece from the starting point of the attachment in the above first lamination step to the ending point of the attachment in the above second lamination step is less than 7000 mm. [5] The method for manufacturing a third laminate as described in any one of the above [1] to [4], wherein the time of transporting the workpiece from the starting point of the attachment in the above first lamination step to the ending point of the attachment in the above second lamination step is less than 150 seconds.

[6] A method for manufacturing a third laminate as described in any one of the above [1] to [5], wherein the above-mentioned electrical surface of the above-mentioned workpiece is protected by an electrical surface protection tape; and after the above-mentioned second lamination step, it includes: a peeling step of peeling the above-mentioned electrical surface protection tape from the above-mentioned electrical surface of the above-mentioned workpiece. [7] A method for manufacturing a third laminate as described in the above [6], wherein the above-mentioned inner surface of the above-mentioned workpiece is a ground surface, and the above-mentioned electrical surface protection tape is an inner surface grinding tape. [8] A method for manufacturing a third laminate as described in any one of the above [1] to [7], wherein the above-mentioned workpiece is a semiconductor wafer. [9] A method for manufacturing a third laminate as described in any one of [1] to [7] above, wherein the workpiece is a semiconductor device panel composed of an assembly of semiconductor devices including at least one electronic component sealed by a sealing resin.

[10] The method for manufacturing a third laminate as described in any one of the above [1] to [9], wherein the support sheet is provided with an adhesive layer on a substrate; the method for manufacturing the third laminate comprises: a second lamination step of attaching the adhesive layer of the support sheet to the smooth surface of the film for forming the inner surface protective film. [11] The method for manufacturing a third laminate as described in the above [10], wherein the adhesive layer is energy ray curable.

[12] A method for manufacturing a third laminate as described in any one of the above [1] to [11], comprising: irradiating the inner surface protective film forming film with a laser from the side of the above support sheet to perform laser marking. [13] A method for manufacturing a fourth laminate, wherein the fourth laminate is formed by sequentially stacking a workpiece, an inner surface protective film and a support sheet, and the method for manufacturing the fourth laminate comprises: hardening the inner surface protective film forming film of the third laminate manufactured by the manufacturing method as described in any one of the above [1] to [12] to form an inner surface protective film. [14] The method for manufacturing the fourth laminate as described in [13] above includes: irradiating the inner protective film with laser from the side of the support sheet to perform laser marking.

[15] A method for manufacturing a semiconductor device with an inner surface protective film, comprising: a step of cutting the workpiece and the inner surface protective film of the fourth laminate body manufactured by the manufacturing method described in [13] or [14] to produce a semiconductor device with an inner surface protective film; and a step of picking up the semiconductor device with the inner surface protective film from the supporting sheet. [16] A method for manufacturing a semiconductor device with an inner surface protective film, comprising: a step of cutting the inner surface protective film forming film of the third laminate body manufactured by the manufacturing method described in any one of items [1] to [12] and the workpiece to form a semiconductor device with an inner surface protective film forming film; a step of hardening the inner surface protective film forming film to form an inner surface protective film; and a step of picking up the semiconductor device with an inner surface protective film forming film or the semiconductor device with an inner surface protective film from the supporting sheet. [17] The method for manufacturing a semiconductor device with an inner surface protective film as described in [15] or [16] above, wherein the film for forming the inner surface protective film is heat-curable, and the step of manufacturing the inner surface protective film is to heat-treat the film for forming the inner surface protective film for heat curing. [18] The method for manufacturing a semiconductor device with an inner surface protective film as described in [15] or [16] above, wherein the film for forming the inner surface protective film is energy-ray-curable, and the step of manufacturing the inner surface protective film is to irradiate the film for forming the inner surface protective film for energy-ray curing.

[19] A third laminated body is formed by laminating a workpiece, a film for forming an inner surface protective film, and a support sheet in sequence; one side of the workpiece is a conductive surface, and the other side is an inner side; one side of the film for forming an inner surface protective film is a smooth surface, and the other side is a rough surface that is rougher than the smooth surface; the rough surface of the film for forming an inner surface protective film is bonded to the inner side of the workpiece; and the support sheet is bonded to the smooth surface of the film for forming an inner surface protective film. [Effect of the invention]

According to the present invention, a method for manufacturing a third laminate is provided, wherein the third laminate is formed by laminating a workpiece, a film for forming an inner surface protective film, and a support sheet in sequence, and the inner surface protective film can be laser-marked through the support sheet, and the laser marking has good visibility. In addition, the present invention provides a method for manufacturing a fourth laminate, wherein the fourth laminate is formed by laminating a workpiece, an inner surface protective film, and a support sheet in sequence, and the inner surface protective film can be laser-marked through the support sheet, and the laser marking has good visibility. Furthermore, the present invention provides a method for manufacturing a semiconductor device with an inner surface protective film, which uses the method for manufacturing the third laminate and the method for manufacturing the fourth laminate.

Hereinafter, a method for manufacturing a third multilayer body, a method for manufacturing a fourth multilayer body, and a method for manufacturing a semiconductor device as embodiments of the present invention will be described in detail. In addition, the drawings used in the following description sometimes enlarge the features for convenience in order to facilitate understanding of the features, and the size ratios of the components are not limited to the same as the actual ones.

[Manufacturing method of the third laminate] FIG1 is a schematic cross-sectional view schematically showing an example of an implementation form of the manufacturing method of the third laminate. The manufacturing method of the third laminate of this implementation form is to manufacture a third laminate 19 formed by laminating a workpiece 14, a film 13 for forming an inner surface protective film, and a support sheet 10 in sequence, and one side of the workpiece 14 is a conductive surface 14a, and the other side is an inner surface 14b (FIG. 1(a)), one side of the film 13 for forming an inner surface protective film is a smooth surface 13b, and the other side is a rough surface that is rougher than the smooth surface 13b. The manufacturing method of the third laminated body sequentially includes: a first lamination step (FIG. 1(b)), in which the rough surface 13a of the inner surface protective film forming film 13 is adhered to the inner surface 14b of the workpiece 14 in a facing manner; a second lamination step (FIG. 1(d)), in which the supporting sheet 10 is adhered to the smooth surface 13b of the inner surface protective film forming film 13 (FIG. 1(a) to FIG. 1(e)).

That is, the third laminate of the present embodiment is formed by laminating the workpiece 14, the film 13 for forming the inner surface protective film and the support sheet 10 in sequence, and one side of the workpiece 14 is a conductive surface 14a, and the other side is an inner surface 14b, one side of the film 13 for forming the inner surface protective film is a smooth surface 13b, and the other side is a rough surface 13a which is rougher than the smooth surface 13b, the rough surface 13a of the film 13 for forming the inner surface protective film is bonded to the inner surface 14b of the workpiece 14, and the support sheet 10 is bonded to the smooth surface 13b of the film 13 for forming the inner surface protective film (Figure 1(e)).

In the present embodiment, a semiconductor wafer is used as the workpiece 14 shown in FIG. 1(a). One side of the semiconductor wafer is a conductive surface 14a on which bumps are formed. In addition, in order to prevent the conductive surface 14a and the bumps of the semiconductor wafer from being crushed when the inner surface of the semiconductor wafer is ground, or to prevent dimples or cracks from being generated on the inner surface of the wafer, the conductive surface 14a and the bumps of the semiconductor wafer are protected by a conductive surface protection tape 17. The conductive surface protection tape 17 is an inner surface grinding tape, and the inner surface of the semiconductor wafer as the workpiece 14 (that is, the inner surface 14b of the workpiece) is a ground surface.

The workpiece 14 is not limited as long as it has an electric path surface 14a on one side and the other side can be called an inner surface. The workpiece 14 may be exemplified by the following workpieces, such as a semiconductor wafer having an electric path surface on one side, or a semiconductor device panel composed of a semiconductor device assembly with terminals, wherein the semiconductor device assembly with terminals is formed by sealing individual electronic components with sealing resin and has a terminal forming surface (in other words, an electric path surface) of the semiconductor device with terminals on one side.

As the electrical pavement protection tape 17, for example, the surface protection sheet disclosed in Japanese Patent Gazette No. 2016-192488 and Japanese Patent Gazette No. 2009-141265 can be used. The electrical pavement protection tape 17 has an adhesive layer with a moderate re-peelable property. The aforementioned adhesive layer can also be formed by a common weak adhesive such as rubber, acrylic, silicone, urethane, vinyl ether, etc. In addition, the aforementioned adhesive layer can also be an energy-ray-hardening adhesive that is hardened by irradiation with energy rays to become re-peelable. The electrical pavement protection tape 17 is in the shape of a double-sided tape, and the outer side of the electrical pavement protection tape 17 can also be fixed to a hard support body, and the workpiece 14 can also be fixed to a hard support body.

In this specification, the term "energy ray" refers to radiation with energy quanta in electromagnetic waves or charged particle beams. Examples of energy rays include ultraviolet rays, radiation, electron beams, etc. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light lamp, or an LED (Light Emitting Diode) lamp as an ultraviolet ray source. As for electron beams, electron beams generated by electron beam accelerators can be irradiated. In addition, in this specification, the term "energy ray curability" refers to the property of curing by irradiation with energy rays, and the term "non-energy ray curability" refers to the property of not curing even if irradiated with energy rays.

In the first lamination step of the present embodiment shown in FIG1(b), the inner surface protective film forming film 13 can be used as the first lamination body 5 shown in FIG2. The first lamination body 5 shown in FIG2 has a first peeling film 151 on one side (i.e., the rough surface 13a) of the inner surface protective film forming film 13, and has a second peeling film 152 on the other side (i.e., the smooth surface 13b) opposite to the rough surface 13a. After the first peeling film 151 on the side of the rough surface 13a is peeled off, in the first lamination step, the rough surface 13a of the inner surface protective film forming film 13 is laminated on the inner surface 14b of the workpiece 14 in a facing manner (FIG1(b)). The inner protective film forming film 13 at this time may be a processed product previously processed according to the shape of the workpiece 14, or may be processed in the device just before lamination. Next, it is preferred to peel off the second release film 152 on the side of the smooth surface 13b to form the second laminate 6 (Fig. 1(c)).

The inner surface protective film forming film shown in FIG2 is formed by coating a protective film forming composition containing a solvent on the release surface of the second release film 152 having a thickness of 38 μm by a blade coater, and then drying the film at 120° C. for 2 minutes in an oven. Then, the inner surface protective film forming film can be overlapped with the release surface of the first release film 151 having a thickness of 38 μm and the two can be bonded together to obtain an inner surface protective film forming film composed of the first release film 151, the inner surface protective film forming film (the inner surface protective film forming film 13 in FIG2) (thickness: 25 μm), and the second release film 152. Such an inner surface protective film forming film is suitable for storage in a roll shape, for example. In addition, by setting the peeling surface of the first peeling film 151 to a rough surface with a surface roughness Ra of 200 nm, for example, and setting the peeling surface of the second peeling film 152 to a smooth surface smoother than the surface roughness of the rough surface, for example, with a surface roughness Ra of 30 nm, one side of the inner surface protective film forming film 13 can be set to a smooth surface 13b, and the other side of the inner surface protective film forming film 13 opposite to the one side can be set to a rough surface 13a rougher than the smooth surface 13b. Then, after the first peeling film 151 on the side of the rough surface 13a is peeled off, the rough surface 13a of the inner surface protective film forming film 13 is attached to the inner surface 14b of the workpiece 14 in the first lamination step.

Alternatively, even if the surface roughness Ra of the peeling surface of the first peeling film 151 and the surface roughness Ra of the peeling surface of the second peeling film 152 are the same smooth surface, for example, one side of the inner surface protective film forming film 13 can be set as a smooth surface 13b, and the other side of the inner surface protective film forming film 13 opposite to the aforementioned side can be set as a rough surface 13a that is rougher than the smooth surface 13b as described below.

That is, after coating the protective film forming composition containing a solvent on the peeling surface of the second peeling film 152 with a surface roughness Ra of 30nm by a blade coater, it is dried in an oven at 120°C for 2 minutes to form an inner surface protective film forming film. Then, the peeling surface of the first peeling film 151 with a thickness of 38μm and a surface roughness Ra of 30nm can be superimposed on the inner surface protective film forming film, and the two can be bonded together under conditions of 23°C and 0.4MPa, to obtain an inner surface protective film forming film composed of the first peeling film 151, the inner surface protective film forming film (the inner surface protective film forming film 13 in FIG. 2) (thickness: 25μm), and the second peeling film 152. Thus, the rough surface 13a of the inner surface protective film forming film 13 and the first peeling film 151 form a light peeling surface, and the smooth surface 13b of the inner surface protective film forming film 13 and the second peeling film 152 form a heavy peeling surface with a peeling strength greater than that of the light peeling surface. Such an inner surface protective film forming film is also suitable for storage in a roll shape, for example.

The surface roughness of the first peeling film 151 side of the inner surface protective film forming film can be adjusted by the temperature and pressure conditions of laminating the peeling surface of the first peeling film 151 to the inner surface protective film forming film. If the temperature and pressure conditions of laminating the peeling surface of the first peeling film 151 to the inner surface protective film forming film are increased, the surface roughness of the first peeling film 151 side of the inner surface protective film forming film becomes the surface roughness of the peeling surface of the first peeling film 151 as it is.

The surface roughness Ra of the rough surface of the film for forming the inner surface protective film facing the inner surface of the workpiece can be 32nm to 1200nm, preferably 32nm to 1000nm, more preferably 32nm to 900nm, and particularly preferably 32nm to 800nm.

When the surface roughness Ra of the rough surface of the inner surface protective film forming film is large, the area in contact with the peeling film is reduced. Therefore, when the surface roughness Ra of the rough surface of the inner surface protective film forming film is greater than the lower limit value, the rough surface side of the inner surface protective film forming film is easily peeled off first. Thus, when the peeling film on the side with the smaller peeling force is peeled, the risk of the following peeling failure (so-called partial peeling) can be reduced: the inner surface protective film forming film is not properly peeled from the peeling film on the side with the smaller peeling force, the inner surface protective film forming film is cohesively destroyed, and a part of the inner surface protective film forming film remains on the peeling film on the side with the smaller peeling force.

The surface roughness Ra of the smooth surface of the inner surface protective film-forming film facing the side of the supporting sheet is preferably 20 nm to 80 nm, more preferably 24 nm to 50 nm, and particularly preferably 28 nm to 32 nm.

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

In the second lamination step shown in FIG. 1( d ), a support sheet 10 is laminated on the smooth surface 13b of the inner surface protective film forming film 13 laminated on the inner surface 14b of the workpiece 14. The support sheet 10 is, for example, a circular polyethylene terephthalate film having a thickness of 80 μm and a diameter of 270 mm, and has a clamp adhesive layer 16 on the outer periphery. In the present embodiment, the workpiece 14 is fixed to a fixing clamp 18 together with the inner surface protective film forming film 13. Subsequently, the support sheet 10 is laminated on the smooth surface 13b of the inner surface protective film forming film 13, and is fixed to the fixing clamp 18 via the clamp adhesive layer 16 ( FIG. 1( e )).

Previously, the device for laminating the inner surface protective film forming film 13 on the inner surface 8b of the semiconductor wafer 8 in FIG. 9(A) and the device for laminating the support sheet 10 on the inner surface protective film 13' in FIG. 9(D) were laminated using different devices, and each laminated body was accommodated in a cassette and transported to the next device. However, in the present embodiment, the process from at least the first lamination step shown in FIG. 1(b) to the second lamination step shown in FIG. 1(d) can be performed by connecting the device for attaching the inner surface protective film forming film and the device for attaching the support sheet, or by using the same device. Therefore, between the aforementioned first lamination step and the aforementioned second lamination step, the second lamination body with the inner surface protective film forming film 13 attached to the workpiece 14 can be transported piece by piece to the second lamination step shown in FIG. 1(d) without being housed in a cassette. By performing the process in the same device, the device space can be further reduced. By performing the process in a connected device, even if the design is not started from scratch, the previous device can be modified to cope with it, and the initial cost can be reduced. Moreover, the second lamination body is not housed in a cassette but transported outside the device, so the manufacturing efficiency is improved, and the contamination and damage of the second lamination body can be suppressed.

In this embodiment, the step of peeling off the second peeling film 152 on the side of the smooth surface 13b from the inner surface protective film forming film 13 after the first lamination step can also be carried out by connecting the device for attaching the inner surface protective film forming film, the device for peeling off the second peeling film, and the device for attaching the supporting sheet, or can also be carried out in the same device.

The inner surface protective film forming film 13 used in the first lamination step can be processed into the shape of the workpiece in advance, or can be processed in the same device just before the first lamination step. When the size of the workpiece is fixed in the manufacturing line used, it is more efficient to be able to process in advance. When the size of the workpiece may change, the inner surface protective film forming film will not be wasted if it is the latter, which has a cost advantage.

Regarding the step of peeling off the first peeling film 151 on the side of the rough surface 13a from the inner surface protective film forming film 13 of the first laminate body 5 before the first lamination step, the step can be carried out by connecting the device for peeling off the first peeling film and the device for attaching the inner surface protective film forming film, or can be carried out in the same device.

In this embodiment, the transport distance of the workpiece 14 from the attachment start point of the aforementioned first lamination step to the attachment end point of the aforementioned second lamination step (or from the attachment start point of the aforementioned first lamination step to the hardening end point of the hardening step) can be designed to be less than 7000 mm, which can reduce the equipment space. The conveying distance of the workpiece 14 from the attachment starting point of the aforementioned first lamination step to the attachment ending point of the aforementioned second lamination step (or from the attachment starting point of the aforementioned first lamination step to the hardening ending point of the hardening step) can also be set to less than 6500 mm, less than 6000 mm, less than 4500 mm, or less than 3000 mm.

In this embodiment, the workpiece 14 conveying time from the start of the first lamination step to the end of the second lamination step can be set to 150 seconds or less, which can shorten the step time. The workpiece 14 conveying time from the start of the first lamination step to the end of the second lamination step can also be set to 130 seconds or less, or 110 seconds or less, or 90 seconds or less, or 70 seconds or less.

In this embodiment, the workpiece 14 transport time from the start of the first lamination step to the end of the curing step can be set to 400 seconds or less, which can shorten the step time. The workpiece 14 transport time from the start of the first lamination step to the end of the curing step can also be set to 300 seconds or less, or 250 seconds or less, or 200 seconds or less, or 150 seconds or less.

In the first lamination step of the method for manufacturing the third laminate, the speed at which the rough surface 13a of the inner surface protective film forming film 13 is attached to the inner surface 14b of the workpiece 14, and in the second lamination step of the method for manufacturing the third laminate, the speed at which the support sheet 10 is attached to the smooth surface 13b of the inner surface protective film forming film 13 can also be set to 100 mm/s or less, or can be set to 80 mm/s or less, or can be set to 60 mm/s or less, or can be set to 40 mm/s or less. By making the aforementioned attaching speed in the first lamination step and the aforementioned attaching speed in the second lamination step below the above-mentioned upper limit value, the adhesion between the workpiece 14 and the film 13 for forming the inner surface protective film, and the adhesion between the film 13 for forming the inner surface protective film and the supporting sheet 10 can be improved.

The above-mentioned attaching speed in the first lamination step and the above-mentioned attaching speed in the second lamination step may also be set to 2 mm/s or more, 5 mm/s or more, or 10 mm/s or more. By making the aforementioned attaching speed in the first lamination step and the aforementioned attaching speed in the second lamination step above the above-mentioned lower limit value, the production efficiency of the second laminate 6 and the third laminate 19 can be improved, and the conveying time of the workpiece 14 from the start of attaching in the first lamination step to the end of attaching in the second lamination step can be set to less than 150 seconds, and the conveying time of the workpiece 14 from the start of attaching in the first lamination step to the end of curing in the curing step can be set to less than 400 seconds.

The conveying distance of the aforementioned workpiece from the attachment start point of the first lamination step of the present embodiment shown in FIG. 1(b) to the attachment end point of the second lamination step shown in FIG. 1(d) can be set to 7000 mm or less, 6500 mm or less, 6000 mm or less, 4500 mm or less, or 3000 mm or less. The conveying time of the aforementioned workpiece from the attachment start point of the first lamination step of the present embodiment shown in FIG. 1(b) to the attachment end point of the second lamination step shown in FIG. 1(d) can be set to 150 seconds or less, 130 seconds or less, or 110 seconds or less.

In addition, the conveying distance of the aforementioned workpiece from the attachment starting point of the first lamination step of the present embodiment shown in FIG. 1(b) to the curing end point of the curing step shown in FIG. 4(g) can be set to 7000 mm or less, 6500 mm or less, 6000 mm or less, 4500 mm or less, or 3000 mm or less. The conveying time of the workpiece 14 from the attachment starting point of the first lamination step of the present embodiment shown in FIG. 1(b) to the curing end point of the curing step shown in FIG. 4(g) can also be set to 400 seconds or less, 300 seconds or less, 250 seconds or less, 200 seconds or less, or 150 seconds or less.

[Protective film forming composition] The protective film forming composition for forming the inner surface protective film-forming film preferably contains a binder polymer component and a curing component.

[Binder polymer component] In order to provide sufficient adhesion and film-forming properties (sheet-forming properties) to the film for forming the inner protective film, a binder polymer component can be used. As the binder polymer component, previously known acrylic polymers, polyester resins, urethane resins, acrylic urethane resins, silicone resins, rubber-based polymers, etc. can be used.

The weight average molecular weight (Mw) of the binder polymer component is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1,200,000. If the weight average molecular weight of the binder polymer component is too low, the adhesion between the inner surface protective film forming film and the support sheet becomes high, which sometimes causes poor transfer of the inner surface protective film forming film. If the weight average molecular weight of the binder polymer component is too high, the adhesion of the inner surface protective film forming film is reduced, which sometimes cannot be transferred to the chip, etc., or the inner surface protective film is peeled off from the chip, etc. after transfer.

As the adhesive polymer component, an acrylic polymer can be preferably used. The glass transition temperature (Tg) of the acrylic polymer is preferably in the range of -60°C to 50°C, particularly preferably in the range of -50°C to 40°C, and even more preferably in the range of -40°C to 30°C. If the glass transition temperature of the acrylic polymer is too low, the peeling force between the inner surface protective film forming film and the support sheet becomes large, sometimes causing poor transfer of the inner surface protective film forming film. If the glass transition temperature of the acrylic polymer is too high, the adhesion of the inner surface protective film forming film is reduced, sometimes failing to transfer to a chip or the like, or the inner surface protective film is peeled off from the chip or the like after transfer.

As the monomer constituting the acrylic polymer, there can be mentioned a (meth)acrylate monomer or a derivative thereof. For example, there can be mentioned a (meth)acrylate alkyl ester having an alkyl group with a carbon number of 1 to 18, specifically, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. In addition, there can be mentioned a (meth)acrylate ester having a cyclic skeleton, specifically, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, imido (meth)acrylate, etc. Furthermore, as monomers having a functional group, there can be listed: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. having a hydroxyl group; in addition, there can be listed glycidyl (meth)acrylate, etc. having an epoxy group. Regarding acrylic polymers, acrylic polymers containing monomers having a hydroxyl group are preferred because they have good compatibility with the curable component described later. In addition, the above acrylic polymers can also be copolymerized with acrylic acid, methacrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, etc.

Furthermore, as an adhesive polymer component, a thermoplastic resin can also be formulated to maintain the flexibility of the protective film after curing. As such a thermoplastic resin, the weight average molecular weight is preferably 1,000 to 100,000, and particularly preferably 3,000 to 80,000. The glass transition temperature of the thermoplastic resin is preferably -30°C to 120°C, and particularly preferably -20°C to 120°C. Examples of thermoplastic resins include: polyester resins, urethane resins, phenoxy resins, polybutene, polybutadiene, polystyrene, and the like. These thermoplastic resins can be used alone or in combination of two or more. By containing the above-mentioned thermoplastic resin, the film for forming the inner surface protective film can follow the transfer surface of the film for forming the inner surface protective film, thereby suppressing the generation of voids and the like.

[Hardening Component] The curing component may be a thermosetting component and/or an energy ray curing component.

As the thermosetting component, a thermosetting resin and a thermosetting agent can be used. As the thermosetting resin, for example, epoxy resin is preferred.

As the epoxy resin, any previously known epoxy resin can be used. Specific examples of the epoxy resin include: epoxy compounds having two or more functional groups in the molecule, such as multifunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether or its hydrogenated product, o-cresol novolac epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, or phenylene skeleton epoxy resin. These epoxy resins can be used alone or in combination of two or more.

The inner protective film forming film preferably contains 1 to 1000 parts by mass, more preferably 10 to 500 parts by mass, and even more preferably 20 to 200 parts by mass of a thermosetting resin relative to 100 parts by mass of the binder polymer component. If the content of the thermosetting resin is less than 1 part by mass, sufficient adhesion may not be obtained. If the content of the thermosetting resin exceeds 1000 parts by mass, the peeling force between the inner protective film forming film and the adhesive sheet or the base film becomes high, which may cause poor transfer of the inner protective film forming film.

Thermosetting agents function as hardeners for thermosetting resins, especially epoxy resins. Preferred thermosetting agents include compounds having two or more functional groups that can react with epoxy groups in one molecule. Examples of the functional groups include phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, and acid anhydrides. Among these, phenolic hydroxyl groups, amino groups, and acid anhydrides are preferred, and phenolic hydroxyl groups and amino groups are particularly preferred.

Specific examples of phenolic hardeners include: multifunctional phenolic resins, biphenol, novolac-type phenolic resins, dicyclopentadiene-type phenolic resins, new novolac (Xylok)-type phenolic resins, and aralkylphenolic resins. Specific examples of amine-based hardeners include DICY (Dicyandiamide). These hardeners may be used alone or in combination of two or more.

The content of the thermosetting agent is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass, relative to 100 parts by mass of the thermosetting resin. If the content of the thermosetting agent is too little, sometimes adhesion cannot be obtained due to insufficient curing, and if the content of the thermosetting agent is excessive, sometimes the moisture absorption rate of the film for forming the inner surface protective film becomes high, which reduces the reliability of the semiconductor device.

As the energy ray curable component, there can be used: a low molecular compound (energy ray polymerizable compound) containing an energy ray polymerizable group, which polymerizes and cures when irradiated with energy rays such as ultraviolet rays, electron beams, etc. Specific examples of such energy ray curable components include: trihydroxymethylpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxy pentaacrylate, dipentaerythritol hexaacrylate, or 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy-modified acrylate, polyether acrylate, and itaconic acid oligomer and other acrylate compounds. Such a compound has at least one polymerizable double bond in the molecule, and generally has a weight average molecular weight of 100 to 30,000, preferably about 300 to 10,000. The amount of the energy ray polymerizable compound to be added is preferably 1 to 1500 parts by mass, more preferably 10 to 500 parts by mass, and particularly preferably 20 to 200 parts by mass, relative to 100 parts by mass of the adhesive polymer component.

In addition, as the energy ray-hardening component, an energy ray-hardening polymer in which an energy ray-polymerizing group is bonded to the main chain or side chain of the binder polymer component can also be used. This energy ray-hardening polymer has both the function of the binder polymer component and the function of the hardening component.

The main skeleton of the energy ray-hardening polymer is not particularly limited and may be an acrylic polymer commonly used as an adhesive polymer component, or may be polyester, polyether, etc. In terms of ease of synthesis and control of physical properties, it is particularly preferred to use an acrylic polymer as the main skeleton.

The energy ray polymerizable group bonded to the main chain or side chain of the energy ray curable polymer is, for example, a group containing an energy ray polymerizable carbon-carbon double bond, and specifically, a (meth)acryloyl group, etc. The energy ray polymerizable group may also be bonded to the energy ray curable polymer via an alkylene group, an alkoxyene group, or a polyalkoxyene group.

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

Energy ray-curable polymers are obtained by reacting an acrylic polymer containing functional groups such as hydroxyl, carboxyl, amine, substituted amine, and epoxy with a compound containing a polymerizable group, wherein each molecule of the compound containing a polymerizable group has 1 to 5 substituents that react with the functional group and an energy ray-polymerizable carbon-carbon double bond. Examples of the substituents that react with the functional group include isocyanate, glycidyl, and carboxyl.

Examples of the polymerizable group-containing compound include (meth)acryloyloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, (meth)acryloyl isocyanate, allyl isocyanate, (meth)glycidyl (meth)acrylate, (meth)acrylic acid, and the like.

The acrylic polymer is preferably a copolymer consisting of a (meth)acrylic monomer or its derivative having a functional group such as a hydroxyl group, a carboxyl group, an amino group, a substituted amino group, an epoxy group, etc. and other (meth)acrylate monomers or their derivatives that can be copolymerized with the (meth)acrylic monomer or its derivative.

Examples of (meth)acrylic acid monomers or their derivatives having functional groups such as a hydroxyl group, a carboxyl group, an amino group, a substituted amino group, and an epoxy group include: 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate having a hydroxyl group; acrylic acid, methacrylic acid, and itaconic acid having a carboxyl group; and glycidyl methacrylate and glycidyl acrylate having an epoxy group.

As other (meth)acrylate monomers or derivatives thereof that can be copolymerized with the above-mentioned monomers, for example, (meth)acrylate alkyl esters having an alkyl group with a carbon number of 1 to 18 can be listed, specifically, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.; (meth)acrylates having a cyclic skeleton can be listed, specifically, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, imide acrylate, etc. In addition, vinyl acetate, acrylonitrile, styrene, etc. can also be copolymerized with the above-mentioned acrylic polymer.

When an energy ray curing polymer is used, the aforementioned energy ray polymerizable compound may be used in combination, and an adhesive polymer component may also be used in combination. With regard to the relationship between the amounts of the three in the inner surface protective film forming film of the present invention, the energy ray polymerizable compound is preferably contained in an amount of 1 to 1500 parts by mass, more preferably 10 to 500 parts by mass, and even more preferably 20 to 200 parts by mass, relative to 100 parts by mass of the sum of the mass of the energy ray curing polymer and the adhesive polymer component.

By giving the inner surface protective film forming film energy ray hardening properties, the inner surface protective film forming film can be hardened simply and in a short time, and the production efficiency of chips with protective films is improved. Previously, protective films for chips were usually formed by thermosetting resins such as epoxy resins, but the curing temperature of thermosetting resins needs to be more than 200°C, and the curing time requires about 2 hours, which hinders the improvement of production efficiency. However, the inner surface protective film forming film with energy ray hardening properties is hardened in a short time by energy ray irradiation, so the protective film can be easily formed, which can help improve production efficiency.

The film for forming an inner surface protective film may further contain the following components in addition to the above-mentioned binder polymer component and curable component.

[Colorant] The film for forming the inner surface protective film preferably contains a colorant. By mixing the colorant in the film for forming the inner surface protective film, when the semiconductor device is assembled into a machine, infrared rays generated by surrounding devices can be shielded to prevent malfunction of the semiconductor device caused by these infrared rays. In addition, when the protective film obtained by curing the film for forming the inner surface protective film is printed with product numbers, the visibility of the text is improved. That is, for semiconductor devices or semiconductor chips formed with a protective film, product numbers and the like are usually printed on the surface of the protective film by laser marking (a method of printing by scraping off the surface of the protective film with laser light). Since the protective film contains a colorant, the contrast difference between the portion of the protective film scraped off by the laser light and the portion not scraped off can be fully obtained, thereby improving visibility. As a colorant, organic or inorganic pigments and dyes can be used. Among these, black pigments are preferred in terms of electromagnetic wave or infrared shielding properties. As black pigments, carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, etc. can be used, but are not limited to these. From the perspective of improving the reliability of semiconductor devices, carbon black is particularly preferred. Colorants can be used alone, or two or more can be used in combination. When a colorant that reduces the transmittance of visible light and/or both infrared and ultraviolet light is used to reduce the transmittance of ultraviolet light, the high curability of the film for forming the inner surface protective film of the present invention can be particularly well utilized. The colorant that reduces the transmittance of visible light and/or both infrared and ultraviolet light is not particularly limited as long as it has absorptivity or reflectivity in the wavelength region of visible light and/or both infrared and ultraviolet light, in addition to the above-mentioned black pigment.

The amount of the colorant to be added is preferably 0.1 to 35 parts by mass, particularly preferably 0.5 to 25 parts by mass, and even more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the total solid content of the film constituting the inner protective film.

[Curing accelerator] The curing accelerator is used to adjust the curing speed of the film for forming the inner surface protective film. The curing accelerator is particularly preferably used when epoxy resin and thermosetting agent are used together as the curing component.

Preferable hardening accelerators include: tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, etc.; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc.; organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine, etc.; tetraphenylborates such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, etc. These hardening accelerators can be used alone or in combination of two or more.

The curing accelerator is preferably contained in an amount of 0.01 to 10 parts by mass, particularly preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the curing component. By containing the curing accelerator in the amount within the above range, excellent adhesion characteristics can be obtained even when exposed to high temperature and high humidity, and high reliability can be achieved even when exposed to severe reflow conditions. If the content of the curing accelerator is small, sufficient adhesion characteristics cannot be obtained due to insufficient curing. If the content of the curing accelerator is excessive, the curing accelerator with high polarity moves to the bonding interface side in the film for forming the inner surface protective film under high temperature and high humidity, segregates, and reduces the reliability of the semiconductor device.

[Coupling agent] A coupling agent can also be used to improve the adhesion and tightness of the inner surface protective film forming film to the wafer and/or the cohesion of the protective film. In addition, by using a coupling agent, the heat resistance of the protective film obtained by curing the inner surface protective film forming film can be improved without damaging the heat resistance of the protective film, thereby improving the water resistance of the protective film.

As the coupling agent, a compound containing a group reactive with a functional group possessed by the polymer component of the adhesive, the curing component, etc. can be preferably used. As the coupling agent, a silane coupling agent is more preferable. Examples of such coupling agents include: γ-glycidyloxypropyl trimethoxysilane, γ-glycidyloxypropyl methyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, γ-(methacryloyloxypropyl)trimethoxysilane, γ-aminopropyl trimethoxysilane, N-6-(aminoethyl)-γ-aminopropyl trimethoxysilane, N-6-(aminoethyl)- γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-butylpropyltrimethoxysilane, γ-butylpropylmethyldimethoxysilane, 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.

The coupling agent is generally contained in an amount of 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass, and more preferably 0.3 to 5 parts by mass, relative to 100 parts by mass of the total of the adhesive polymer component and the curing component. If the content of the coupling agent is less than 0.1 parts by mass, the above-mentioned effect may not be obtained, and if the content of the coupling agent exceeds 20 parts by mass, outgassing may occur.

[Inorganic filler] By adding inorganic filler to the inner protective film forming film, the thermal expansion coefficient of the protective film after curing can be adjusted. By optimizing the thermal expansion coefficient of the protective film after curing for the semiconductor chip, the reliability of the semiconductor device can be improved. In addition, the moisture absorption rate of the protective film after curing can also be reduced.

Preferred inorganic fillers include: powders of silicon dioxide, aluminum oxide, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride, etc., beads obtained by sphericalizing these powders, single crystal fibers, and glass fibers. Among these inorganic fillers, silicon dioxide fillers and aluminum oxide fillers are preferred. The above-mentioned inorganic fillers can be used alone or in combination of two or more. The content of the inorganic filler can usually be adjusted within the range of 1 to 80 parts by mass relative to 100 parts by mass of the total solids constituting the film for forming the inner surface protective film.

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

Specific examples of such photopolymerization initiators include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoic acid methyl ester, benzoin dimethyl ketal, 2,4-diethylthiothionone, α-hydroxycyclohexylphenyl ketone, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzoyl, dibenzoyl, diacetyl, 1,2-diphenylmethane, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone, 2,4,6-trimethylbenzyldiphenylphosphine oxide, and β-chloroanthraquinone. The photopolymerization initiators may be used alone or in combination of two or more.

The mixing ratio of the photopolymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the energy ray curable component. If it is less than 0.1 parts by mass, satisfactory transfer properties may not be obtained due to insufficient photopolymerization, and if it exceeds 10 parts by mass, residues that do not contribute to photopolymerization may be generated, and the curability of the film for forming the inner protective film may become insufficient.

[Crosslinking agent] A crosslinking agent may be added to adjust the initial adhesion and cohesive force of the film for forming the inner protective film. Examples of the crosslinking agent include organic polyisocyanate compounds, organic polyimide compounds, and the like.

Examples of the organic polyisocyanate compound include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, trimers of these organic polyisocyanate compounds, and terminal isocyanate urethane prepolymers obtained by reacting these organic polyisocyanate compounds with a polyol compound.

Examples of the organic polyisocyanate compound include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, trihydroxymethylpropane addition toluene diisocyanate, and lysamine isocyanate.

Examples of the organic polyimide compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxylic acid amide), trihydroxymethylpropane-tri-β-aziridine propionate, tetrahydroxymethylmethane-tri-β-aziridine propionate, and N,N'-toluene-2,4-bis(1-aziridinecarboxylic acid amide) triethyl melamine.

The crosslinking agent is used in a ratio of usually 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 total amount of the adhesive polymer component and the energy ray-hardening polymer.

[General additives] In addition to the above components, various additives can be formulated as needed for the film used to form the inner protective film. Examples of various additives include: leveling agents, plasticizers, antistatic agents, antioxidants, ion scavengers, degassing agents, chain transfer agents, etc.

[Solvent] The protective film forming composition preferably further contains a solvent. The protective film forming composition containing a solvent has good operability. The aforementioned solvent is not particularly limited, and examples of preferred solvents include: 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; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone, etc. The solvent contained in the protective film forming composition may be only one kind, or may be two or more kinds. In the case of two or more kinds, the combination and ratio of these solvents may be selected arbitrarily.

From the viewpoint of being able to more uniformly mix the components contained in the protective film forming composition, the solvent contained in the protective film forming composition is preferably methyl ethyl ketone or the like.

The inner surface protective film forming film obtained by applying and drying the protective film forming composition composed of the above-mentioned components has adhesion and curability, and can be easily bonded to a workpiece (semiconductor wafer or chip, etc.) by pressing it in an uncured state. The inner surface protective film forming film can also be heated during pressing. Moreover, it can finally form a highly impact-resistant protective film after curing, and it also has excellent bonding strength, and can maintain sufficient protective function under severe high temperature and high humidity conditions. Furthermore, the inner surface protective film forming film can be a single-layer structure. In addition, as long as it contains one or more layers containing the above-mentioned components, it can also be a multi-layer structure.

The thickness of the film for forming the inner surface protective film is not particularly limited, but is preferably 3 μm to 300 μm, particularly preferably 5 μm to 250 μm, and even more preferably 7 μm to 200 μm.

[Supporting sheet] As the supporting sheet 10 used in one aspect of the present invention, there can be listed a sheet consisting only of a substrate 11, or an adhesive sheet having an adhesive layer 12 on the substrate 11. The supporting sheet possessed by the third laminate of one aspect of the present invention plays the role of a peeling sheet for preventing dust and the like from adhering to the surface of the film for forming the inner surface protective film, or a cutting sheet for protecting the surface of the film for forming the inner surface protective film in a cutting step, etc.

The thickness of the support sheet can be appropriately selected according to the application. From the perspective of giving the composite sheet sufficient flexibility and good adhesion to the silicon wafer, it is preferably 10μm to 500μm, more preferably 20μm to 350μm, and particularly preferably 30μm to 200μm. Furthermore, the thickness of the support sheet mentioned above refers not only to the thickness of the substrate constituting the support sheet, but also to the thickness of these layers or films when there is an adhesive layer.

[Substrate] The substrate 11 constituting the support sheet 10 is preferably a resin film. Examples of the resin film include polyethylene films such as LDPE (Low Density Polyethylene) film or LLDPE (Linear Low Density Polyethylene) film, ethylene-propylene copolymer film, polypropylene film, polybutylene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, ionic polymer resin film, ethylene-(meth)acrylic acid copolymer film, ethylene-(meth)acrylate copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film, and the like. The substrate used in one aspect of the present invention may be a single-layer film composed of one resin film, or a laminated film formed by laminating two or more resin films. In addition, in one aspect of the present invention, a sheet having a surface treatment applied to the surface of the substrate such as the resin film may be used as a supporting sheet.

These resin films may also be cross-linked films. In addition, films obtained by coloring these resin films or by printing these resin films may also be used. Furthermore, the resin film may be formed by extruding a thermoplastic resin into a sheet, or may be stretched, or may be formed into a sheet by thinning and curing a curable resin by a predetermined method.

Among these resin films, a substrate containing a polypropylene film is preferred from the viewpoint of excellent heat resistance, expansion suitability due to moderate softness, and easy pick-up suitability. Furthermore, the structure of the substrate containing a polypropylene film may be a single-layer structure consisting of only a polypropylene film, or a multi-layer structure consisting of a polypropylene film and other resin films. When the film used to form the inner surface protective film is thermosetting, the resin film constituting the substrate has heat resistance, which can suppress damage to the substrate caused by heat and suppress defects in the manufacturing process of the semiconductor device.

When a sheet consisting only of a substrate is used as a supporting sheet, the surface tension of the surface of the substrate that contacts the surface of the film for forming the inner surface protective film is preferably 20mN/m to 50mN/m, more preferably 23mN/m to 45mN/m, and particularly preferably 25mN/m to 40mN/m from the viewpoint of adjusting the peeling force to a certain range.

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

[Adhesive sheet] As an adhesive sheet used as the supporting sheet 10 in one embodiment of the present invention, there can be cited an adhesive sheet having an adhesive layer 12 formed of an adhesive on a substrate 11 such as the above-mentioned resin film. FIG11 is a schematic cross-sectional view showing an example of a supporting sheet 10 having an adhesive layer 12 on a substrate 11. When the supporting sheet 10 has the adhesive layer 12, the adhesive layer 12 of the supporting sheet 10 is attached to the smooth surface 13b of the inner protective film forming film 13 in the second lamination step.

Regarding the adhesive as the forming material of the adhesive layer, an adhesive composition containing an adhesive resin can be listed, and the adhesive composition can also further contain the above-mentioned general additives such as the crosslinking agent or thickener. As the adhesive resin, when focusing on the structure of the resin, for example, acrylic resin, urethane resin, rubber resin, silicone resin, vinyl ether resin, etc. can be listed, and when focusing on the function of the resin, for example, energy ray curing adhesive or heat foaming adhesive, energy ray foaming adhesive, etc. can be listed. In one aspect of the present invention, from the viewpoint of adjusting the peeling force to a certain range and improving the pick-up property, an adhesive sheet having an energy ray-hardening adhesive layer formed of an adhesive composition containing an energy ray-hardening resin or an adhesive sheet having a slightly adhesive adhesive layer is preferred. The energy ray-hardening resin may be any resin having a polymerizable group such as a (meth)acryl group or a vinyl group, and an adhesive resin having a polymerizable group is preferred.

In the first lamination step, when the inner surface protective film forming film is poorly adhered to the workpiece such as a semiconductor wafer, (a) the inner surface protective film forming film is not adhered to the entire surface, (b) the inner surface protective film forming film is bulged, or (c) the inner surface protective film forming film is wrinkled, the support sheet can also serve as a sheet for removing the inner surface protective film forming film. Even if the inner surface protective film forming film is poorly adhered to the first lamination step, the third lamination body can be directly manufactured through the second lamination step. Then, by separating the inner surface protective film forming film and the support sheet from the workpiece such as a semiconductor wafer, the workpiece such as a semiconductor wafer can be reprocessed. At this time, if the production cycle is taken into consideration, the support sheet needs to be quickly removed from the fixing jig such as the ring frame, and the jig adhesive layer is preferably energy-ray-hardening. In addition, by using a support sheet having an energy-ray-hardening adhesive layer on the base material, the support sheet can be directly fixed to the fixing jig such as the ring frame without passing through the jig adhesive layer, and by irradiating energy rays such as ultraviolet rays, excellent reworkability can be achieved.

In addition, from the viewpoint of adjusting the peeling force to a certain range, an adhesive containing an acrylic resin is preferred. As the acrylic resin, an acrylic polymer having a constituent unit (x1) derived from an alkyl (meth)acrylate is preferred, and an acrylic copolymer having a constituent unit (x1) and a constituent unit (x2) derived from a monomer containing a functional group is more preferred.

The carbon number of the alkyl group of the above-mentioned (meth)acrylate alkyl ester is preferably 1 to 18, more preferably 1 to 12, and particularly preferably 1 to 8. As the (meth)acrylate alkyl ester, the same (meth)acrylate alkyl ester as the (meth)acrylate alkyl ester described in the above-mentioned adhesive polymer component can be listed. Furthermore, the (meth)acrylate alkyl ester can also be used alone or in combination of two or more. Relative to the total constituent units (100 mass %) of the acrylic polymer, the content of the constituent unit (x1) is usually 50 mass % to 100 mass %, preferably 50 mass % to 99.9 mass %, more preferably 60 mass % to 99 mass %, and particularly preferably 70 mass % to 95 mass %.

As the above-mentioned functional group-containing monomers, for example, hydroxyl-containing monomers, carboxyl-containing monomers, epoxy-containing monomers, etc. can be listed, and specific examples of each monomer can be the same monomers as those exemplified in the adhesive polymer component. Furthermore, these monomers can be used alone or in combination of two or more. Relative to the total constituent units (100 mass %) of the acrylic polymer, the content of the constituent unit (x2) is usually 0 mass % to 40 mass %, preferably 0.1 mass % to 40 mass %, more preferably 1 mass % to 30 mass %, and particularly preferably 5 mass % to 20 mass %.

In addition, the acrylic resin used in one embodiment of the present invention may be an energy ray-curable acrylic resin obtained by reacting an acrylic copolymer having the above-mentioned constituent unit (x1) and constituent unit (x2) with a compound having an energy ray-polymerizable group. The compound having an energy ray-polymerizable group may be a compound having a polymerizable group such as a (meth)acryl group or a vinyl group.

When using an adhesive containing an acrylic resin, from the viewpoint of adjusting the peeling force to a certain range, it is preferable to contain a crosslinking agent together with the acrylic resin. As the crosslinking agent, for example, isocyanate crosslinking agents, imine crosslinking agents, epoxy crosslinking agents, oxazoline crosslinking agents, carbodiimide crosslinking agents, etc. From the viewpoint of adjusting the peeling force to a certain range, isocyanate crosslinking agents are preferred. The content of the crosslinking agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, particularly preferably 0.5 to 10 parts by mass, and even more preferably 1 to 8 parts by mass, relative to the total mass (100 parts by mass) of the acrylic resin contained in the adhesive.

The support sheet 10 may be composed of one layer (single layer) or may be composed of two or more layers. When the support sheet is composed of multiple layers, the constituent materials and thicknesses of the multiple layers may be the same or different, and the combination of the multiple layers is not particularly limited as long as it does not impair the effects of the present invention.

Furthermore, in this specification, not limited to the case of supporting sheets, the so-called "multiple layers may be the same or different from each other" means "all layers may be the same, or all layers may be different, or only some layers may be the same", and further, the so-called "multiple layers are different from each other" means "at least one of the constituent materials and thicknesses of each layer is different from each other".

The support sheet may be transparent or opaque, and may be colored according to the purpose. For example, when the film for forming the inner surface protective film has energy ray curing properties, the support sheet preferably allows the energy ray to pass through. For example, in order to optically inspect the film for forming the inner surface protective film through the support sheet, the support sheet is preferably transparent.

In the present embodiment, the electric surface surface 14a of the workpiece 14 is protected by the electric surface surface protection tape 17. After the aforementioned second lamination step, a peeling step of peeling the electric surface surface protection tape 17 from the electric surface surface 14a of the workpiece 14 may be included. In the present embodiment, the electric surface surface protection tape 17 has an energy ray hardening adhesive layer on the side attached to the electric surface surface 14a, which is hardened by irradiation with energy rays to become re-peelable. In the aforementioned peeling step, the adhesive layer of the electric surface surface protection tape 17 is irradiated with energy rays to harden the adhesive layer to become re-peelable, so that the electric surface surface protection tape 17 can be easily peeled from the electric surface surface 14a of the workpiece 14.

The manufacturing method of the third laminated body of the present embodiment may also include the following step: laser marking is performed by irradiating the inner surface protective film forming film 13 from the side of the support sheet 10. The manufacturing method of the third laminated body of the present embodiment is to laminate the support sheet 10 on the smooth surface 13b of the inner surface protective film forming film 13. Therefore, if the laser is irradiated from the side of the support sheet 10 through the support sheet, the smooth surface 13b of the inner surface protective film forming film 13 is laser marked, and the laser marking can be performed more clearly than the case of laser marking the rough surface 13a.

In one example of a method for manufacturing a semiconductor chip with an inner surface protective film as shown in FIG10, the smooth surface 13b of the inner surface protective film forming film 13 of the protective film forming composite sheet 1 is attached to the inner surface 8b of the semiconductor wafer 8 in FIG10(A'). Therefore, when the laser is irradiated from the side of the support sheet 10 through the support sheet in FIG10(D'), the rough surface 13a of the inner surface protective film forming film 13 is laser marked. The adhesion of the interface between the rough surface 13a of the inner surface protective film forming film 13 and the support sheet 10 is impaired. Therefore, if the laser is irradiated through the support sheet, the outline of the characters or marks printed at the interface between the inner surface protective film forming film 13 and the support sheet 10 at the laser irradiated portion is blurred, and the visibility after printing is impaired.

On the other hand, the manufacturing method of the third laminate of the present embodiment is to laminate the support sheet 10 on the smooth surface 13b of the inner surface protective film forming film 13, so that the interface between the smooth surface 13b of the inner surface protective film forming film 13 and the support sheet 10 maintains good adhesion. Therefore, when the laser is subsequently irradiated from the side of the support sheet 10 through the support sheet, as shown in Figures 1(b) to 1(e) and 4(f), the smooth surface 13b of the inner surface protective film forming film 13 is laser marked, and the text or mark printed on the interface between the smooth surface 13b of the inner surface protective film forming film 13 and the support sheet 10 is prevented from smudging, so that the laser marking can be performed more clearly than when the rough surface 13a is laser marked.

In addition, the manufacturing method of the third laminate of the present embodiment is to laminate the support sheet 10 on the smooth surface 13b of the inner surface protective film forming film 13. Therefore, even after the inner surface protective film forming film 13 is subsequently cured to form the inner surface protective film 13', the smooth surface 13'b of the inner surface protective film 13' will be laser marked by irradiating the support sheet from the side of the support sheet 10 through the support sheet, and the laser marking can be performed more clearly than the case of laser marking the rough surface 13'a.

In one example of the method for manufacturing a semiconductor wafer with an inner surface protective film shown in FIG9, in FIG9(B), thermal curing is performed with the smooth surface 13b of the inner surface protective film forming film 13 exposed. On the other hand, in the method for manufacturing the third laminate of the present embodiment, the support sheet 10 is laminated on the smooth surface 13b of the inner surface protective film forming film 13, so that when the inner surface protective film forming film 13 is cured, it comes into contact with the support sheet 10, and the smooth surface 13b is protected. Therefore, even if the laser is subsequently irradiated through the support sheet 10 from the side, the smooth surface 13’b of the inner protective film 13’ that is protected by the support sheet 10 during the curing step will be laser marked. This enables clearer laser marking than the case where the smooth surface 13’b of the inner protective film 13’ that has been heat-cured in an exposed state is laser marked.

Fig. 3 is a schematic cross-sectional view schematically showing another example of an implementation form of the method for manufacturing the third laminate. In Fig. 3 and subsequent figures, the same components as those shown in the previously described figures are marked with the same symbols as those in the previously described figures, and detailed descriptions are omitted.

In the present embodiment, the workpiece 14 is a semiconductor device panel, which is composed of a collection of semiconductor devices sealed with at least one electronic component 62 by a sealing resin layer 64 arranged in a planar form. The manufacturing method of the third laminate of the present embodiment is to manufacture a third laminate 19 in which the semiconductor device panel as the workpiece 14, the film 13 for forming an inner surface protective film, and the support sheet 10 are sequentially laminated, and one side of the semiconductor device panel as the workpiece 14 is a conductive surface, and the other side is an inner surface 14b (Figure 3 (a')), one side of the film 13 for forming an inner surface protective film is a smooth surface 13b, and the other side is a relatively smooth surface. The manufacturing method of the third laminated body sequentially comprises: a first lamination step (FIG. 3(b’)), in which the rough surface 13a of the inner surface protective film forming film 13 is adhered to the inner surface 14b of the workpiece 14; and a second lamination step (FIG. 3(c’)), in which the support sheet 10 is adhered to the smooth surface 13b of the inner surface protective film forming film 13 (FIG. 3(a’) to FIG. 3(d’)).

In this embodiment, the semiconductor device panel can be formed by arranging each semiconductor device in a plane in a substantially circular area, or can be formed by arranging each semiconductor device in a plane in a substantially rectangular area.

In the present embodiment shown in FIG. 3 , similarly to the embodiment shown in FIG. 1 , the support sheet 10 is laminated on the smooth surface 13b of the film 13 for forming the inner surface protective film. Therefore, if the laser is irradiated from the side of the support sheet 10 through the support sheet, the smooth surface 13b of the film 13 for forming the inner surface protective film or the smooth surface 13'b of the inner surface protective film 13' will be laser marked, and the laser marking can be performed more clearly than the case where the rough surface 13a or the rough surface 13'a is laser marked. In addition, laser marking will be performed subsequently on the smooth surface 13’b of the inner surface protective film 13’ which is protected by the support sheet 10 during the curing step. Therefore, even if the laser is irradiated from the side of the support sheet 10 through the support sheet, laser marking can be performed more clearly than when laser marking is performed on the smooth surface 13’b of the inner surface protective film 13’ which has been heat-cured in an exposed state.

[Manufacturing method of the fourth laminate] The manufacturing method of the fourth laminate of the present embodiment is to manufacture a fourth laminate 19' formed by laminating a workpiece 14, an inner surface protective film 13' and a support sheet 10 in sequence. The manufacturing method of the fourth laminate includes: a hardening step, wherein the inner surface protective film forming film 13 of the third laminate 19 manufactured by the aforementioned third laminate manufacturing method is hardened to form an inner surface protective film 13'.

FIG4 is a schematic cross-sectional view schematically showing an example of an embodiment of the method for manufacturing the fourth laminate. The method for manufacturing the fourth laminate of this embodiment includes, after the aforementioned second lamination step, a peeling step (FIG. 4(e)) of peeling the surface protection tape 17 from the surface 14a of the workpiece 14; a step of laser marking by irradiating the inner surface protection film forming film 13 from the side of the support sheet 10 (FIG. 4(f)); and a curing step (FIG. 4(g)) of curing the inner surface protection film forming film 13 to form an inner surface protection film 13'. In this embodiment, a thermosetting inner surface protection film forming film is used, and in the curing step of this embodiment, thermal curing is performed at 130°C for 2 hours.

The curing conditions when the thermosetting inner surface protective film is heat-treated and heat-cured to form the inner surface protective film are not particularly limited as long as the inner surface protective film has a degree of curing that fully exhibits the function of the inner surface protective film, and can be appropriately selected according to the type of the thermosetting inner surface protective film.

For example, the heating temperature during heat curing is preferably 100°C to 200°C, more preferably 110°C to 180°C, and particularly preferably 120°C to 170°C. In addition, the heating time during the aforementioned heat curing is preferably 0.5 hours to 5 hours, more preferably 0.5 hours to 3 hours, and particularly preferably 1 hour to 2 hours. When heat curing is performed in the curing step, considering the heat resistance of the electrical road surface protection tape 17, the aforementioned stripping step is preferably performed before the curing step.

In the present embodiment shown in FIG. 4 , as described above, the support sheet 10 is laminated on the smooth surface 13b of the inner surface protective film forming film 13. Therefore, if the laser is irradiated from the side of the support sheet 10 through the support sheet, the smooth surface 13b of the inner surface protective film forming film 13 will be laser marked, and the laser marking can be performed more clearly than the case of laser marking the rough surface 13a.

Fig. 5 is a schematic cross-sectional view schematically showing another example of an implementation form of the manufacturing method of the fourth laminate. The manufacturing method of the fourth laminate of this implementation form includes, after the aforementioned second lamination step: a peeling step (Fig. 5(e)) to peel off the electrical surface protection tape 17 from the electrical surface 14a of the workpiece 14; a hardening step (Fig. 5(f')) to harden the inner surface protection film forming film 13 to form an inner surface protection film 13'; and a step of irradiating the inner surface protection film 13' with a laser from the side of the support sheet 10 to perform laser marking (Fig. 5(g')).

In the present embodiment shown in FIG. 5 , as described above, the support sheet 10 is laminated on the smooth surface 13b of the film 13 for forming the inner protective film. Therefore, if the laser is irradiated from the side of the support sheet 10 through the support sheet, the smooth surface 13’b of the inner protective film 13’ will be laser marked, and the laser marking can be performed more clearly than the case of laser marking the rough surface 13’a. In addition, since the smooth surface 13'b of the inner surface protective film 13' which is protected by the support sheet 10 in the curing step is laser marked, if the laser is irradiated from the side of the support sheet 10 through the support sheet, laser marking can be performed more clearly than when the smooth surface 13'b of the inner surface protective film 13' which has been heat-cured in an exposed state is laser marked.

[Manufacturing method of semiconductor device with inner surface protective film] Fig. 6 is a schematic cross-sectional view schematically showing an example of an implementation form of the manufacturing method of a semiconductor device with inner surface protective film. The manufacturing method of a semiconductor device with inner surface protective film of this implementation form includes: a step of cutting the workpiece 14 and the inner surface protective film 13' of the fourth multilayer body 19' manufactured by the aforementioned manufacturing method of the fourth multilayer body to produce a semiconductor device 21 with inner surface protective film (Fig. 6 (h) and Fig. 6 (i)); and a step of picking up the semiconductor device 21 with inner surface protective film from the support sheet 10 (Fig. 6 (j)).

Fig. 7 is a schematic cross-sectional view schematically showing another example of an implementation form of the method for manufacturing a semiconductor device with an inner surface protective film. The method for manufacturing a semiconductor device with an inner surface protective film of this implementation form includes: a step of cutting the inner surface protective film forming film 13 and the workpiece 14 of the third laminate 19 manufactured by the aforementioned method for manufacturing a third laminate to form a semiconductor device 21' with an inner surface protective film forming film (Fig. 7(h') and Fig. 7(i')); a step of picking up the semiconductor device 21' with an inner surface protective film forming film from the support sheet 10 (Fig. 7(j')); and a hardening step of hardening the inner surface protective film forming film 13 to form an inner surface protective film 13' (Fig. 7(k')).

FIG8 is a schematic cross-sectional view schematically showing another example of an implementation form of the method for manufacturing a semiconductor device with an inner surface protective film. The method for manufacturing a semiconductor device with an inner surface protective film of this implementation form includes: a step of cutting the inner surface protective film forming film 13 and the workpiece 14 of the third laminate 19 manufactured by the aforementioned method for manufacturing a third laminate to manufacture a semiconductor device 21' with an inner surface protective film forming film (FIG. 8(h) and FIG8(i)); a step of hardening the inner surface protective film forming film 13 to manufacture an inner surface protective film 13' (FIG. 8(j')); and a step of picking up the semiconductor device 21 with an inner surface protective film from the support sheet 10.

In the method for manufacturing a semiconductor device with an inner surface protective film of this embodiment, the film 13 for forming the inner surface protective film is thermosetting. In the step of forming the inner surface protective film of this embodiment, the film 13 for forming the inner surface protective film is thermosetted at 130°C for 2 hours, for example.

Regarding the curing conditions when thermally curing the thermosetting film for forming an inner surface protective film to form an inner surface protective film, as described above, there is no particular limitation as long as the inner surface protective film has a degree of curing that fully exhibits the function of the inner surface protective film, and it can be appropriately selected according to the type of thermosetting film for forming an inner surface protective film.

The manufacturing method of the semiconductor device with an inner surface protective film of this embodiment may be as follows: the film 13 for forming the inner surface protective film is energy ray-curable, and the step of forming the inner surface protective film is a step of irradiating the film 13 for forming the inner surface protective film with energy rays for energy ray curing.

The curing conditions when the energy-ray-curable film for forming an inner surface protective film is subjected to energy-ray curing to form a protective film are not particularly limited as long as the protective film is cured to a degree that fully exhibits the function of the protective film, and may be appropriately selected according to the type of the energy-ray-curable film for forming an inner surface protective film. For example, the illuminance of the energy ray when the energy-ray-curable film for forming an inner surface protective film is energy-ray-cured is preferably 4mW/ ^cm2 to 280mW/ ^cm2 . Furthermore, the light intensity of the energy ray during the curing is preferably 3mJ/ ^cm2 to 1000mJ/ ^cm2 .

As a film for forming an energy-ray-curable inner surface protective film, for example, the films disclosed in International Publication No. 2017/188200 and International Publication No. 2017/188218 can also be used. [Example]

The present invention will be described in more detail below by way of specific embodiments. However, the present invention is not limited to the embodiments shown below.

[Example 1] The following components were mixed in the mixing ratio (solid conversion) shown in Table 1, and diluted with methyl ethyl ketone in a manner such that the solid concentration became 50 mass % relative to the total mass of the protective film forming composition, to prepare a protective film forming composition for forming a film for inner surface protective film formation. (A-1): Binder polymer: (Meth)acrylate copolymer obtained by copolymerizing 55 parts by mass of n-butyl acrylate, 10 parts by mass of methyl acrylate, 20 parts by mass of glycidyl methacrylate and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 800,000, glass transition temperature: -28°C) (B-1) Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER828, epoxy equivalent 184 g/eq to 194 g/eq) (B-2) Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER1055, epoxy equivalent 800 g/eq to 900 g/eq) (B-3) Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, Epiclon HP-7200HH, epoxy equivalent 255g/eq to 260g/eq) (B-4) Cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104, epoxy equivalent 220g/eq) (C-1) Thermally active latent epoxy resin hardener: dicyandiamide (manufactured by ADEKA, Adeka Hardener EH-3636AS, active hydrogen 21g/eq) (D-1) Hardening accelerator: 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Chemical Industries, Ltd., Curezol 2PHZ) (E-1) Amorphous silica filler (manufactured by Ronson Co., Ltd., SV-10, average particle size 8 μm) (F-1) Silane coupling agent: γ-glycidyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403, methoxy equivalent: 12.7 mmol/g, molecular weight: 236.3) (G-1) Coloring agent: 32 parts by mass of phthalocyanine blue pigment (Pigment Blue 15:3), 18 parts by mass of isoindolinone yellow pigment (Pigment Yellow 139), and 50 parts by mass of anthraquinone red pigment (Pigment Red 177) are mixed and pigmented in a ratio of the total amount of the above three pigments/the amount of styrene acrylic resin = 1/3 (mass ratio).

[Formation of a film for forming an inner protective film] The composition (III-1) obtained above was applied to the peeling-treated surface (surface roughness Ra: 30 nm) of a peeling film ("SP-PET501031" manufactured by Lintec, 50 μm thick, equivalent to the aforementioned second peeling film) obtained by peeling one side of a polyethylene terephthalate (PET) film by silicone treatment, and dried at 100°C for 3 minutes to form a film for forming an inner protective film with a thickness of 25 μm. Furthermore, on the exposed surface of the inner protective film forming film (the surface opposite to the side with the peeling film), a single side of a polyethylene terephthalate (PET) film was peeled off by a laminating roller at a temperature of 23°C ± 5°C, a pressure of 0.4 MPa, and a speed of 1 m/min to form a peeling film. The peeling-treated surface (surface roughness Ra: 30 nm) of a film ("SP-PET381031" manufactured by Lintec, with a thickness of 38 μm, which corresponds to the aforementioned first peeling film) is laminated from the first peeling film side to produce a laminated sheet (i.e., a first laminated body) having peeling films laminated on both sides of the film for forming an inner surface protective film.

[Evaluation of the frequency of peeling failure] 10 laminated sheets of the second peeling film/film for forming the inner protective film/first peeling film were prepared in A4 size. From the laminated sheets, the first peeling film was peeled off from the short side of the A4 size. When the first peeling film was peeled off from the short side of the A4 size among the 10 laminated sheets, the number of sheets with peeling failure was determined according to the following criteria to evaluate the frequency of peeling failure.

·0 to 1 pieces had peeling failure···A: Very good. ·2 to 3 pieces had peeling failure···B: Good. ·4 to 5 pieces had peeling failure···C: Fair. ·6 to 10 pieces had peeling failure···D: Poor.

[Measurement of surface roughness (Ra)] The surface roughness (Ra) of the surface of the object to be measured was measured at 10 points on the surface using an optical interferometer surface profile measuring device (manufactured by Veeco Metrology Group, product name "WYKO WT1100") in PSI (Phase-Shifting Interferometry) mode at a magnification of 10 times, and the first decimal place of the average value was rounded off to an integer value. For the laminated sheet of the second release film/the film for forming the inner surface protective film/the first release film, the surface roughness (Ra) of the uncured inner surface protective film forming film on the workpiece side was measured by peeling off the first release film, and the surface roughness (Ra) of the inner surface protective film forming film on the support sheet side was measured by peeling off the second release film.

[Manufacturing of support sheet] An adhesive composition was applied to the peeling-treated surface of a peeling film ("SP-PET381031" manufactured by Lintec, thickness 38μm), and dried at 100°C for 3 minutes to form a UV-curing adhesive layer (10μm thickness after drying). A polypropylene film (80μm thickness, manufactured by Gunze) was bonded as a base material to the exposed surface (the surface opposite to the side with the peeling film) to obtain a support sheet.

The adhesive composition contains 100 parts by mass (solid) of an alkyl (meth)acrylate copolymer, 6.6 parts by mass (solid) of a trifunctional xylene diisocyanate crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemicals Co., Ltd.), and 3.0 parts by mass (solid) of a photopolymerization initiator ("Irgacure 127" manufactured by BASF Corporation), and a mixed solvent of methyl ethyl ketone, toluene, and ethyl acetate is used to adjust the solid concentration to 30% by mass. The alkyl (meth)acrylate copolymer is a UV-curable acrylic copolymer having a weight average molecular weight of 700,000, and is obtained by copolymerizing 70 parts by mass of 2-ethylhexyl acrylate (hereinafter sometimes referred to as "2EHA"), 10 parts by mass of vinyl acetate (hereinafter sometimes referred to as "VAc"), and 20 parts by mass of 2-hydroxyethyl acrylate (hereinafter sometimes referred to as "HEA") to obtain a prepolymer, and then reacting 21.4 parts by mass of 2-methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate, hereinafter sometimes referred to as "MOI") (the total molar number of isocyanate groups in MOI is 0.8 times the total molar number of hydroxyl groups in HEA) with the prepolymer.

[Workpiece] As the workpiece, a 12-inch silicon wafer (thickness 100 μm) with a #2000 polished surface was used.

[Manufacturing of the third laminate] When manufacturing the third laminate, a mechanism for peeling off the first peeling film, a mechanism for attaching a film for forming an inner surface protective film, a mechanism for peeling off the second peeling film, and a mechanism for attaching a support sheet are connected in succession in the same device, and a transfer arm is used between each mechanism to transfer the second laminate having the film for forming an inner surface protective film attached to a silicon wafer as a workpiece piece by piece to perform manufacturing.

First, from a laminate composed of the second peeling film/the film for forming the inner surface protective film/the first peeling film (i.e., the first laminate), the film for forming the inner surface protective film and the first peeling film are punched into the shape of the silicon wafer as a workpiece and the first peeling film is peeled off, and the second peeling film/the film for forming the inner surface protective film is attached to the #2000 polished surface of the aforementioned silicon wafer at a temperature of 23°C and a pressure of 0.5MPa. Then, the second peeling film is peeled off from the laminate consisting of the second peeling film/the film for forming the inner surface protective film/the silicon wafer, thereby obtaining a second laminate in which the film for forming the inner surface protective film is attached to the silicon wafer as a workpiece.

Furthermore, the peeling film of the supporting sheet is peeled off, and the exposed surface of the adhesive layer of the supporting sheet and the exposed surface of the inner surface protective film forming film are bonded together using a wafer bonding machine in the same device at a bonding speed of 20 mm/s and a bonding pressure of 0.3 MPa, thereby obtaining a third laminated body consisting of the supporting sheet, the inner surface protective film forming film and the semiconductor wafer laminated in sequence.

The workpiece transfer time from the start of the first lamination step of laminating the inner surface protective film forming film to the silicon wafer to the end of the second lamination step of laminating the inner surface protective film forming film to the support sheet is 60 seconds.

The workpiece conveyance distance from the first lamination step of laminating the inner surface protective film forming film to the silicon wafer to the second lamination step of laminating the inner surface protective film forming film to the support sheet is 2900 mm.

[Thermal curing] The third laminate is heat treated at 130°C for 2 hours to obtain a fourth laminate consisting of a support sheet, an inner surface protective film and a silicon wafer laminated in sequence.

[Laser marking evaluation] For the fourth laminate, a laser printing device ("CSM300M" manufactured by EO Technics) was used to irradiate the adhesive layer side of the inner protective film in the fourth laminate through the support sheet to print. At this time, the printing was performed with a size of 0.3mm×0.2mm.

Next, the printing (laser printing) on the inner protective film was visually observed through the support sheet, and the visibility of the printing (text) was evaluated according to the following criteria. The results are shown in Table 1. ○: The printing is clear and can be easily recognized. ×: The printing is not clear and cannot be recognized.

[Table 1] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Components of the protective film forming composition (content (weight)) Binder polymer (A) A-1 20.0 Thermosetting resin (B) B-1 13.0 B-2 1.0 B-3 1.0 B-4 1.0 Heat curing agent (C) C-1 0.5 Hardening accelerator (D) D-1 0.5 Filling material (E) E-1 60 Silane coupling agent (F) F-1 1.0 Colorant(G) G-1 2.0 Temperature and pressure conditions when attaching the first peeling film to the inner protective film forming film 23℃ 0.4MPa 40℃ 0.5MPa 50℃ 0.5MPa 60℃ 0.5MPa Number of pieces with peeling defects/10 0／10 0／10 0／10 0／10 Evaluation of the frequency of peeling failure A A A A Surface roughness of the workpiece side of the film for forming the inner protective film (nm) 640 372 253 158 Surface roughness of the support sheet side of the film for forming the inner protective film (nm) 30 30 30 30 Surface roughness of the film for forming the inner protective film on the workpiece side / Surface roughness of the support sheet side 21.33 12.40 8.43 5.27 Laser Marking Reviews ○ ○ ○ ○

[Example 2] In Example 1, when preparing a laminated sheet of the second peeling film/film for forming the inner surface protective film/first peeling film (i.e., the first laminate), the conditions for laminating the first peeling film on the exposed surface of the film for forming the inner surface protective film were set to temperature: 40°C, pressure: 0.5 MPa, and speed: 1 m/min. In addition, the number of sheets with poor peeling was investigated, the frequency of poor peeling was evaluated, and the surface roughness (Ra) was measured in the same manner as in Example 1. In addition, the second laminate, the third laminate, and the fourth laminate were manufactured in the same manner as in Example 1 and evaluated by laser marking. The results are shown in Table 1.

[Example 3] In Example 1, when preparing a laminated sheet of the second peeling film/film for forming the inner surface protective film/first peeling film (i.e., the first laminate), the conditions for laminating the first peeling film on the exposed surface of the film for forming the inner surface protective film were set to temperature: 50°C, pressure: 0.5 MPa, and speed: 1 m/min. In addition, the number of sheets with poor peeling was investigated, the frequency of poor peeling was evaluated, and the surface roughness (Ra) was measured in the same manner as in Example 1. In addition, the second laminate, the third laminate, and the fourth laminate were manufactured in the same manner as in Example 1 and evaluated by laser marking. The results are shown in Table 1.

[Example 4] In Example 1, when preparing a laminated sheet of the second peeling film/film for forming the inner surface protective film/first peeling film (i.e., the first laminate), the conditions for laminating the first peeling film on the exposed surface of the film for forming the inner surface protective film were set to temperature: 60°C, pressure: 0.5 MPa, and speed: 1 m/min. In addition, the number of sheets with poor peeling was investigated, the frequency of poor peeling was evaluated, and the surface roughness (Ra) was measured in the same manner as in Example 1. In addition, the second laminate, the third laminate, and the fourth laminate were manufactured in the same manner as in Example 1 and evaluated by laser marking. The results are shown in Table 1.

[Example 5] In Example 1, the conditions for laminating the first peeling film on the exposed surface of the inner protective film forming film when preparing the second peeling film/inner protective film forming film/first peeling film laminate (i.e., the first laminate) were changed to temperature: 70°C, pressure: 0.5 MPa, speed: 1 m/min. In addition, the number of sheets with poor peeling was investigated, the frequency of poor peeling was evaluated, and the surface roughness (Ra) was measured in the same manner as in Example 1. In addition, the second laminate, the third laminate, and the fourth laminate were manufactured in the same manner as in Example 1 and evaluated by laser marking. The results are shown in Table 1.

[Example 6] In Example 1, the conditions for laminating the first peeling film on the exposed surface of the inner protective film forming film when preparing the second peeling film/inner protective film forming film/first peeling film laminate (i.e., the first laminate) were changed to temperature: 70°C, pressure: 0.7 MPa, speed: 1 m/min. In addition, the number of sheets with poor peeling was investigated, the frequency of poor peeling was evaluated, and the surface roughness (Ra) was measured in the same manner as in Example 1. In addition, the second laminate, the third laminate, and the fourth laminate were manufactured in the same manner as in Example 1 and evaluated by laser marking. The results are shown in Table 1.

[Example 7] In Example 1, the conditions for laminating the first peeling film on the exposed surface of the inner protective film forming film when preparing the second peeling film/inner protective film forming film/first peeling film laminate (i.e., the first laminate) were changed to temperature: 70°C, pressure: 0.8 MPa, speed: 1 m/min. In addition, the number of sheets with poor peeling was investigated, the frequency of poor peeling was evaluated, and the surface roughness (Ra) was measured in the same manner as in Example 1. In addition, the second laminate, the third laminate, and the fourth laminate were manufactured in the same manner as in Example 1 and evaluated by laser marking. The results are shown in Table 1.

[Example 8] In Example 1, the conditions for laminating the first peeling film on the exposed surface of the inner protective film forming film when preparing the second peeling film/inner protective film forming film/first peeling film laminate (i.e., the first laminate) were changed to temperature: 70°C, pressure: 0.9 MPa, speed: 1 m/min. In addition, the number of sheets with poor peeling was investigated, the frequency of poor peeling was evaluated, and the surface roughness (Ra) was measured in the same manner as in Example 1. In addition, the second laminate, the third laminate, and the fourth laminate were manufactured in the same manner as in Example 1 and evaluated by laser marking. The results are shown in Table 1.

[Comparative Example 1] [Formation of a film for forming an inner surface protective film] The composition (III-1) obtained above was applied to the peeling-treated surface (surface roughness: 218 nm) of a peeling film (manufactured by Dupont Teijin Films, U4Z-50, thickness: 50 μm, equivalent to the aforementioned second peeling film) obtained by peeling one side of a polyethylene terephthalate (PET) film by silicone treatment, and dried at 100°C for 3 minutes to form a film for forming an inner surface protective film with a thickness of 25 μm. Furthermore, on the exposed surface of the inner protective film forming film (the surface opposite to the side with the peeling film), a peeling film (a film made of polyethylene terephthalate (PET)) was peeled off on one side by a silicone treatment by a laminating roller at a temperature of 70°C, a pressure of 0.9 MPa, and a speed of 1 m/min. The peeling-treated surface (surface roughness: 30 nm) of "SP-PET381031" manufactured by Lintec Corporation (thickness 38 μm, equivalent to the aforementioned first peeling film) was laminated from the first peeling film side to produce a laminated sheet (i.e., the first laminate) with the peeling film laminated on both sides of the film for forming the inner surface protective film. The number of sheets with poor peeling was investigated in the same manner as in Example 1, the frequency of poor peeling was evaluated, and the surface roughness (Ra) was measured. In addition, the second laminate, the third laminate, and the fourth laminate were produced in the same manner as in Example 1 and evaluated by laser marking. The results are shown in Table 1.

[Table 2] Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Comparison Example 1 Components of the protective film forming composition (content (mass fraction)) Binder polymer (A) A-1 20.0 Thermosetting resin (B) B-1 13.0 B-2 1.0 B-3 1.0 B-4 1.0 Heat curing agent (C) C-1 0.5 Hardening accelerator (D) D-1 0.5 Filling material (E) E-1 60 Silane coupling agent (F) F-1 1.0 Colorant(G) G-1 2.0 Temperature and pressure conditions when attaching the first peeling film to the inner protective film forming film 70℃ 0.5MPa 70℃ 0.7MPa 70℃ 0.8MPa 70℃ 0.9MPa 70℃ 0.9MPa Number of pieces with peeling defects/10 2/10 3/10 5/10 7/10 8/10 Evaluation of the frequency of peeling failure B B C D D Surface roughness of the workpiece side of the film for forming the inner protective film (nm) 88 49 38 34 30 Surface roughness of the support sheet side of the film for forming the inner protective film (nm) 29 29 29 29 218 Surface roughness of the film for forming the inner protective film on the workpiece side / Surface roughness of the support sheet side 3.03 1.69 1.31 1.17 0.14 Laser Marking Reviews ○ ○ ○ ○ × [Industry Availability]

The third multilayer manufacturing method and the fourth multilayer manufacturing method of the present invention can be used to manufacture a semiconductor device with an inner surface protective film.

1: Composite sheet for forming protective film 5: First laminate 6: Second laminate 7: Semiconductor chip with inner protective film 8: Semiconductor wafer 8b: Inner surface of semiconductor wafer 9: Semiconductor chip 10: Support sheet 11: Substrate 12: Adhesive layer 13: Film for forming inner protective film 13': Inner protective film 13'a: Rough surface of inner protective film 13'b: Smooth surface of inner protective film 13a: Rough surface of film for forming inner protective film 13b: Smooth surface of film for forming inner protective film Surface 14: Workpiece 14a: Electrical surface of workpiece 14b: Inner surface of workpiece 16: Adhesive layer for clamp 17: Electrical surface protection tape 18: Fixing clamp 19: Third laminate 19': Fourth laminate 20: Semiconductor device 21: Semiconductor device with inner surface protective film 21': Semiconductor device with film for forming inner surface protective film 62: Electronic component 63: Circuit board 63a: Terminal forming surface 64: Sealing resin layer 151: First peeling film 152: Second peeling film

[Figure 1] is a schematic cross-sectional view schematically showing an example of an implementation form of the method for manufacturing a third multilayer body. [Figure 2] is a schematic cross-sectional view schematically showing an example of a film for forming an inner surface protective film. [Figure 3] is a schematic cross-sectional view schematically showing another example of an implementation form of the method for manufacturing a third multilayer body. [Figure 4] is a schematic cross-sectional view schematically showing another example of an implementation form of the method for manufacturing a fourth multilayer body. [Figure 5] is a schematic cross-sectional view schematically showing another example of an implementation form of the method for manufacturing a fourth multilayer body. [Figure 6] is a schematic cross-sectional view schematically showing an example of an implementation form of a method for manufacturing a semiconductor device with an inner surface protective film. [Figure 7] is a schematic cross-sectional view schematically showing another example of an implementation form of a method for manufacturing a semiconductor device with an inner surface protective film. [Fig. 8] is a schematic cross-sectional view schematically showing another example of an implementation form of a method for manufacturing a semiconductor device with an inner surface protective film. [Fig. 9] is a schematic cross-sectional view schematically showing an example of a method for manufacturing a semiconductor chip with an inner surface protective film. [Fig. 10] is a schematic cross-sectional view schematically showing another example of a method for manufacturing a semiconductor chip with an inner surface protective film. [Fig. 11] is a schematic cross-sectional view showing an example of a support sheet 10 having an adhesive layer 12 provided on a substrate 11.

6: Second layer

10: Support sheet

13: Film for forming inner protective film

13a: Rough surface of the film used to form the inner protective film

13b: Smooth surface of the film used to form the inner protective film

14: Workpiece

14a: Electrical path of workpiece

14b: Inner surface of the workpiece

16: Adhesive layer for clamps

17: Electrical road surface protection tape

18: Fixing clamp

19: The third layer

152: Second peeling membrane

Claims (19)

A method for manufacturing a third laminate is to manufacture a third laminate by laminating a workpiece, a film for forming an inner surface protective film, and a support sheet in sequence; one side of the workpiece is a conductive surface, and the other side is an inner surface; one side of the film for forming an inner surface protective film is a smooth surface, and the other side is a rough surface rougher than the smooth surface; the surface roughness Ra of the rough surface is 88nm to 1200nm; the The ratio of the surface roughness Ra of the rough surface to the surface roughness Ra of the smooth surface of the inner surface protective film forming film is 3.03 to 50; the manufacturing method of the third laminated body comprises: a first lamination step, attaching the rough surface of the inner surface protective film forming film to the inner surface of the workpiece in a facing manner; and a second lamination step, attaching the support sheet to the smooth surface of the inner surface protective film forming film. The manufacturing method of the third laminate as described in claim 1, wherein at least the process from the aforementioned first lamination step to the aforementioned second lamination step is performed by connecting a device for attaching a film for forming an inner surface protective film to a device for attaching a support sheet, or is performed in the same device. A method for manufacturing a third multilayer body as described in claim 1 or 2, wherein between the first multilayer step and the second multilayer step, the second multilayer body having the inner surface protective film formed film attached to the workpiece is transported piece by piece. The manufacturing method of the third laminate as described in claim 1 or 2, wherein the conveying distance of the workpiece from the starting point of the attachment of the first lamination step to the ending point of the attachment of the second lamination step is less than 7000 mm. The manufacturing method of the third laminate as described in claim 1 or 2, wherein the transport time of the workpiece from the start of the attachment of the first lamination step to the end of the attachment of the second lamination step is less than 150 seconds. The manufacturing method of the third laminate as described in claim 1 or 2, wherein the aforementioned electrical surface of the aforementioned workpiece is protected by an electrical surface protection tape; after the aforementioned second lamination step, it includes: a peeling step of peeling the aforementioned electrical surface protection tape from the aforementioned electrical surface of the aforementioned workpiece. The manufacturing method of the third laminate as described in claim 6, wherein the inner surface of the workpiece is a ground surface, and the electrical surface protection belt is an inner surface grinding belt. A method for manufacturing a third multilayer structure as described in claim 1 or 2, wherein the workpiece is a semiconductor wafer. The manufacturing method of the third laminate as described in claim 1 or 2, wherein the aforementioned workpiece is a semiconductor device panel, and the aforementioned semiconductor device panel is composed of a collection of semiconductor devices in which at least one electronic component is sealed by a sealing resin. The manufacturing method of the third laminate as described in claim 1 or 2, wherein the aforementioned support sheet is provided with an adhesive layer on a substrate; the manufacturing method of the aforementioned third laminate comprises: a second lamination step, which is to attach the aforementioned adhesive layer of the aforementioned support sheet to the aforementioned smooth surface of the aforementioned film for forming the inner surface protective film. The manufacturing method of the third multilayer body as described in claim 10, wherein the aforementioned adhesive layer is energy ray curable. The manufacturing method of the third multilayer body as described in claim 1 or 2 includes: irradiating the inner surface protective film forming film with laser from the side of the supporting sheet to perform laser marking. A method for manufacturing a fourth laminate, wherein the fourth laminate is formed by sequentially stacking a workpiece, an inner surface protective film, and a support sheet, and the method for manufacturing the fourth laminate comprises: hardening the inner surface protective film forming film of the third laminate manufactured by the method for manufacturing a third laminate as described in any one of claims 1 to 12 to form an inner surface protective film. The manufacturing method of the fourth laminate as described in claim 13 includes: a step of irradiating the inner protective film with laser from the side of the support sheet to perform laser marking. A method for manufacturing a semiconductor device with an inner surface protective film comprises: a step of cutting the workpiece and the inner surface protective film of the fourth multilayer body manufactured by the manufacturing method of the fourth multilayer body as described in claim 13 or 14 to produce a semiconductor device with an inner surface protective film; and a step of picking up the semiconductor device with an inner surface protective film from the supporting sheet. A method for manufacturing a semiconductor device with an inner surface protective film comprises: a step of cutting the inner surface protective film forming film of the third laminate manufactured by the manufacturing method of the third laminate described in any one of claims 1 to 12 and the workpiece to manufacture a semiconductor device with an inner surface protective film forming film; a step of hardening the inner surface protective film forming film to manufacture an inner surface protective film; and a step of picking up the semiconductor device with an inner surface protective film forming film or the semiconductor device with an inner surface protective film from the supporting sheet. The method for manufacturing a semiconductor device with an inner surface protective film as described in claim 15 or 16, wherein the film for forming the inner surface protective film is thermosetting, and the step of manufacturing the inner surface protective film is to heat-treat the film for forming the inner surface protective film to perform thermosetting. A method for manufacturing a semiconductor device with an inner surface protective film as described in claim 15 or 16, wherein the inner surface protective film forming film is energy ray curable, and the step of manufacturing the inner surface protective film is to irradiate the inner surface protective film forming film with energy rays to perform energy ray curing. A third laminate is formed by laminating a workpiece, a film for forming an inner surface protective film, and a support sheet in sequence; one side of the workpiece is a conductive surface, and the other side is an inner surface; one side of the film for forming an inner surface protective film is a smooth surface, and the other side is a rough surface that is rougher than the smooth surface; the surface roughness Ra of the rough surface is 88nm to 1200nm; the ratio of the surface roughness Ra of the rough surface of the film for forming an inner surface protective film to the surface roughness Ra of the smooth surface of the film for forming an inner surface protective film is 3.03 to 50; the rough surface of the film for forming an inner surface protective film is bonded to the inner surface of the workpiece; the support sheet is bonded to the smooth surface of the film for forming an inner surface protective film.

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