Resin film, composite sheet, and method for manufacturing semiconductor device

Abstract

The present invention provides a resin film, wherein a test piece of the resin film having a diameter of 25 mm and a thickness of 1 mm is strained under the conditions of a temperature of 90°C and a frequency of 1 Hz and the storage modulus of the test piece is measured, when the storage modulus of the test piece when the strain of the test piece is 1% is set to Gc1, and the storage modulus of the test piece when the strain of the test piece is 300% is set to Gc300, the value of X calculated by the following formula is greater than 19 and less than 10000, X = Gc1 / Gc300. The present invention also provides a composite sheet, which comprises a substrate, a buffer layer disposed on the substrate, and the resin film disposed on the buffer layer.

Description

Technical Field

[0001] The present invention relates to a resin film, a composite sheet, and a method for manufacturing a semiconductor device.

[0002] This application claims priority based on Japanese Patent Application No. 2020-031717 filed in Japan on February 27, 2020, and uses the contents thereof herein. Background Art

[0003] Until now, a flip chip mounting method has been used when mounting a multi-pin LSI package for an MPU or gate array on a printed wiring substrate. In this mounting method, a semiconductor chip having convex electrodes (hereinafter referred to as "bumps" in this specification) formed on its connection pads with eutectic solder, high-temperature solder, gold, etc. is used as a semiconductor chip. These bumps are made to face and contact with corresponding terminal portions on the chip mounting substrate through a so-called flip-chip method to perform melt / diffusion bonding.

[0004] The semiconductor chip used in the mounting method can be obtained, for example, by grinding or cutting the surface of a semiconductor wafer having bumps formed on the circuit surface opposite to the circuit surface (in other words, the bump forming surface) to separate the semiconductor chips. In the process of obtaining the above-mentioned semiconductor chips, usually, in order to protect the bump forming surface and the bumps of the semiconductor wafer, a curable resin film is attached to the bump forming surface and the film is cured, thereby forming a protective film on the bump forming surface.

[0005] On the other hand, the semiconductor device is expected to have higher functions, so the size of the semiconductor chip tends to be enlarged. However, the enlarged semiconductor chip will be warped when mounted on the substrate, so the bumps are easily deformed, especially the bumps located at the end of the semiconductor chip or near it are prone to cracks. Therefore, it is also expected that the protective film formed on the bump formation surface can suppress such bump damage.

[0006] For a method of forming a protective film on a bump formation surface of a semiconductor wafer, refer to Figures 8A to 8D Provide explanation.

[0007] Used in the formation of protective films Fig. 8A The protective film forming sheet 8 is shown. The protective film forming sheet 8 is formed by laminating a buffer layer 83 and a curable resin film 82 in this order on a base material 81. The buffer layer 83 has a buffering effect on the force applied to the buffer layer 83 and the layers adjacent thereto.

[0008] First, the protective film forming sheet 8 is arranged so that the curable resin film 82 faces the bump forming surface 9 a of the semiconductor wafer 9 .

[0009] Then, if Figure 8B As shown, the protective film forming sheet 8 is pressed onto the semiconductor wafer 9 so that the curable resin film 82 of the protective film forming sheet 8 is bonded to the bump forming surface 9a of the semiconductor wafer 9. At this time, the curable resin film 82 is bonded while being heated. Thus, the curable resin film 82 is bonded to the bump forming surface 9a of the semiconductor wafer 9 and the surface 91a of the bump 91. However, if the bump 91 penetrates the curable resin film 82, a part of the surface 91a of the bump 91 is bonded to the buffer layer 83.

[0010] After the curable resin film 82 is bonded in this way, the surface (back side) 9b of the semiconductor wafer 9 opposite to the bump forming surface 9a is further polished as needed, and then a protective film forming sheet (not shown) is attached to the back side 9b of the semiconductor wafer 9 to protect the back side 9b.

[0011] Then, if Figure 8C As shown, the base material 81 and the buffer layer 83 are removed from the curable resin film 82 .

[0012] Next, the curable resin film 82 is cured. Fig.8D As shown, a protection film 82' is formed.

[0013] The method for forming the protective film requires that the upper portion 910 of the bump 91 penetrate the protective film 82' and protrude. Therefore, as described above, it is important to form a state in which the upper portion 910 of the bump 91 penetrates the curable resin film 82 and protrudes, and the curable resin film 82 does not remain on the upper portion 910 of the bump 91 when the substrate 81 and the buffer layer 83 are peeled off. Fig. 9 , an example of a state where the curable resin film 82 remains on the upper portion 910 of the bump 91 is shown. In the example, the entire surface 91a of the bump 91 is covered with the curable resin film 82, but this is only an example of a state where the curable resin film 82 remains. For example, there is a case where a part of the surface 91a of the upper portion 910 of the bump 91 is not covered with the curable resin film 82 and is exposed.

[0014] Thus, as a protective film forming sheet capable of forming a protective film in a manner that no curable resin film remains on the upper part of the bump, a protective film forming sheet is disclosed, which is constructed in a manner that the shear modulus of the buffer layer when the buffer layer is strained by 300% under the conditions of a temperature of 90°C and a frequency of 1 Hz is equal to or greater than the shear modulus of the curable resin film when the curable resin film is strained by 300% under the same conditions (see patent document 1).

[0015] Prior art literature

[0016] Patent Literature

[0017] Patent Document 1: Japanese Patent No. 6344811 Summary of the invention

[0018] Technical Problems to be Solved by the Invention

[0019] On the other hand, as described above, at the stage where the protective film forming sheet is attached to the bump forming surface of the semiconductor wafer using the curable resin film while heating the curable resin film in the protective film forming sheet (for example, Figure 8B In the stage of bonding, the width of the curable resin film sometimes becomes wider than that before bonding, and the curable resin film overflows from the original size. Moreover, the curable resin film which can suppress the residual curable resin film on the upper part of the bump as described above is prone to such overflow. If the curable resin film overflows in this way, various devices may be contaminated by the adhesion of the overflowed curable resin film in the subsequent processes of using the semiconductor wafer or the semiconductor chip obtained by dividing the semiconductor wafer. Moreover, in the conventional protective film forming sheets, there is no protective film forming sheet which is intended to suppress the overflow of the above-mentioned curable resin film.

[0020] So far, the case where a curable resin film is attached to the bump forming surface of a semiconductor wafer has been cited as an example for explanation, but it is not limited to the curable resin film. Sometimes, the resin film is attached to the concave-convex surface of the semiconductor wafer other than the bump forming surface. In addition, similar to the case of the upper part of the bump, sometimes it is also required to suppress the residual resin film on the upper part of the convex part of the concave-convex surface. In this regard, when the concave-convex surface is fully attached as described above, the resin film may overflow.

[0021] The object of the present invention is to provide a resin film that can be suitable for attaching to a concave-convex surface and a composite sheet having the resin film for use when attaching the resin film to a concave-convex surface. When the resin film is attached to the concave-convex surface, the convex portion can penetrate it, and it can be prevented from remaining on the upper part of the convex portion and from overflowing beyond the initial size.

[0022] Technical means to solve technical problems

[0023] The present invention provides a resin film, wherein a test piece of the resin film having a diameter of 25 mm and a thickness of 1 mm is strained under the conditions of a temperature of 90° C. and a frequency of 1 Hz and the storage modulus of the test piece is measured, when the storage modulus of the test piece when the strain of the test piece is 1% is set to Gc1 and the storage modulus of the test piece when the strain of the test piece is 300% is set to Gc300, the value of X calculated by the following formula is 19 or more and less than 10000,

[0024] X=Gc1 / Gc300.

[0025] The resin film of the present invention is used for bonding to an uneven surface.

[0026] The resin film of the present invention may be curable.

[0027] Furthermore, the present invention provides a composite sheet including a substrate, a buffer layer provided on the substrate, and a resin film provided on the buffer layer, wherein the resin film is the resin film of the present invention.

[0028] In addition, the present invention provides a method for manufacturing a semiconductor device, which includes: an attaching process of attaching the curable resin film in the composite sheet of the present invention to the surface having bumps of a semiconductor wafer so that the top end of the bumps protrudes from the resin film, thereby arranging the composite sheet on the semiconductor wafer; a removal process of removing the layers in the composite sheet other than the resin film from the resin film after the attaching process; a curing process of curing the resin film after the removing process to form a first protective film; a dividing process of dividing the semiconductor wafer after the curing process to thereby produce a semiconductor chip; a cutting process of cutting the first protective film after the curing process; and an installation process of flip-chip bonding the semiconductor chip with the first protective film obtained after the dividing process and the cutting process, which has the semiconductor chip and the first protective film arranged on the surface having bumps of the semiconductor chip and the top end of the bumps protruding from the first protective film, to a substrate at the top end of the bump.

[0029] Effects of the Invention

[0030] According to the present invention, a resin film that can be suitable for attaching to a concave-convex surface and a composite sheet having the resin film for use when attaching the resin film to a concave-convex surface can be provided. When the resin film is attached to the concave-convex surface, the convex portion can penetrate it, and it can be prevented from remaining on the upper part of the convex portion, and it can be prevented from overflowing beyond the initial size. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 It is a cross-sectional view schematically showing an example of a resin film according to an embodiment of the present invention.

[0032] Figure 2 It is a top view for schematically explaining the overflow amount of the resin film when the planar shape of the resin film is a circle.

[0033] Figure 3 This is a cross-sectional view schematically showing an example of a composite sheet according to an embodiment of the present invention.

[0034] Figure 4 This is a cross-sectional view schematically showing another example of a composite sheet according to one embodiment of the present invention.

[0035] Figure 5A To schematically illustrate the use Figure 3 0 is a cross-sectional view of an example of a method for manufacturing a semiconductor device using a composite sheet shown in .

[0036] Figure 5B To schematically illustrate the use Figure 3 0 is a cross-sectional view of an example of a method for manufacturing a semiconductor device using a composite sheet shown in .

[0037] Figure 5C To schematically illustrate the use Figure 3 0 is a cross-sectional view of an example of a method for manufacturing a semiconductor device using a composite sheet shown in .

[0038] Figure 5D To schematically illustrate the use Figure 3 0 is a cross-sectional view of an example of a method for manufacturing a semiconductor device using a composite sheet shown in .

[0039] Fig. 6A To schematically illustrate the use Figure 4 0 is a cross-sectional view of an example of a method for manufacturing a semiconductor device using a composite sheet shown in .

[0040] Figure 6B To schematically illustrate the use Figure 4 0 is a cross-sectional view of an example of a method for manufacturing a semiconductor device using a composite sheet shown in .

[0041] Figure 6C To schematically illustrate the use Figure 4 0 is a cross-sectional view of an example of a method for manufacturing a semiconductor device using a composite sheet shown in .

[0042] Fig.6D To schematically illustrate the use Figure 4 0 is a cross-sectional view of an example of a method for manufacturing a semiconductor device using a composite sheet shown in .

[0043] Figure 7 This is a top view schematically showing a laminate including a thermosetting resin film produced when measuring the overflow amount of the thermosetting resin film in Example 1.

[0044] Fig. 8A It is a cross-sectional view for schematically illustrating a method for forming a protective film on a bump formation surface of a semiconductor wafer.

[0045] Figure 8B It is a cross-sectional view for schematically illustrating a method for forming a protective film on a bump formation surface of a semiconductor wafer.

[0046] Figure 8CIt is a cross-sectional view for schematically illustrating a method for forming a protective film on a bump formation surface of a semiconductor wafer.

[0047] Fig.8D It is a cross-sectional view for schematically illustrating a method for forming a protective film on a bump formation surface of a semiconductor wafer.

[0048] Fig. 9 This is a cross-sectional view schematically showing an example of a state where a curable resin film remains on the upper part of the bump. DETAILED DESCRIPTION

[0049] ◇Resin film and method for producing the same

[0050] A resin film according to one embodiment of the present invention is a resin film in which a test piece of a resin film having a diameter of 25 mm and a thickness of 1 mm is strained under the conditions of a temperature of 90° C. and a frequency of 1 Hz and the storage modulus of the test piece is measured. When the storage modulus of the test piece when the strain of the test piece is 1% is Gc1 and the storage modulus of the test piece when the strain of the test piece is 300% is Gc300, the value of X calculated by the following formula is 19 or more and less than 10000,

[0051] X=Gc1 / Gc300.

[0052] The test piece for the strain dispersion measurement was in the form of a film, and its planar shape was circular.

[0053] The test piece may be a single-layer resin film having a thickness of 1 mm, but is preferably a laminated film formed by laminating a plurality of single-layer resin films having a thickness of less than 1 mm from the viewpoint of ease of production.

[0054] The thicknesses of the plurality of single-layer resin films constituting the laminated film may all be the same, may all be different, or may only partially be the same. However, from the viewpoint of easy production, the thicknesses of all are preferably the same.

[0055] In this specification, not limited to the above-mentioned Gc1 and Gc300, "storage modulus of the test piece" refers to "the storage modulus of the test piece corresponding to the strain when a test piece of a resin film with a diameter of 25 mm and a thickness of 1 mm is strained under the conditions of a temperature of 90°C and a frequency of 1 Hz".

[0056] For example, as described later, the resin film of the present embodiment can constitute a composite sheet by being stacked with a base material and a buffer layer.

[0057] Figure 1 It is a cross-sectional view schematically showing an example of a resin film according to an embodiment of the present invention.

[0058] In order to facilitate understanding of the features of the present invention, some drawings used in the following description may show main parts in an exaggerated manner for convenience, and the dimensional ratios of the components are not necessarily the same as the actual ones.

[0059] The resin film 12 shown here has a first peeling film 151 on one surface (sometimes referred to as the "first surface" in this specification) 12a thereof, and has a second peeling film 152 on the other surface (sometimes referred to as the "second surface" in this specification) 12b on the opposite side of the first surface 12a.

[0060] Such a resin film 12 is preferably stored in a roll form, for example.

[0061] The X value of the test piece of the resin film 12 is 19 or more and less than 10,000.

[0062] Both the first release film 151 and the second release film 152 may be known release films.

[0063] The first release film 151 and the second release film 152 may be the same as or different from each other. For example, the release forces required when the first release film 151 and the second release film 152 are released from the resin film 12 may be different from each other.

[0064] for Figure 1 The resin film 12 shown in the figure has an exposed surface formed by removing any one of the first peeling film 151 and the second peeling film 152 as a surface to be attached to the concave-convex surface. Then, the exposed surface formed by removing the remaining other of the first peeling film 151 and the second peeling film 152 is an attachment surface for other layers (such as a buffer layer, etc.) used to constitute the composite sheet described later.

[0065] exist Figure 1 , an example in which a release film is provided on two surfaces (the first surface 12a and the second surface 12b) of the resin film 12 is shown, but the release film may be provided on only one surface of the resin film 12, that is, the release film may be provided only on the first surface 12a or only on the second surface 12b.

[0066] The resin film of the present embodiment may be curable or non-curable. For example, the resin film may function as a protective film (e.g., the first protective film described later, the same below) by curing, or may function as a protective film in an uncured state.

[0067] The curable resin film may be either thermosetting or energy-ray-curable, or may have both thermosetting and energy-ray-curable properties.

[0068] When a protective film is formed using the resin film of the present embodiment, the resin film is preferably curable from the viewpoint of being able to form a protective film having higher protective performance.

[0069] In this specification, "energy ray" refers to a ray having an energy quantum in an electromagnetic wave or a charged particle beam. Examples of energy ray include ultraviolet rays, radiation, electron beams, etc. For example, ultraviolet rays can be irradiated by using a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light lamp, or an LED lamp as an ultraviolet source. For an electron beam, an electron beam generated by an electron beam accelerator, etc. can be irradiated.

[0070] In the present specification, “energy ray-curable” means a property of being cured by irradiation with energy rays, and “non-energy ray-curable” means a property of not being cured even by irradiation with energy rays.

[0071] In addition, "non-curable" means a property that is not cured by any means such as heating or irradiation with energy rays. The non-curable film for protective film formation is regarded as a protective film after being provided (formed) on a target object.

[0072] The resin film of the present embodiment contains a resin component, and may or may not contain components other than the resin component.

[0073] Preferred resin films include, for example, resin films containing a resin component, a filler, and various additives that are not either of the two components (resin component and filler) and have an effect of adjusting the storage elastic modulus of the resin film.

[0074] Examples of the additive having the effect of adjusting the storage modulus of the resin film include a rheology control agent (thixotropic agent), a surfactant, and silicone oil.

[0075] The resin film of this embodiment is soft and suitable for being attached to an uneven surface.

[0076] When the resin film of the present embodiment is attached to the concave-convex surface while being heated, the convex portion of the concave-convex surface penetrates the resin film, and the upper portion of the convex portion protrudes from the resin film. Furthermore, the softened resin film is spread between the convex portions in a manner covering the convex portions, thereby fitting closely to the concave-convex surface, and at the same time covering the surface of the convex portion, especially covering the surface of the vicinity of the concave-convex surface of the convex portion, thereby filling the bottom of the convex portion. In this state, the resin film can be suppressed from remaining on the upper portion of the convex portion. Furthermore, when the resin film is curable, the cured product of the resin film in this state can be inevitably suppressed from adhering to the upper portion of the convex portion. Furthermore, since the attached resin film can be suppressed from overflowing beyond the initial size, for example, the resin film can be suppressed from overflowing from the concave-convex surface. The reason why the residue and overflow of the resin film can be suppressed in this way is that the resin film satisfies the condition of the X value (19≤X value<10000).

[0077] Furthermore, when the resin film is used, in a state where the resin film and its cured product are disposed on the concavo-convex surface, it is possible to prevent the area other than the upper part of the convex part of the concavo-convex surface (for example, the bottom near the concavo-convex surface) or the area near the convex part of the concavo-convex surface from being accidentally uncovered by the resin film and its cured product and exposed, thereby preventing so-called shrinkage. Therefore, the reason why the basic characteristics of the resin film are good is that the resin film satisfies the condition of the X value (19≤X value<10000).

[0078] Therefore, the resin film of the present embodiment has extremely excellent properties in that the convex portions can be exposed and the entire concavo-convex surface can be covered by the resin film itself and its cured product.

[0079] The heating temperature and the attaching pressure of the resin film of this embodiment when attaching it to the uneven surface can be appropriately adjusted according to other attaching conditions, but can be set to be the same as when attaching it to the bump formation surface of the semiconductor wafer described later, for example.

[0080] Whether or not there is a residual resin film on the upper part of the convex part of the uneven surface can be confirmed by, for example, obtaining SEM imaging data of the upper part of the convex part.

[0081] In addition, whether the resin film has protruded from the uneven surface or whether the resin film has shrunk on the uneven surface can be confirmed by, for example, acquiring SEM imaging data of the corresponding portion on the uneven surface.

[0082] When the resin film of this embodiment is attached to a concavo-convex surface, the composite sheet including the resin film of this embodiment can be used. The composite sheet will be described in detail later.

[0083] More specifically, as an object having the uneven surface to which the resin film is attached, for example, there can be mentioned a semiconductor wafer having bumps.

[0084] That is, the resin film can be attached to the semiconductor wafer before being divided into semiconductor chips. In this case, the resin film is attached to the surface of the semiconductor wafer having bumps and used.

[0085] In this specification, a surface having bumps of any of a semiconductor wafer and a semiconductor chip may be referred to as a "bump formation surface".

[0086] At this time, by heating the resin film while attaching it to the bump forming surface, the bumps penetrate the resin film and the top of the bump protrudes from the resin film. In addition, the softened resin film is spread between the bumps in a manner that covers the bumps, closely fits the bump forming surface, and covers the surface of the bumps, especially the surface of the parts near the bump forming surface, thereby filling the bottom of the bumps. In this state, it is possible to suppress the resin film from remaining in the upper part headed by the top of the bump. In addition, when the resin film is curable, it is also necessary to suppress the cured product of the resin film in this state from adhering to the upper part of the bump. Further, since the resin film after attachment can be suppressed from overflowing beyond the initial size, for example, the resin film can be suppressed from overflowing from the bump forming surface of the semiconductor wafer. Further, when the resin film is used, in a state where the resin film and its cured product are set on the bump forming surface, it is possible to suppress the area other than the upper part of the bump or the area near the bump of the bump forming surface from accidentally exposing (i.e. shrinking). The reasons for obtaining these effects are as described above.

[0087] When the resin film is curable, the resin film in this state (the state of filling the bottom of the bump) will subsequently form a first protective film through curing. When the resin film is non-curable, the resin film in this state (the state of filling the bottom of the bump) becomes the first protective film.

[0088] In this specification, the protective film disposed on the bump forming surface of the semiconductor wafer or semiconductor chip is referred to as the "first protective film". In addition, the protective film disposed on the surface (i.e., the back surface) opposite to the bump forming surface of the semiconductor wafer or semiconductor chip is referred to as the "second protective film".

[0089] When attaching a resin film to an object such as an uneven surface, when the resin film overflows beyond its initial size, look down from above the overflowing resin film to find the maximum value of the length of the line segment connecting two different points on the periphery of the resin film at this time, and further find the value of the initial (i.e., before overflow) width of the resin film at the position where it overlaps with the line segment representing the maximum value. The amount of resin film overflow can be calculated by subtracting the value of the resin film width from the maximum value of the line segment length.

[0090] Figure 2 It is a top view for schematically explaining the overflow amount of the resin film when the planar shape of the resin film is a circle.

[0091] In addition, Figure 2 In the subsequent drawings, the same components as those shown in the drawings that have already been described are denoted by the same reference numerals as those in the drawings that have already been described, and detailed description thereof will be omitted.

[0092] The resin film 101 shown here is in a state of overflowing from the initial size when attached to the attachment object 102. The reference numeral 101' shows the resin film in the initial size, and it is shown for convenience in order to make it easier to understand the overflow amount. The plane shape of the initial resin film 101' is circular, while the plane shape of the resin film 101 in the overflowing state is non-circular. This is only an example, and the plane shape of the resin film 101 in the overflowing state is not limited to the shape shown here.

[0093] In order to find the overflow amount of the resin film 101, it is only necessary to find the maximum value of the length D1 of the line segment connecting a point 1010a on the periphery 1010 of the resin film 101 and another point 1010b different therefrom, and further find the value D0 of the initial width (i.e., before the overflow) of the resin film 101' at the position where the line segment representing the maximum value overlaps. The difference between D1 and D0 (D1-D0) is the overflow amount.

[0094] In a plan view, the line segment indicating the maximum value on the resin film 101 sometimes passes through the center of the circle of the initial resin film 101'. In this case, the width of the initial resin film 101' at the position overlapping with the line segment indicating the maximum value is the diameter of the resin film 101'.

[0095] Here, the overflow amount of the resin film when the planar shape of the resin film is a circle is described with reference to the drawings. However, when the planar shape is a shape other than a circle, the overflow amount of the resin film can be calculated by the same method.

[0096] When a resin film is attached to a concave-convex surface of an attached object, the degree of strain of the resin film is greatly different in the middle stage when the upper part of the convex part of the concave-convex surface (when the attached object is a semiconductor wafer with bumps, the upper part of the bumps) penetrates the resin film and is about to protrude, and in the final stage when the upper part of the convex part penetrates the resin film and protrudes, and the resin film fills the bottom of the convex part. More specifically, the strain of the resin film in the middle stage is large, and the strain of the resin film in the final stage is small.

[0097] The resin film of this embodiment adopts Gc1 as its storage modulus when the strain is small, and adopts Gc300 as its storage modulus when the strain is large. By setting Gc1 high and Gc300 low, the X value (= Gc1 / Gc300) is limited to a specific range, and has the excellent effect described above.

[0098] The resin film may have an X value of 19 or more and less than 10,000. For example, the X value may be 5,000 or less, 2,000 or less, 1,000 or less, 500 or less, 300 or less, 100 or less, or 70 or less.

[0099] For example, the value of X may be in any range of 19-5000, 19-2000, 19-1000, 19-500, 19-300, 19-100, and 19-70.

[0100] Different from the resin film of this embodiment, other resin films having an X value of 10,000 or more do not exhibit the shrinkage suppression effect even if the upper part of the convex part protrudes from the other resin film by being attached to the concave-convex surface, and the cured product of the other resin film remains in a state of shrinkage.

[0101] In the resin film, as long as the X value is 19 or more and less than 10,000, Gc1 is not particularly limited.

[0102] As described above, Gc1 is preferably 1×10 4 ~1×10 6 Pa.

[0103] In the resin film, as long as the X value is 19 or more and less than 10,000, Gc300 is not particularly limited.

[0104] Among them, Gc300 is preferably 1 to 5000 Pa for the same reason as that of Gc1 described above.

[0105] For the resin film, it is preferred that the above conditions are satisfied at the same time, that is, Gc1 is preferably 1×10 4 ~1×10 6 Pa and Gc300 is 1~5000Pa.

[0106] Not limited to the case of Gc1 and Gc300, the storage modulus of the resin film can be easily adjusted by adjusting the type or content of the components contained in the resin film. Therefore, it is sufficient to adjust the type or content of the components contained in the composition for forming the resin film. For example, when using the thermosetting resin film forming composition (III) described later, the storage modulus of the resin film can be easily adjusted by adjusting the type or content of the main components contained such as the polymer component (A) and the filler (D) in the composition or adjusting the type or content of the additive (I) such as the rheology control agent, surfactant or silicone oil.

[0107] For example, when the content of the filler (D) or the additive (I) in the thermosetting resin film and the composition (III) is increased, the X value tends to increase.

[0108] Regardless of whether the resin film is curable or non-curable, and when the resin film is curable, regardless of whether it is thermosetting or energy-ray curable, the resin film may be composed of one layer (single layer) or more than two layers. When the resin film is composed of multiple layers, these multiple layers may be the same as or different from each other, and the combination of these multiple layers is not particularly limited.

[0109] In this specification, not limited to the case of the resin film, "multiple layers may be the same as or different from each other" means "all layers may be the same, all layers may be different, or only some layers may be the same", and further, "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".

[0110] Regardless of whether the resin film is curable or non-curable, and when the resin film is curable, regardless of whether it is thermosetting or energy-ray curable, the thickness of the resin film is preferably 1 to 100 μm, more preferably 5 to 75 μm, and particularly preferably 5 to 50 μm. By making the thickness of the resin film above the lower limit, the effect of the resin film becomes higher. For example, when a protective film is formed using a resin film, a protective film with higher protective performance can be formed. On the other hand, by making the thickness of the resin film below the upper limit, excessive thickness can be suppressed.

[0111] Here, “the thickness of the resin film” refers to the thickness of the entire resin film. For example, the thickness of a resin film composed of a plurality of layers refers to the total thickness of all the layers constituting the resin film.

[0112] <<Resin film forming composition>>

[0113] The resin film can be formed using a resin film-forming composition containing its constituent materials. For example, the resin film can be formed by applying the resin film-forming composition on the surface of the object to be formed and drying it as needed. The content ratio between the components that do not vaporize at room temperature in the resin film-forming composition is usually the same as the content ratio between the components in the resin film. In this specification, "normal temperature" refers to a temperature that is not particularly cooled or heated, that is, a normal temperature, for example, a temperature of 15 to 25°C, etc.

[0114] Thermosetting resin film can be formed using a thermosetting resin film-forming composition, energy-ray curable resin film can be formed using an energy-ray curable resin film-forming composition, and non-curable resin film can be formed using a non-curable resin film-forming composition. In addition, in this specification, when the resin film has both thermosetting and energy-ray curing properties, and the contribution of thermal curing of the resin film to its curing (for example, the formation of a protective film) is greater than the contribution of energy-ray curing to its curing, the resin film can be regarded as a thermosetting resin film. On the contrary, when the contribution of energy-ray curing of the resin film to its curing is greater than the contribution of thermal curing to its curing, the resin film can be regarded as an energy-ray curable resin film.

[0115] In the resin film, the total content of one or two or more components described below in the resin film is not more than 100% by mass based on the total mass of the resin film.

[0116] Similarly, in the resin film forming composition, the total content of one or two or more components described below in the resin film forming composition is not more than 100 mass % relative to the total mass of the resin film forming composition.

[0117] The resin film-forming composition can be applied by a known method, for example, methods using various coaters such as an air knife coater, a blade coater, a rod coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater, a Meyer rod coater, and a kiss coater.

[0118] Regardless of whether the resin film is curable or non-curable, and when the resin film is curable, whether it is thermosetting or energy-ray curable, the drying conditions of the resin film-forming composition are not particularly limited. Among them, when the resin film-forming composition contains a solvent described later, it is preferably heated and dried. In addition, for a resin film-forming composition containing a solvent, it is preferably heated and dried at 70 to 130° C. for 10 seconds to 5 minutes. Among them, for a thermosetting resin film-forming composition, it is preferably heated and dried in a manner that does not cause the composition itself and the thermosetting resin film formed by the composition to be thermally cured.

[0119] Hereinafter, the thermosetting resin film and the energy ray curable resin film will be described in further detail.

[0120] ◎Thermosetting resin film

[0121] The curing conditions when the thermosetting resin film is cured to form a cured product, especially the curing conditions when a protective film is formed, are not particularly limited as long as the degree of curing of the cured product is such that its function can be fully exerted, and may be appropriately selected according to the type of the thermosetting resin film, the purpose of the cured product, etc.

[0122] For example, in the case of forming a protective film, the heating temperature during the curing of the thermosetting resin film is preferably 100 to 200° C., more preferably 110 to 170° C., and particularly preferably 120 to 150° C. In addition, the heating time during the thermal curing is preferably 0.5 to 5 hours, more preferably 0.5 to 4 hours, and particularly preferably 1 to 3 hours.

[0123] <Thermosetting resin film-forming composition>

[0124] Examples of the thermosetting resin film-forming composition include a thermosetting resin film-forming composition (III) (sometimes simply referred to as "composition (III)" in this specification) containing a polymer component (A), a thermosetting component (B), a filler (D), and an additive (I).

[0125] [Polymer component (A)]

[0126] The polymer component (A) is a polymer compound for imparting film-forming properties, flexibility, etc. to the thermosetting resin film. In the present specification, the polymer compound also includes a product of a polycondensation reaction.

[0127] The polymer component (A) contained in the composition (III) and the thermosetting resin film may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio thereof may be arbitrarily selected.

[0128] Examples of the polymer component (A) include polyvinyl acetal, acrylic resin, urethane resin, phenoxy resin, silicone resin, and saturated polyester resin.

[0129] Among them, the polymer component (A) is preferably polyvinyl acetal.

[0130] Examples of the polyvinyl acetal in the polymer component (A) include known polyvinyl acetals.

[0131] Among these, examples of preferred polyvinyl acetals include polyvinyl formal and polyvinyl butyral, and polyvinyl butyral is more preferred.

[0132] Examples of the polyvinyl butyral include polyvinyl butyrals having structural units represented by the following formulae (i)-1, (i)-2, and (i)-3.

[0133] [Chemical formula 1]

[0134]

[0135] In the formula, l, m and n are each independently an integer of 1 or more.

[0136] The weight average molecular weight (Mw) of the polyvinyl acetal is preferably 5000 to 200000, more preferably 8000 to 100000. By making the weight average molecular weight of the polyvinyl acetal within the above range, when the thermosetting resin film is attached to the concavo-convex surface, the effect of suppressing the thermosetting resin film from remaining on the upper part of the convex part of the concavo-convex surface (for example, when the thermosetting resin film is attached to the convex point forming surface, the effect of suppressing the thermosetting resin film from remaining on the upper part of the convex point, the same below), the effect of suppressing the thermosetting resin film on the concavo-convex surface from overflowing beyond the initial size (for example, when the thermosetting resin film is attached to the convex point forming surface, the effect of suppressing the thermosetting resin film on the convex point forming surface from overflowing beyond the initial size, the same below), and the effect of suppressing the shrinkage of the thermosetting resin film and its cured product on the concavo-convex surface (for example, when the thermosetting resin film is attached to the convex point forming surface, the effect of suppressing the shrinkage of the thermosetting resin film and its cured product on the convex point forming surface, the same below) become higher.

[0137] In addition, in this specification, unless otherwise specified, the "weight average molecular weight" is a polystyrene conversion value measured by gel permeation chromatography (GPC) method.

[0138] The glass transition temperature (Tg) of polyvinyl acetal is preferably 40 to 80° C., more preferably 50 to 70° C. By setting the Tg of polyvinyl acetal to be within the above range, when the thermosetting resin film is attached to the concavo-convex surface, the effect of suppressing the thermosetting resin film from remaining on the upper part of the convex part of the concavo-convex surface, the effect of suppressing the thermosetting resin film from overflowing on the concavo-convex surface, and the effect of suppressing the shrinkage of the thermosetting resin film and its cured product on the concavo-convex surface become higher.

[0139] The ratio of three or more monomers constituting polyvinyl acetal can be arbitrarily selected.

[0140] Examples of the acrylic resin in the polymer component (A) include known acrylic polymers.

[0141] The weight average molecular weight (Mw) of the acrylic resin is preferably 5000 to 1000000, more preferably 8000 to 800000. By making the weight average molecular weight of the acrylic resin within the above range, when the thermosetting resin film is attached to the concavo-convex surface, the effect of suppressing the thermosetting resin film from remaining on the upper part of the convex part of the concavo-convex surface, the effect of suppressing the thermosetting resin film from overflowing on the concavo-convex surface, and the effect of suppressing the shrinkage of the thermosetting resin film and its cured product on the concavo-convex surface become higher.

[0142] The glass transition temperature (Tg) of the acrylic resin is preferably -50 to 70° C., more preferably -30 to 60° C. By setting the Tg of the acrylic resin within the above range, when the thermosetting resin film is attached to the concavo-convex surface, the effect of suppressing the thermosetting resin film from remaining on the upper part of the convex part of the concavo-convex surface, the effect of suppressing the thermosetting resin film from overflowing on the concavo-convex surface, and the effect of suppressing the shrinkage of the thermosetting resin film and its cured product on the concavo-convex surface become higher.

[0143] When the acrylic resin has two or more structural units, the glass transition temperature (Tg) of the acrylic resin can be calculated using the Fox equation. As the Tg of the monomer from which the structural unit is derived, the value described in a polymer data handbook or an adhesive handbook can be used.

[0144] The monomers constituting the acrylic resin may be one kind or two or more kinds. When there are two or more kinds, the combination and ratio thereof may be arbitrarily selected.

[0145] Examples of the acrylic resin include polymers of one or more (meth)acrylates;

[0146] A copolymer of two or more monomers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene and N-hydroxymethyl acrylamide;

[0147] Copolymers of one or two or more (meth)acrylates and one or two or more monomers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-hydroxymethyl acrylamide, and the like.

[0148] In this specification, "(meth)acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid, for example, "(meth)acrylate" is a concept including both "acrylate" and "methacrylate", and "(meth)acryloyl" is a concept including both "acryloyl" and "methacryloyl".

[0149] Examples of the (meth)acrylates constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, and tert-butyl (meth)acrylate. (meth)acrylate alkyl esters whose alkyl group constituting the alkyl ester is a chain structure having 1 to 18 carbon atoms, such as ester, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearate (meth)acrylate);

[0150] Cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate;

[0151] Aralkyl (meth)acrylates such as benzyl (meth)acrylate;

[0152] Cycloalkenyl (meth)acrylates such as dicyclopentenyl (meth)acrylate;

[0153] Cycloalkenyloxyalkyl (meth)acrylates such as dicyclopentenyloxyethyl (meth)acrylate;

[0154] (Meth)acrylic acid imide;

[0155] Glycidyl (meth)acrylates such as glycidyl (meth)acrylate;

[0156] (meth)acrylates containing hydroxy groups, such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate;

[0157] (Meth)acrylates containing a substituted amino group such as N-methylaminoethyl (meth)acrylate, etc. Here, "substituted amino group" means a group in which one or two hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom.

[0158] The acrylic resin may have a functional group such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, etc. that can be bonded to other compounds. The functional group of the acrylic resin may be bonded to other compounds via a crosslinking agent (F) described later, or may be directly bonded to other compounds without a crosslinking agent (F). The acrylic resin is bonded to other compounds via the functional group, and thus, for example, the reliability of the package obtained by using a thermosetting resin film tends to be improved.

[0159] In the composition (III), regardless of the type of the polymer component (A), the ratio of the content of the polymer component (A) to the total content of all components except the solvent (i.e., the ratio of the content of the polymer component (A) in the thermosetting resin film to the total mass of the thermosetting resin film) is preferably 5 to 25% by mass, and more preferably 5 to 15% by mass.

[0160] [Thermosetting component (B)]

[0161] The thermosetting component (B) has thermosetting properties and is a component for thermally curing the thermosetting resin film to form a hard cured product.

[0162] The thermosetting component (B) contained in the composition (III) and the thermosetting resin film may be one kind or two or more kinds. When there are two or more kinds, the combination and ratio thereof may be arbitrarily selected.

[0163] Examples of the thermosetting component (B) include epoxy-based thermosetting resins, polyimide resins, and unsaturated polyester resins.

[0164] Among them, the thermosetting component (B) is preferably an epoxy-based thermosetting resin.

[0165] (Epoxy thermosetting resin)

[0166] The epoxy thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2).

[0167] The epoxy-based thermosetting resin contained in the composition (III) and the thermosetting resin film may be of one kind or of two or more kinds. When there are two or more kinds, the combination and ratio thereof may be arbitrarily selected.

[0168] Epoxy resin (B1)

[0169] As the epoxy resin (B1), known epoxy resins can be listed, for example, epoxy compounds with difunctionality or higher such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydride, o-cresol novolac epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, and phenylene skeleton epoxy resin can be listed.

[0170] The epoxy resin (B1) may be an epoxy resin having an unsaturated hydrocarbon group. Compared with epoxy resins without unsaturated hydrocarbon groups, epoxy resins having unsaturated hydrocarbon groups have high compatibility with acrylic resins. Therefore, by using epoxy resins having unsaturated hydrocarbon groups, for example, the reliability of the package obtained by using a thermosetting resin film tends to be improved.

[0171] Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which part of the epoxy groups of a polyfunctional epoxy resin is converted into groups having an unsaturated hydrocarbon group. Such compounds can be obtained, for example, by subjecting (meth)acrylic acid or a derivative thereof to an epoxy group by an addition reaction.

[0172] Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin.

[0173] The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethylene (vinyl) group, a 2-propenyl (allyl) group, a (meth)acryloyl group, and a (meth)acrylamide group. An acryloyl group is preferred.

[0174] The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000, from the viewpoint of the curability of the thermosetting resin film and the strength and heat resistance of the cured product of the thermosetting resin film (e.g., protective film).

[0175] The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000 g / eq, more preferably 200 to 800 g / eq.

[0176] The epoxy resin (B1) may be used alone or in combination of two or more. When two or more kinds are used in combination, the combination and ratio thereof may be arbitrarily selected.

[0177] Thermal curing agent (B2)

[0178] The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).

[0179] Examples of the thermosetting agent (B2) include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. Examples of the functional group include phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, and groups obtained by anhydriding acid groups. Phenolic hydroxyl groups, amino groups, or groups obtained by anhydriding acid groups are preferred, and phenolic hydroxyl groups or amino groups are more preferred.

[0180] Examples of the phenolic curing agent having a phenolic hydroxyl group in the thermosetting agent (B2) include polyfunctional phenol resins, biphenol, novolac-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol resins.

[0181] Examples of the amine curing agent having an amino group in the thermosetting agent (B2) include dicyandiamide (hereinafter, sometimes abbreviated to "DICY") and the like.

[0182] The heat curing agent (B2) may have an unsaturated hydrocarbon group.

[0183] Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include compounds in which part of the hydroxyl groups of a phenolic resin are substituted with a group having an unsaturated hydrocarbon group, and compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring of a phenolic resin.

[0184] The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.

[0185] In the thermosetting agent (B2), for example, the number average molecular weight of the resin component such as a polyfunctional phenol resin, a novolac phenol resin, a dicyclopentadiene phenol resin, an aralkyl phenol resin is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000.

[0186] In the thermosetting agent (B2), the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

[0187] The thermosetting agent (B2) may be used alone or in combination of two or more. When two or more are used in combination, the combination and ratio thereof may be arbitrarily selected.

[0188] In the composition (III) and the thermosetting resin film, the content of the thermosetting agent (B2) 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 epoxy resin (B1), for example, it can be any range of 5 to 150 parts by mass, 10 to 100 parts by mass, and 15 to 75 parts by mass. By making the content of the thermosetting agent (B2) above the lower limit, it is easier to cure the thermosetting resin film. By making the content of the thermosetting agent (B2) below the upper limit, the moisture absorption rate of the thermosetting resin film can be reduced, for example, the reliability of the package obtained using the thermosetting resin film is further improved.

[0189] In the composition (III) and the thermosetting resin film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is preferably 600 to 1000 parts by mass relative to 100 parts by mass of the polymer component (A). By making the content of the thermosetting component (B) within the above range, when the thermosetting resin film is attached to the concavo-convex surface, the effect of suppressing the thermosetting resin film from remaining on the upper part of the convex part of the concavo-convex surface, the effect of suppressing the overflow of the thermosetting resin film on the concavo-convex surface, and the effect of suppressing the shrinkage of the thermosetting resin film and its cured product on the concavo-convex surface become higher, and a hard cured product (for example, a protective film) can be formed.

[0190] Furthermore, in order to obtain such effects more significantly, the content of the thermosetting component (B) can be appropriately adjusted according to the type of the polymer component (A).

[0191] For example, when the polymer component (A) is the polyvinyl acetal, in the composition (III) and the thermosetting resin film, the content of the thermosetting component (B) is preferably 600 to 1000 parts by mass, more preferably 650 to 1000 parts by mass, and particularly preferably 650 to 950 parts by mass, relative to 100 parts by mass of the polymer component (A).

[0192] [Filling material (D)]

[0193] The X value can be more easily adjusted by adjusting the amount of the filler (D) in the composition (III) and the thermosetting resin film. In addition, the thermal expansion coefficient of the cured product (e.g., protective film) of the thermosetting resin film can be more easily adjusted by adjusting the amount of the filler (D) in the composition (III) and the thermosetting resin film. For example, by optimizing the thermal expansion coefficient of the protective film (e.g., the first protective film) relative to the object of formation of the protective film, the reliability of the package obtained using the thermosetting resin film is further improved. In addition, by using a thermosetting resin film containing a filler (D), the moisture absorption rate of the cured product (e.g., protective film) of the thermosetting resin film can be reduced and the heat release can be improved.

[0194] The filler (D) may be any of an organic filler and an inorganic filler, but is preferably an inorganic filler.

[0195] Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium dioxide, red iron oxide, silicon carbide, boron nitride, etc.; beads obtained by sphericalizing these inorganic fillers; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc.

[0196] Among them, the inorganic filler is preferably silicon dioxide or aluminum oxide.

[0197] The filler (D) contained in the composition (III) and the thermosetting resin film may be one type or two or more types. When there are two or more types, the combination and ratio thereof may be arbitrarily selected.

[0198] In the composition (III), the ratio of the content of the filler (D) to the total content of all components except the solvent (i.e., the ratio of the content of the filler (D) in the thermosetting resin film to the total mass of the thermosetting resin film) is preferably 5 to 45% by mass, more preferably 5 to 40% by mass, and further preferably 5 to 30% by mass. By making the ratio within the above range, when the thermosetting resin film is attached to the concavo-convex surface, the effect of suppressing the thermosetting resin film from remaining on the upper part of the convex part of the concavo-convex surface, the effect of suppressing the overflow of the thermosetting resin film on the concavo-convex surface, and the effect of suppressing the shrinkage of the thermosetting resin film and its cured product on the concavo-convex surface become higher, and the above-mentioned thermal expansion coefficient can be further easily adjusted.

[0199] [Additive (I)]

[0200] The X value can be more easily adjusted by adjusting the type or amount of the additive (I) in the composition (III) and the thermosetting resin film.

[0201] Among them, from the viewpoint of being able to more easily adjust the X value, preferred examples of the additive (I) include rheology control agents, surfactants, silicone oils, and the like.

[0202] More specifically, examples of the rheology control agent include polyhydroxycarboxylate, polycarboxylic acid, and polyamide resin.

[0203] Examples of the surfactant include modified silicone and acrylic polymer.

[0204] Examples of the silicone oil include aralkyl-modified silicone oil and modified polydimethylsiloxane, and examples of the modifying group include aralkyl groups; polar groups such as hydroxyl groups; and groups having an unsaturated bond such as vinyl groups and phenyl groups.

[0205] As the additive (I), examples of the additive other than the above-mentioned ones include various other general-purpose additives such as plasticizers, antistatic agents, antioxidants, gettering agents, ultraviolet absorbers, and thickeners.

[0206] The additive (I) contained in the composition (III) and the thermosetting resin film may be one kind or two or more kinds. When there are two or more kinds, the combination and ratio thereof may be arbitrarily selected.

[0207] The content of the additive (I) in the composition (III) and the thermosetting resin film is not particularly limited and can be appropriately adjusted depending on the type and purpose.

[0208] For example, when the purpose is to adjust the X value, in the composition (III), the ratio of the content of the additive (I) to the total content of all components except the solvent (i.e., the ratio of the content of the additive (I) in the thermosetting resin film to the total mass of the thermosetting resin film) is preferably 0.5 to 10% by mass, more preferably 0.5 to 7% by mass, and even more preferably 0.5 to 5% by mass.

[0209] [Curing accelerator (C)]

[0210] The composition (III) and the thermosetting resin film may contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing speed of the composition (III).

[0211] Preferred curing accelerators (C) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; imidazoles (imidazoles in which one or more hydrogen atoms are replaced by groups other than hydrogen atoms) such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; organic phosphines (phosphines in which one or more hydrogen atoms are replaced by organic groups) such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenylboron salts such as tetraphenylphosphine tetraphenylborate, and triphenylphosphine tetraphenylborate; and the like.

[0212] The curing accelerator (C) contained in the composition (III) and the thermosetting resin film may be one kind or two or more kinds. When there are two or more kinds, the combination and ratio thereof may be arbitrarily selected.

[0213] When using a curing accelerator (C), in the composition (III) and the thermosetting resin film, the content of the curing accelerator (C) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the content of the thermosetting component (B). By making the content of the curing accelerator (C) above the lower limit, the effect of using the curing accelerator (C) can be more significantly obtained. By making the content of the curing accelerator (C) below the upper limit, for example, the effect of suppressing the high-polarity curing accelerator (C) from moving to the bonding surface side with the adherend in the thermosetting resin film under high temperature and high humidity conditions and segregating becomes higher, for example, the reliability of the package obtained using the thermosetting resin film is further improved.

[0214] [Coupling agent (E)]

[0215] The composition (III) and the thermosetting resin film may contain a coupling agent (E). By using a coupling agent having a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (E), the adhesion and tightness of the thermosetting resin film to the adherend can be improved. In addition, by using the coupling agent (E), the heat resistance of the cured product (e.g., protective film) of the thermosetting resin film will not be impaired, and the water resistance can be improved.

[0216] The coupling agent (E) is preferably a compound having a functional group reactive with a functional group possessed by the polymer component (A), the thermosetting component (B), etc., and is more preferably a silane coupling agent.

[0217] Preferred silane coupling agents include, for example, 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl methyl diethoxysilane, 3-glycidyloxypropyl triethoxysilane, 3-glycidyloxymethyl diethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-(2-aminoethylamino)propyl trimethoxysilane, and 3-(2-aminoethylamino)propyl trimethoxysilane. Oxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureapropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, etc.

[0218] The coupling agent (E) contained in the composition (III) and the thermosetting resin film may be one kind or two or more kinds. When there are two or more kinds, the combination and ratio thereof may be arbitrarily selected.

[0219] When a coupling agent (E) is used, the content of the coupling agent (E) is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total content of the polymer component (A) and the thermosetting component (B) in the composition (III) and the thermosetting resin film. By making the content of the coupling agent (E) above the lower limit, the effects of using the coupling agent (E), such as improving the dispersibility of the filler (D) in the resin and improving the adhesion between the thermosetting resin film and the adherend, can be more significantly obtained. By making the content of the coupling agent (E) below the upper limit, the generation of outgassing can be further suppressed.

[0220] [Crosslinking agent (F)]

[0221] When a substance having a functional group such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, etc. that can bond with other compounds is used as the polymer component (A), the composition (III) and the thermosetting resin film may contain a crosslinking agent (F). The crosslinking agent (F) is a component that allows the functional group in the polymer component (A) to bond with other compounds and crosslink, and by crosslinking in this way, the initial adhesive force and cohesive force of the thermosetting resin film can be adjusted.

[0222] Examples of the crosslinking agent (F) include organic polyisocyanate compounds, organic polyimide compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), and aziridine crosslinking agents (crosslinking agents having an aziridine group).

[0223] As the organic polyisocyanate compound, for example, aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds and alicyclic polyisocyanate compounds (hereinafter, these compounds are sometimes collectively abbreviated as "aromatic polyisocyanate compounds, etc."); trimers, isocyanurates and adducts of the aromatic polyisocyanate compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the aromatic polyisocyanate compounds, etc. with polyol compounds, etc. The "adduct" refers to the reaction product of the aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound with a low molecular weight active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. As an example of the adduct, the xylene diisocyanate adduct of trimethylolpropane, etc., which will be described later, can be cited. In addition, the "terminal isocyanate urethane prepolymer" refers to a prepolymer having a urethane bond and an isocyanate group at the terminal of the molecule.

[0224] More specifically, the organic polyisocyanate compound includes, for example, 2,4-

[0225] 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; a compound obtained by adding any one or more of toluene diisocyanate, hexamethylene diisocyanate and xylene diisocyanate to all or part of the hydroxyl groups of a polyol such as trimethylolpropane; lysine diisocyanate, etc.

[0226] Examples of the organic polyimide compound include N,N′-diphenylmethane-4,4′-bis(1-aziridinecarboxamide), trimethylolpropane-tris-β-aziridine propionate, tetramethylolmethane-tris-β-aziridine propionate, and N,N′-toluene-2,4-bis(1-aziridinecarboxamide)triethylenemelamine.

[0227] When an organic polyisocyanate compound is used as the crosslinking agent (F), a hydroxyl-containing polymer is preferably used as the polymer component (A). When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, a crosslinking structure can be easily introduced into the thermosetting resin film by the reaction of the crosslinking agent (F) and the polymer component (A).

[0228] The crosslinking agent (F) contained in the composition (III) and the thermosetting resin film may be one kind or two or more kinds. When there are two or more kinds, the combination and ratio thereof may be arbitrarily selected.

[0229] When a crosslinking agent (F) is used, in the composition (III), the content of the crosslinking agent (F) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the content of the polymer component (A). By making the content of the crosslinking agent (F) above the lower limit, the effect of using the crosslinking agent (F) can be more significantly obtained. By making the content of the crosslinking agent (F) below the upper limit, excessive use of the crosslinking agent (F) can be suppressed.

[0230] [Other ingredients]

[0231] Within the scope of not impairing the effect of the present invention, the composition (III) and the thermosetting resin film may contain other components that are not any of the above-mentioned polymer component (A), thermosetting component (B), filler (D), additive (I), curing accelerator (C), coupling agent (E) and cross-linking agent (F).

[0232] Examples of the other components include energy-ray-curable resins and photopolymerization initiators.

[0233] The other components contained in the composition (III) and the thermosetting resin film may be one kind or two or more kinds. When there are two or more kinds, the combination and ratio thereof may be arbitrarily selected.

[0234] The content of the other components in the composition (III) and the thermosetting resin film is not particularly limited and may be appropriately selected depending on the intended purpose.

[0235] [Solvent]

[0236] The composition (III) preferably further contains a solvent. The composition (III) containing a solvent has good handleability.

[0237] The solvent is not particularly limited, but preferred solvents include, for example, hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone, etc.

[0238] The solvent contained in the composition (III) may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio thereof may be arbitrarily selected.

[0239] From the viewpoint of being able to more uniformly mix the components contained in the composition (III), more preferable examples of the solvent contained in the composition (III) include methyl ethyl ketone and the like.

[0240] The content of the solvent in the composition (III) is not particularly limited and may be appropriately selected, for example, depending on the types of components other than the solvent.

[0241] <Method for preparing thermosetting resin film-forming composition>

[0242] The thermosetting resin film-forming composition such as the composition (III) can be obtained by blending the respective components constituting the composition.

[0243] The order of adding the components when blending them is not particularly limited, and two or more components may be added simultaneously.

[0244] The method for mixing the components during blending is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirring bar or a stirring blade, a method of mixing using a mixer, a method of mixing by applying ultrasonic waves, and the like.

[0245] The temperature and time for adding and mixing the components are not particularly limited as long as the components are not degraded, and may be appropriately adjusted. However, the temperature is preferably 15°C to 30°C.

[0246] ◎Energy ray curable resin film

[0247] As long as the cured product has a degree of cure to the extent that it can fully exert its functions, the curing conditions when curing the energy-ray-curable resin film to form a cured product, especially the curing conditions when forming a protective film, are not particularly limited and can be appropriately selected according to the type of energy-ray-curable resin film, the purpose of the cured product, etc.

[0248] For example, when forming a protective film, the illuminance of the energy ray when curing the energy ray curable resin film is preferably 180 to 280 mW / cm 2 Furthermore, the amount of energy ray during curing is preferably 450 to 1000 mJ / cm 2 .

[0249] <Energy ray-curable resin film-forming composition>

[0250] Examples of the energy-ray-curable resin film-forming composition include an energy-ray-curable resin film-forming composition (IV) (sometimes simply referred to as “composition (IV)” in this specification) containing an energy-ray-curable component (a), a filler and an additive.

[0251] [Energy beam curable component (a)]

[0252] The energy-ray-curable component (a) is a component that is cured by irradiation with energy rays, and is also a component that imparts film-forming properties, flexibility, and the like to the energy-ray-curable resin film.

[0253] The energy ray-curable component (a) is preferably uncured, preferably has adhesiveness, and more preferably is uncured and has adhesiveness.

[0254] Examples of the energy-curable component (a) include a polymer (a1) having an energy-curable group and a weight average molecular weight of 80,000 to 2,000,000, and a compound (a2) having an energy-curable group and a molecular weight of 100 to 80,000. At least a portion of the polymer (a1) may be crosslinked by a crosslinking agent or may not be crosslinked.

[0255] (Polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80,000 to 2,000,000)

[0256] Examples of the polymer (a1) having an energy-ray-curable group and having a weight-average molecular weight of 80,000 to 2,000,000 include an acrylic resin (a1-1) obtained by polymerizing an acrylic polymer (a11) having a functional group capable of reacting with a group possessed by other compounds and an energy-ray-curable compound (a12) having an energy-ray-curable group such as a group reactive with the functional group and an energy-ray-curable double bond.

[0257] Examples of the functional group that can react with groups possessed by other compounds include hydroxyl, carboxyl, amino, substituted amino (a group in which one or two hydrogen atoms of an amino group are replaced by groups other than hydrogen atoms), epoxy, etc. Among them, from the perspective of preventing corrosion of circuits such as semiconductor wafers or semiconductor chips, the functional group is preferably a group other than a carboxyl group.

[0258] Among them, the functional group is preferably a hydroxyl group.

[0259] Acrylic polymer having functional groups (a11)

[0260] Examples of the acrylic polymer (a11) having a functional group include a polymer obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer not having the functional group, and a polymer obtained by copolymerizing a monomer other than the acrylic monomer (non-acrylic monomer) in addition to these monomers.

[0261] Furthermore, the acrylic polymer (a11) may be a random copolymer or a block copolymer.

[0262] Examples of the acrylic monomer having the functional group include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.

[0263] Examples of the hydroxyl-containing monomer include hydroxyalkyl (meth)acrylates such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; and non-(meth)acrylic unsaturated alcohols (unsaturated alcohols not having a (meth)acryloyl skeleton) such as vinyl alcohol and allyl alcohol.

[0264] Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having ethylenically unsaturated bonds) such as fumaric acid, itaconic acid, maleic acid, and citraconic acid; anhydrides of the ethylenically unsaturated dicarboxylic acids; (meth)acrylic acid carboxylalkyl esters such as 2-carboxyethyl methacrylate, and the like.

[0265] The acrylic monomer having the functional group is preferably a hydroxyl group-containing monomer or a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.

[0266] The acrylic monomer having the functional group constituting the acrylic polymer (a11) may be of one kind or of two or more kinds. When there are two or more kinds, the combination and ratio thereof may be arbitrarily selected.

[0267] Examples of the acrylic monomer not having the functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, and tert-butyl (meth)acrylate. Alkyl (meth)acrylates whose alkyl groups constituting the alkyl esters are chain structures having 1 to 18 carbon atoms, such as decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearate (meth)acrylate), and the like.

[0268] Examples of acrylic monomers not having the functional group include alkoxyalkyl-containing (meth)acrylates such as methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate; (meth)acrylates having aromatic groups such as (meth)acrylate aryl esters such as phenyl (meth)acrylate; non-crosslinking (meth)acrylamide and its derivatives; and non-crosslinking (meth)acrylates having tertiary amino groups such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate.

[0269] The acrylic monomer not having the functional group constituting the acrylic polymer (a11) may be one kind or two or more kinds. When there are two or more kinds, the combination and ratio thereof may be arbitrarily selected.

[0270] Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; and styrene.

[0271] The non-acrylic monomer constituting the acrylic polymer (a11) may be one kind only or two or more kinds. When there are two or more kinds, the combination and ratio thereof may be arbitrarily selected.

[0272] In the acrylic polymer (a11), the ratio (content) of the amount of the structural unit derived from the acrylic monomer having the functional group relative to the total amount of the structural units constituting the polymer is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass. By making the ratio within the above range, in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy-ray curable compound (a12), the content of the energy-ray curable group can easily adjust the degree of curing of the cured product (e.g., protective film) of the energy-ray curable resin film within a preferred range.

[0273] The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be one type or two or more types. When two or more types are used, the combination and ratio thereof may be arbitrarily selected.

[0274] In the composition (IV), the ratio of the content of the acrylic resin (a1-1) to the total content of the components other than the solvent (i.e., the ratio of the content of the acrylic resin (a1-1) in the energy-ray-curable resin film to the total mass of the film) is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass.

[0275] Energy ray curable compound (a12)

[0276] The energy-ray curable compound (a12) preferably has one or more selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group as a group capable of reacting with the functional group possessed by the acrylic polymer (a11), and more preferably has an isocyanate group as the group. For example, when the energy-ray curable compound (a12) has an isocyanate group as the group, the isocyanate group is easy to react with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

[0277] The energy ray-curable compound (a12) preferably has 1 to 5 energy ray-curable groups in one molecule, and more preferably has 1 to 2 energy ray-curable groups.

[0278] Examples of the energy-ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

[0279] Acryloyl monoisocyanate compounds obtained by reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth)acrylate;

[0280] Acryloyl monoisocyanate compounds obtained by reaction of a diisocyanate compound or a polyisocyanate compound with a polyol compound and hydroxyethyl (meth)acrylate, and the like.

[0281] Among them, the energy ray curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.

[0282] The energy ray curable compound (a12) constituting the acrylic resin (a1-1) may be one kind or two or more kinds. When there are two or more kinds, the combination and ratio thereof may be arbitrarily selected.

[0283] In the acrylic resin (a1-1), the content of the energy-ray curable group from the energy-ray curable compound (a12) relative to the content of the functional group from the acrylic polymer (a11) is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. By making the content ratio within the above range, the adhesive force of the cured product (e.g., protective film) of the energy-ray curable resin film becomes greater. In addition, when the energy-ray curable compound (a12) is a monofunctional compound (having one group in one molecule), the upper limit of the content ratio is 100 mol%, but when the energy-ray curable compound (a12) is a polyfunctional compound (having two or more groups in one molecule), the upper limit of the content ratio is sometimes greater than 100 mol%.

[0284] The weight average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 2,000,000, and more preferably 300,000 to 1,500,000.

[0285] When at least a portion of the polymer (a1) is cross-linked by a cross-linking agent, the polymer (a1) may be a polymer obtained by polymerizing a monomer that does not belong to any of the above-mentioned monomers described as components constituting the acrylic polymer (a11) and has a group that reacts with the cross-linking agent, and cross-linking at the group that reacts with the cross-linking agent, or a polymer obtained by cross-linking at a group that reacts with the functional group from the energy-ray-curable compound (a12).

[0286] The polymer (a1) contained in the composition (IV) and the energy-ray-curable resin film may be one kind or two or more kinds. When two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.

[0287] (Compound (a2) having an energy ray curable group and a molecular weight of 100 to 80,000)

[0288] Examples of the energy-curable group in the compound (a2) having an energy-curable group and having a molecular weight of 100 to 80,000 include groups containing energy-curable double bonds, and examples of preferred groups include (meth)acryloyl groups and vinyl groups.

[0289] The compound (a2) is not particularly limited as long as the above conditions are satisfied, and examples thereof include low molecular weight compounds having an energy ray curable group, epoxy resins having an energy ray curable group, phenolic resins having an energy ray curable group, and the like.

[0290] Examples of the low molecular weight compound having an energy-ray curable group in the compound (a2) include polyfunctional monomers and oligomers, and an acrylate compound having a (meth)acryloyl group is preferred.

[0291] Examples of the acrylate compound include 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloyloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate, and 1,10-decanediol. di(meth)acrylates, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloyloxypropane and the like;

[0292] Multifunctional (meth)acrylates such as tris(2-(meth)acryloyloxyethyl)isocyanurate, ε-caprolactone-modified tris(2-(meth)acryloyloxyethyl)isocyanurate, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, di(trimethylolpropane) tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, and dipentaerythritol hexa(meth)acrylate;

[0293] Polyfunctional (meth)acrylate oligomers such as urethane (meth)acrylate oligomers, and the like.

[0294] As the epoxy resin having an energy-ray curable group and the phenolic resin having an energy-ray curable group in the compound (a2), for example, the compounds described in paragraph 0043 of "Japanese Patent Application Laid-Open No. 2013-194102" can be used. Although the above resins also belong to the resins constituting the thermosetting component described later, they are regarded as the compound (a2) in the present invention.

[0295] The weight average molecular weight of the compound (a2) is preferably 100 to 30,000, more preferably 300 to 10,000.

[0296] The compound (a2) contained in the composition (IV) and the energy-ray-curable resin film may be one kind or two or more kinds. When two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.

[0297] [Polymer (b) Not Having an Energy-Ray Curable Group]

[0298] When the composition (IV) and the energy-ray curable resin film contain the compound (a2) as the energy-ray curable component (a), it is preferred that they further contain a polymer (b) having no energy-ray curable group.

[0299] At least a part of the polymer (b) may be crosslinked by a crosslinking agent, or may not be crosslinked.

[0300] Examples of the polymer (b) having no energy ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, and acrylic urethane resins.

[0301] Among them, the polymer (b) is preferably an acrylic polymer (hereinafter, sometimes abbreviated as "acrylic polymer (b-1)").

[0302] The acrylic polymer (b-1) may be a known acrylic polymer, for example, a homopolymer of one acrylic monomer, a copolymer of two or more acrylic monomers, or a copolymer of one or more acrylic monomers and one or more monomers other than acrylic monomers (non-acrylic monomers).

[0303] Examples of the acrylic monomer constituting the acrylic polymer (b-1) include alkyl (meth)acrylates, (meth)acrylates having a cyclic skeleton, glycidyl group-containing (meth)acrylates, hydroxyl group-containing (meth)acrylates, and substituted amino group-containing (meth)acrylates, etc. The “substituted amino group” is as described above.

[0304] Examples of the (meth)acrylic acid alkyl ester include the same as the acrylic monomer having no functional group constituting the acrylic polymer (a11) described above (such as (meth)acrylic acid alkyl ester in which the alkyl group constituting the alkyl ester is a chain structure having 1 to 18 carbon atoms).

[0305] Examples of the (meth)acrylate having a cyclic skeleton include cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate;

[0306] Aralkyl (meth)acrylates such as benzyl (meth)acrylate;

[0307] Cycloalkenyl (meth)acrylates such as dicyclopentenyl (meth)acrylate;

[0308] Cycloalkenyloxyalkyl (meth)acrylates such as dicyclopentenyloxyethyl (meth)acrylate and the like.

[0309] Examples of the glycidyl group-containing (meth)acrylate include glycidyl (meth)acrylate and the like.

[0310] Examples of the hydroxyl group-containing (meth)acrylate include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0311] Examples of the substituted amino group-containing (meth)acrylate include N-methylaminoethyl (meth)acrylate and the like.

[0312] Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; and styrene.

[0313] Examples of the polymer (b) which is at least partially crosslinked by a crosslinking agent and does not have the energy ray-curable group include a polymer obtained by reaction of a reactive functional group in the polymer (b) with a crosslinking agent.

[0314] The reactive functional group can be appropriately selected according to the type of cross-linking agent, etc., and is not particularly limited. For example, when the cross-linking agent is a polyisocyanate compound, as the reactive functional group, hydroxyl, carboxyl, amino, etc. can be listed, among which hydroxyl with high reactivity with isocyanate group is preferred. In addition, when the cross-linking agent is an epoxy compound, as the reactive functional group, carboxyl, amino, amide, etc. can be listed, among which carboxyl with high reactivity with epoxy group is preferred. However, from the perspective of preventing corrosion of the circuit of the semiconductor wafer or semiconductor chip, the reactive functional group is preferably a group other than the carboxyl group.

[0315] As the polymer (b) having the reactive functional group and not having an energy-ray curable group, for example, a polymer obtained by polymerizing a monomer having at least the reactive functional group can be cited. In the case of an acrylic polymer (b-1), any one or both of the acrylic monomers and non-acrylic monomers listed as monomers constituting the polymer can be a polymer having the reactive functional group. As the polymer (b) having a hydroxyl group as a reactive functional group, for example, a polymer obtained by polymerizing a hydroxyl-containing (meth)acrylate can be cited. In addition, a polymer obtained by polymerizing a monomer in which one or more hydrogen atoms in the acrylic monomer or non-acrylic monomer listed above are replaced by the reactive functional group can be cited.

[0316] In the polymer (b) having a reactive functional group, the ratio (content) of the amount of the structural unit derived from the monomer having a reactive functional group to the total amount of the structural units constituting the polymer is preferably 1 to 20% by mass, more preferably 2 to 10% by mass. By making the ratio within the above range, in the polymer (b), the degree of crosslinking is more preferably within the range of.

[0317] The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000, from the viewpoint of better film-forming properties of the composition (IV).

[0318] The polymer (b) having no energy-ray-curable group contained in the composition (IV) and the energy-ray-curable resin film may be one type or two or more types. When there are two or more types, the combination and ratio thereof may be arbitrarily selected.

[0319] As the composition (IV), there can be mentioned a composition containing any one or both of the polymer (a1) and the compound (a2). In addition, when the composition (IV) contains the compound (a2), it is preferred to further contain a polymer (b) having no energy ray curable group, in which case it is preferred to further contain the (a1). In addition, the composition (IV) may not contain the compound (a2) but may contain the polymer (a1) and the polymer (b) having no energy ray curable group.

[0320] When the composition (IV) contains the polymer (a1), the compound (a2) and the polymer (b) not having an energy-ray-curable group, in the composition (IV), the content of the compound (a2) is preferably 10 to 400 parts by mass, and more preferably 30 to 350 parts by mass, relative to 100 parts by mass of the total content of the polymer (a1) and the polymer (b) not having an energy-ray-curable group.

[0321] In the composition (IV), the ratio of the total content of the energy-ray curable component (a) and the polymer (b) not having an energy-ray curable group to the total content of the components other than the solvent (i.e., the ratio of the total content of the energy-ray curable component (a) and the polymer (b) not having an energy-ray curable group in the energy-ray curable resin film to the total mass of the film) is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass. By making the ratio within the above range, the energy-ray curability of the energy-ray curable resin film becomes better.

[0322] [Filling material]

[0323] The X value can be more easily adjusted by adjusting the amount of filler in the composition (IV) and the energy-ray curable resin film. In addition, the thermal expansion coefficient of the cured product (e.g., protective film) of the energy-ray curable resin film can be more easily adjusted by adjusting the amount of filler in the composition (IV) and the energy-ray curable resin film. For example, by optimizing the thermal expansion coefficient of the protective film (e.g., the first protective film) relative to the object of formation of the protective film, the reliability of the package obtained using the energy-ray curable resin film is further improved. In addition, by using an energy-ray curable resin film containing a filler, the moisture absorption rate of the cured product (e.g., protective film) of the energy-ray curable resin film can be reduced and the heat release can be improved.

[0324] The filler contained in the composition (IV) and the energy-ray-curable resin film is the same as the filler (D) contained in the composition (III) and the thermosetting resin film described above.

[0325] The form in which the filler in the composition (IV) and the energy-ray curable resin film is contained may be the same as the form in which the filler (D) in the composition (III) and the thermosetting resin film is contained.

[0326] The filler contained in the composition (IV) and the energy-ray-curable resin film may be one kind or two or more kinds of fillers. When two or more kinds of fillers are used, the combination and ratio thereof may be arbitrarily selected.

[0327] In the composition (IV), the ratio of the content of the filler to the total content of all components except the solvent (i.e., the ratio of the content of the filler to the total mass of the energy-ray curable resin film in the energy-ray curable resin film) can be, for example, 5 to 45% by mass. By making the ratio within the above range, when the energy-ray curable resin film is attached to the concavo-convex surface, the effect of suppressing the residual energy-ray curable resin film on the upper part of the convex part of the concavo-convex surface, the effect of suppressing the overflow of the energy-ray curable resin film on the concavo-convex surface, and the effect of suppressing the shrinkage of the energy-ray curable resin film and its cured product on the concavo-convex surface become higher, and the above-mentioned thermal expansion coefficient can be further easily adjusted.

[0328] [additive]

[0329] The X value can be more easily adjusted by adjusting the type or amount of additives in the composition (IV) and the energy-ray-curable resin film.

[0330] The additives contained in the composition (IV) and the energy-ray-curable resin film are the same as the additives (I) contained in the composition (III) and the thermosetting resin film described above.

[0331] For example, from the viewpoint of being able to more easily adjust the X value, preferred additives include rheology control agents, surfactants, silicone oils, and the like.

[0332] The form in which the additives of the composition (IV) and the energy-ray curable resin film are contained may be the same as the form in which the additives (I) of the composition (III) and the thermosetting resin film are contained.

[0333] The additives contained in the composition (IV) and the energy-ray-curable resin film may be one kind or two or more kinds. When two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.

[0334] The content of the additives in the composition (IV) and the energy-ray-curable resin film is not particularly limited and can be appropriately adjusted depending on the type and purpose.

[0335] For example, when the purpose is to adjust the X value, in the composition (IV), the ratio of the content of the additive to the total content of all components except the solvent (that is, the ratio of the content of the additive in the energy-ray curable resin film to the total mass of the energy-ray curable resin film) can be, for example, 0.5 to 10% by mass.

[0336] [Other ingredients]

[0337] The composition (IV) and the energy-curable resin film may contain other components that are not any of the energy-curable component (a), the filler, the additive, and the polymer (b) that does not have an energy-curable group, within the range that does not impair the effects of the present invention.

[0338] As the other components, for example, thermosetting components, photopolymerization initiators, coupling agents, crosslinking agents, etc. For example, by using the composition (IV) containing the energy-ray curable component (a) and the thermosetting component, the adhesion of the energy-ray curable resin film to the adherend is improved, and the strength of the cured product of the energy-ray curable resin film (for example, a protective film) is also improved.

[0339] Examples of the thermosetting component, photopolymerization initiator, coupling agent and crosslinking agent in the composition (IV) include the same components as the thermosetting component (B), photopolymerization initiator, coupling agent (E) and crosslinking agent (F) in the composition (III).

[0340] The other components contained in the composition (IV) and the energy-ray-curable resin film may be one kind or two or more kinds. When there are two or more kinds, the combination and ratio thereof may be arbitrarily selected.

[0341] The content of the other components in the composition (IV) and the energy-ray-curable resin film is not particularly limited and may be appropriately selected depending on the intended purpose.

[0342] [Solvent]

[0343] It is preferred that the composition (IV) further contains a solvent. The composition (IV) containing a solvent has good handleability.

[0344] Examples of the solvent contained in the composition (IV) include the same solvents as those contained in the composition (III) described above.

[0345] The solvent contained in the composition (IV) may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio thereof may be arbitrarily selected.

[0346] The content of the solvent in the composition (IV) is not particularly limited and may be appropriately selected depending on the types of components other than the solvent, for example.

[0347] <Method for preparing energy-beam-curable resin film-forming composition>

[0348] The energy-ray-curable resin film-forming composition such as the composition (IV) can be obtained by blending the respective components constituting the composition.

[0349] The energy ray-curable resin film-forming composition can be prepared, for example, by the same method as the thermosetting resin film-forming composition described above, except that the types of the blended components are different.

[0350] As an example of a preferred resin film of the present embodiment, there can be mentioned a resin film in which:

[0351] A test piece of the resin film having a diameter of 25 mm and a thickness of 1 mm is strained under the conditions of a temperature of 90° C. and a frequency of 1 Hz, and the storage modulus of the test piece is measured. When the storage modulus of the test piece when the strain of the test piece is 1% is Gc1, and the storage modulus of the test piece when the strain of the test piece is 300% is Gc300, the value of X calculated by the following formula is 19 or more and less than 10000,

[0352] X=Gc1 / Gc300

[0353] The resin film is a thermosetting resin film containing a polymer component (A), an epoxy resin (B1), a thermosetting agent (B2), a filler (D) and an additive (I).

[0354] In the resin film, the content of the polymer component (A) is 5 to 25% by mass relative to the total mass of the resin film.

[0355] In the resin film, the content of the thermosetting agent (B2) is 0.1 to 500 parts by mass based on 100 parts by mass of the epoxy resin (B1).

[0356] In the resin film, the total content of the epoxy resin (B1) and the thermosetting agent (B2) is 600 to 1000 parts by mass relative to 100 parts by mass of the polymer component (A).

[0357] In the resin film, the content of the filler (D) is 5 to 45% by mass relative to the total mass of the resin film.

[0358] In the resin film, the content of the additive (I) is 0.5 to 10% by mass relative to the total mass of the resin film.

[0359] In the resin film, the total content of the polymer component (A), epoxy resin (B1), thermosetting agent (B2), filler (D) and additive (I) is not greater than 100% by mass relative to the total mass of the resin film.

[0360] As another example of a preferred resin film of the present embodiment, there can be cited a resin film, wherein a test piece of the resin film having a diameter of 25 mm and a thickness of 1 mm is strained under the conditions of a temperature of 90° C. and a frequency of 1 Hz and the storage modulus of the test piece is measured, and when the storage modulus of the test piece when the strain of the test piece is 1% is set to Gc1 and the storage modulus of the test piece when the strain of the test piece is 300% is set to Gc300, the value of X calculated by the following formula is 19 or more and less than 10000,

[0361] X=Gc1 / Gc300

[0362] The resin film is a thermosetting resin film containing a polymer component (A), an epoxy resin (B1), a thermosetting agent (B2), a filler (D) and an additive (I).

[0363] The polymer component (A) is polyvinyl acetal,

[0364] The additive (I) is one or more selected from the group consisting of a rheology control agent, a surfactant and silicone oil,

[0365] In the resin film, the content of the polymer component (A) is 5 to 25% by mass relative to the total mass of the resin film.

[0366] In the resin film, the content of the thermosetting agent (B2) is 0.1 to 500 parts by mass based on 100 parts by mass of the epoxy resin (B1).

[0367] In the resin film, the total content of the epoxy resin (B1) and the thermosetting agent (B2) is 600 to 1000 parts by mass relative to 100 parts by mass of the polymer component (A).

[0368] In the resin film, the content of the filler (D) is 5 to 45% by mass relative to the total mass of the resin film.

[0369] In the resin film, the content of the additive (I) is 0.5 to 10% by mass relative to the total mass of the resin film.

[0370] In the resin film, the total content of the polymer component (A), epoxy resin (B1), thermosetting agent (B2), filler (D) and additive (I) is not greater than 100% by mass relative to the total mass of the resin film.

[0371] ◇Composite film

[0372] A composite sheet according to one embodiment of the present invention includes a substrate, a buffer layer provided on the substrate, and a resin film provided on the buffer layer. The resin film is the resin film according to one embodiment of the present invention described above.

[0373] By using the composite sheet of this embodiment, as described above, the resin film can be well attached to the concave-convex surface of the object to which it is attached, and at this time, excellent effects such as suppressing the resin film from remaining on the upper part of the convex part of the concave-convex surface, suppressing the resin film from overflowing beyond the initial size, and suppressing the shrinkage of the resin film and its cured product on the concave-convex surface can be obtained.

[0374] In the present specification, when the resin film is used to form the first protective film, the composite sheet is referred to as a "first protective film forming sheet", and the substrate in the first protective film forming sheet is referred to as a "first substrate".

[0375] On the other hand, in order to provide a second protective film on the surface (back side) opposite to the bump forming surface of the semiconductor wafer or semiconductor chip, a second protective film forming sheet having a second protective film forming film for forming the second protective film is used. As the second protective film forming sheet, for example, a second protective film forming sheet having a cutting sheet and a second protective film forming film provided on the cutting sheet can be cited. When the cutting sheet has a substrate that is the same as the substrate, the substrate is referred to as a "second substrate".

[0376] Figure 3 This is a cross-sectional view schematically showing an example of the composite sheet according to the present embodiment.

[0377] The composite sheet 1 shown therein includes a substrate 11 , a buffer layer 13 provided on the substrate 11 , and a resin film 12 provided on the buffer layer 13 (on the upper portion of the buffer layer 13 on the side opposite to the substrate 11 ).

[0378] That is, the composite sheet 1 is formed by laminating the base material 11 , the buffer layer 13 , and the resin film 12 in this order in the thickness direction thereof.

[0379] Reference numeral 13 a denotes a surface of the buffer layer 13 on which the resin film 12 is provided (hereinafter, sometimes referred to as a “first surface”).

[0380] Figure 4This is a cross-sectional view schematically showing another example of the composite sheet according to the present embodiment.

[0381] The composite sheet 2 shown in the figure has a bonding layer 14 between the substrate 11 and the buffer layer 13 (in other words, has a bonding layer 14 provided on the substrate 11 and a buffer layer 13 provided on the bonding layer 14). Figure 3 The same as the composite sheet 1 shown in FIG.

[0382] That is, the composite sheet 2 is formed by laminating the base material 11 , the adhesion layer 14 , the buffer layer 13 , and the resin film 12 in this order in the thickness direction thereof.

[0383] The composite sheet of this embodiment is not limited to Figure 3 and Figure 4 The composite sheet shown in the above can be used without damaging the effect of the present invention. Figure 3 and Figure 4 Part of the configuration of the composite sheet shown in the figure may be changed, deleted, or added.

[0384] For example, the composite sheet of this embodiment may have an outermost layer (on the side opposite to the substrate) Figure 3 and Figure 4 In the composite sheet shown, a release film is provided on the resin film 12).

[0385] Next, each layer constituting the composite sheet of the present embodiment will be described.

[0386] ◎Base material

[0387] The substrate is in a sheet or film shape, and examples of its constituent material include various resins.

[0388] Examples of the resin include polyethylenes such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resins; ethylene-vinyl acetate copolymers, ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylate copolymers, and ethylene-norbornene copolymers (copolymers obtained using ethylene as a monomer); and vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers. (resin obtained using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene 2,6-naphthalate, and wholly aromatic polyesters in which all structural units have aromatic cyclic groups; copolymers of two or more of the above polyesters; poly(meth)acrylate; polyurethane; polyurethane acrylate; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; polysulfone; polyether ketone, etc.

[0389] In addition, the resin may include, for example, a polymer alloy such as a mixture of the polyester and other resins. In the polymer alloy of the polyester and other resins, the amount of the resin other than the polyester is preferably small.

[0390] In addition, examples of the resin include crosslinked resins obtained by crosslinking one or more of the resins listed above; and modified resins such as ionomers using one or more of the resins listed above.

[0391] The resin constituting the substrate may be one type or two or more types. When there are two or more types, the combination and ratio thereof may be arbitrarily selected.

[0392] The substrate may be a single layer (single layer) or may be a plurality of layers of two or more. When the substrate is a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited.

[0393] The thickness of the substrate is preferably 5 to 1000 μm, more preferably 10 to 500 μm, further preferably 15 to 300 μm, and particularly preferably 20 to 150 μm.

[0394] Here, the “thickness of the substrate” refers to the thickness of the entire substrate. For example, the thickness of a substrate composed of a plurality of layers refers to the total thickness of all layers constituting the substrate.

[0395] The substrate is preferably a substrate with high thickness precision, that is, a substrate that can suppress the deviation of the thickness at any position. Among the above-mentioned constituent materials, as materials that can be used to constitute the substrate with high thickness precision, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, etc. can be listed.

[0396] In addition to the above-mentioned main constituent materials such as the resin, the base material may contain various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer).

[0397] The substrate may be transparent or opaque, may be colored according to the purpose, and may have other layers deposited thereon.

[0398] When the resin film is energy ray-curable, the substrate is preferably energy ray-transmissive.

[0399] The substrate can be produced using a known method. For example, a substrate containing a resin can be produced by molding a resin composition containing the resin.

[0400] ◎Buffer layer

[0401] The buffer layer has a buffering effect on the force applied to the buffer layer and the layer adjacent to the buffer layer. The "layer adjacent to the buffer layer" mainly refers to the resin film and a layer equivalent to a cured product of the resin film (for example, a protective film such as the first protective film).

[0402] The constituent material of the buffer layer is not particularly limited.

[0403] As a preferable buffer layer, the buffer layer containing urethane (meth)acrylate etc. is mentioned, for example.

[0404] Similar to the case of the resin film described above, a test piece of a buffer layer having a diameter of 25 mm and a thickness of 1 mm is strained at a temperature of 90°C and a frequency of 1 Hz and the storage modulus of the test piece is measured. When the storage modulus of the test piece when the strain of the test piece is 300% is set to Gb300, Gb300 is preferably greater than Gc300 (Gb300 ≥ Gc300). By using the composite sheet that meets this condition and attaching the resin film to the concave-convex surface, the upper part of the convex part of the concave-convex surface (for example, the bump of a semiconductor wafer) can more easily penetrate the resin film.

[0405] As described above, the test piece of the buffer layer is strained in the range of 0.01% to 1000% and the storage modulus Gb of the test piece is measured, and the test piece of the resin film is strained in the range of 0.01% to 1000% and the storage modulus Gc of the test piece is measured. When Gb and Gc are compared when the strains are the same, it is more preferred that Gb is greater than Gc (Gb≥Gc) in the entire range of 0.01% to 1000% strain, and it is further preferred that Gb is greater than Gc in the entire range of 10% to 1000% strain. By using the composite sheet that meets the above conditions and attaching the resin film to the concave-convex surface, the upper part of the convex part of the concave-convex surface (for example, the bump of a semiconductor wafer) can more easily penetrate the resin film.

[0406] The buffer layer may be a single layer (single layer) or a plurality of layers of two or more. When the buffer layer is a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited.

[0407] The thickness of the buffer layer is preferably 150 to 1000 μm, more preferably 150 to 800 μm, further preferably 200 to 600 μm, and particularly preferably 250 to 500 μm.

[0408] Here, “the thickness of the buffer layer” refers to the thickness of the entire buffer layer. For example, the thickness of a buffer layer composed of a plurality of layers refers to the total thickness of all the layers constituting the buffer layer.

[0409] <<Composition for forming buffer layer>>

[0410] The buffer layer can be formed by using a buffer layer forming composition containing the constituent material of the buffer layer such as the resin. For example, by extruding the buffer layer forming composition against the formation target surface of the buffer layer, the buffer layer can be formed at the target position. A more specific formation method of the buffer layer will be described in detail later together with the formation method of other layers. The content ratio between the components that do not vaporize at room temperature in the buffer layer forming composition is usually the same as the content ratio between the components in the buffer layer.

[0411] <Buffer layer forming composition (V)>

[0412] As a buffer layer forming composition, the buffer layer forming composition (V) containing urethane (meth)acrylate etc. are mentioned, for example.

[0413] The content of the urethane (meth)acrylate in the buffer layer-forming composition (V) and the buffer layer is preferably 80 to 100% by mass.

[0414] [Other ingredients]

[0415] The buffer layer-forming composition (V) and the buffer layer may contain other components besides the urethane (meth)acrylate within a range not impairing the effects of the present invention.

[0416] The other components are not particularly limited and can be appropriately selected depending on the purpose.

[0417] The composition (V) for forming a buffer layer and the other components contained in the buffer layer may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio thereof may be arbitrarily selected.

[0418] The content of the buffer layer-forming composition (V) and the other components of the buffer layer is not particularly limited and may be appropriately selected depending on the intended purpose.

[0419] ◎Resin film

[0420] The resin film in the composite sheet of the present embodiment is the same as the resin film described above, and therefore a detailed description thereof is omitted here.

[0421] ◎Sealing layer

[0422] The adhesion layer can improve the adhesion between the substrate and the buffer layer, and highly suppress the peeling of the substrate and the buffer layer in the composite sheet. Therefore, when using a composite sheet equipped with an adhesion layer, the laminated structure of the substrate, the adhesion layer and the buffer layer can be more stably maintained.

[0423] The sealing layer is in sheet or film form.

[0424] As a preferable adhesion layer, the adhesion layer containing ethylene-vinyl acetate copolymer resin (EVA) etc. is mentioned, for example.

[0425] The adhesion layer may be only one layer (single layer) or may be two or more layers. When it is a plurality of layers, these multiple layers may be the same as or different from each other, and the combination of these multiple layers is not particularly limited.

[0426] The thickness of the adhesion layer is preferably 10 to 100 μm, more preferably 25 to 85 μm, and particularly preferably 40 to 70 μm.

[0427] Here, “the thickness of the adhesion layer” refers to the thickness of the entire adhesion layer. For example, the thickness of an adhesion layer composed of a plurality of layers refers to the total thickness of all the layers constituting the adhesion layer.

[0428] <<Adhesion layer forming composition>>

[0429] The adhesion layer can be formed by using an adhesion layer forming composition containing the constituent materials of the adhesion layer. For example, by extruding the adhesion layer forming composition against the object surface of the adhesion layer, the adhesion layer can be formed on the target part. A more specific formation method of the adhesion layer will be described in detail later together with the formation method of other layers. The content ratio between the components that do not vaporize at room temperature in the adhesion layer forming composition is usually the same as the content ratio between the components of the adhesion layer.

[0430] <Adhesion layer forming composition (VI)>

[0431] Examples of the adhesion layer forming composition include an adhesion layer forming composition (VI) containing an ethylene-vinyl acetate copolymer resin (EVA).

[0432] The density of ethylene-vinyl acetate copolymer resin is preferably 1100 kg / m 3 Below, more preferably 850 to 1100 kg / m 3 , particularly preferably 900 to 1000 kg / m 3 .

[0433] In this specification, unless otherwise specified, the "density of ethylene-vinyl acetate copolymer resin" means a value measured in accordance with JIS K7112:1999.

[0434] The melting point of the ethylene-vinyl acetate copolymer resin is preferably 50 to 95°C, more preferably 65 to 85°C.

[0435] The melt flow rate (MFR) of the ethylene-vinyl acetate copolymer resin at 190° C. is preferably 1 to 10 g / 10 min, more preferably 3 to 8 g / 10 min.

[0436] In this specification, unless otherwise specified, the "melt flow rate of ethylene-vinyl acetate copolymer resin" means a value measured in accordance with JIS K7210:1999.

[0437] The content of the ethylene-vinyl acetate copolymer resin in the adhesion layer-forming composition (VI) and the adhesion layer is preferably 80 to 100% by mass.

[0438] [Other ingredients]

[0439] The adhesion layer-forming composition (VI) and the adhesion layer may contain other components in addition to the ethylene-vinyl acetate copolymer resin within a range not impairing the effects of the present invention.

[0440] The other components are not particularly limited and can be appropriately selected depending on the purpose.

[0441] The other components contained in the adhesion layer-forming composition (VI) and the adhesion layer may be one kind or two or more kinds. When two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.

[0442] The content of the adhesion layer-forming composition (VI) and the other components of the adhesion layer is not particularly limited and may be appropriately selected depending on the intended purpose.

[0443] As an example of a preferred composite sheet of the present embodiment, there can be cited a composite sheet including a substrate, a buffer layer provided on the substrate, and a resin film provided on the buffer layer.

[0444] A test piece of the resin film having a diameter of 25 mm and a thickness of 1 mm is strained under the conditions of a temperature of 90° C. and a frequency of 1 Hz, and the storage modulus of the test piece is measured. When the storage modulus of the test piece when the strain of the test piece is 1% is Gc1, and the storage modulus of the test piece when the strain of the test piece is 300% is Gc300, the value of X calculated by the following formula is 19 or more and less than 10000,

[0445] X=Gc1 / Gc300

[0446] The resin film is a thermosetting resin film containing a polymer component (A), an epoxy resin (B1), a thermosetting agent (B2), a filler (D) and an additive (I).

[0447] In the resin film, the content of the polymer component (A) is 5 to 25% by mass relative to the total mass of the resin film.

[0448] In the resin film, the content of the thermosetting agent (B2) is 0.1 to 500 parts by mass based on 100 parts by mass of the epoxy resin (B1).

[0449] In the resin film, the total content of the epoxy resin (B1) and the thermosetting agent (B2) is 600 to 1000 parts by mass relative to 100 parts by mass of the polymer component (A).

[0450] In the resin film, the content of the filler (D) is 5 to 45% by mass relative to the total mass of the resin film.

[0451] In the resin film, the content of the additive (I) is 0.5 to 10% by mass relative to the total mass of the resin film.

[0452] In the resin film, the total content of the polymer component (A), epoxy resin (B1), thermosetting agent (B2), filler (D) and additive (I) is not greater than 100% by mass relative to the total mass of the resin film.

[0453] As another example of a preferred composite sheet of the present embodiment, there can be cited a composite sheet comprising a substrate, a buffer layer provided on the substrate, and a resin film provided on the buffer layer.

[0454] A test piece of the resin film having a diameter of 25 mm and a thickness of 1 mm is strained under the conditions of a temperature of 90° C. and a frequency of 1 Hz, and the storage modulus of the test piece of the resin film is measured. When the storage modulus of the test piece of the resin film when the strain of the test piece of the resin film is 1% is set to Gc1, and the storage modulus of the test piece of the resin film when the strain of the test piece of the resin film is 300% is set to Gc300, the value of X calculated by the following formula is greater than 19 and less than 10000,

[0455] X=Gc1 / Gc300

[0456] Under the conditions of temperature of 90°C and frequency of 1 Hz, a test piece of the buffer layer with a diameter of 25 mm and a thickness of 1 mm is strained and the storage modulus of the test piece of the buffer layer is measured. When the storage modulus of the test piece of the buffer layer when the strain of the test piece of the buffer layer is 300% is set to Gb300, the Gb300 is greater than the Gc300.

[0457] As another example of a preferred composite sheet of the present embodiment, there can be cited a composite sheet comprising a substrate, a buffer layer provided on the substrate, and a resin film provided on the buffer layer.

[0458] A test piece of the resin film having a diameter of 25 mm and a thickness of 1 mm is strained under the conditions of a temperature of 90° C. and a frequency of 1 Hz, and the storage modulus of the test piece of the resin film is measured. When the storage modulus of the test piece of the resin film when the strain of the test piece of the resin film is 1% is set to Gc1, and the storage modulus of the test piece of the resin film when the strain of the test piece of the resin film is 300% is set to Gc300, the value of X calculated by the following formula is greater than 19 and less than 10000,

[0459] X=Gc1 / Gc300

[0460] Under the conditions of temperature of 90°C and frequency of 1 Hz, a test piece of the buffer layer with a diameter of 25 mm and a thickness of 1 mm is strained within the range of 0.01% to 1000% and the storage modulus Gb of the buffer layer test piece is measured. A test piece of the resin film is strained within the range of 0.01% to 1000% and the storage modulus Gc of the resin film test piece is measured. When comparing the Gb and Gc when the strains are the same, the Gb is greater than the Gc in the entire range of the strain of 0.01% to 1000%.

[0461] As another example of a preferred composite sheet of the present embodiment, there can be cited a composite sheet comprising a substrate, a buffer layer provided on the substrate, and a resin film provided on the buffer layer.

[0462] A test piece of the resin film having a diameter of 25 mm and a thickness of 1 mm is strained under the conditions of a temperature of 90° C. and a frequency of 1 Hz, and the storage modulus of the test piece of the resin film is measured. When the storage modulus of the test piece of the resin film when the strain of the test piece of the resin film is 1% is set to Gc1, and the storage modulus of the test piece of the resin film when the strain of the test piece of the resin film is 300% is set to Gc300, the value of X calculated by the following formula is greater than 19 and less than 10000,

[0463] X=Gc1 / Gc300

[0464] A test piece of the buffer layer having a diameter of 25 mm and a thickness of 1 mm is strained under the conditions of a temperature of 90° C. and a frequency of 1 Hz, and the storage modulus of the test piece of the buffer layer is measured. When the storage modulus of the test piece of the buffer layer when the strain of the test piece of the buffer layer is 300% is set to Gb300, Gb300 is greater than Gc300,

[0465] The resin film is a thermosetting resin film containing a polymer component (A), an epoxy resin (B1), a thermosetting agent (B2), a filler (D) and an additive (I).

[0466] In the resin film, the content of the polymer component (A) is 5 to 25% by mass relative to the total mass of the resin film.

[0467] In the resin film, the content of the thermosetting agent (B2) is 0.1 to 500 parts by mass based on 100 parts by mass of the epoxy resin (B1).

[0468] In the resin film, the total content of the epoxy resin (B1) and the thermosetting agent (B2) is 600 to 1000 parts by mass relative to 100 parts by mass of the polymer component (A).

[0469] In the resin film, the content of the filler (D) is 5 to 45% by mass relative to the total mass of the resin film.

[0470] In the resin film, the content of the additive (I) is 0.5 to 10% by mass based on the total mass of the resin film.

[0471] In the resin film, the total content of the polymer component (A), epoxy resin (B1), thermosetting agent (B2), filler (D) and additive (I) is not greater than 100% by mass relative to the total mass of the resin film.

[0472] As another example of a preferred composite sheet of the present embodiment, there can be cited a composite sheet comprising a substrate, a buffer layer provided on the substrate, and a resin film provided on the buffer layer.

[0473] A test piece of the resin film having a diameter of 25 mm and a thickness of 1 mm is strained under the conditions of a temperature of 90° C. and a frequency of 1 Hz, and the storage modulus of the test piece of the resin film is measured. When the storage modulus of the test piece of the resin film when the strain of the test piece of the resin film is 1% is set to Gc1, and the storage modulus of the test piece of the resin film when the strain of the test piece of the resin film is 300% is set to Gc300, the value of X calculated by the following formula is greater than 19 and less than 10000,

[0474] X=Gc1 / Gc300

[0475] Under the conditions of a temperature of 90° C. and a frequency of 1 Hz, a test piece of the buffer layer having a diameter of 25 mm and a thickness of 1 mm is strained within a range of 0.01% to 1000% and the storage modulus Gb of the test piece of the buffer layer is measured, and a test piece of the resin film is strained within a range of 0.01% to 1000% and the storage modulus Gc of the test piece of the resin film is measured. When the Gb and the Gc are compared when the strains are the same, the Gb is greater than the Gc in the entire range of the strain of 0.01% to 1000%.

[0476] The resin film is a thermosetting resin film containing a polymer component (A), an epoxy resin (B1), a thermosetting agent (B2), a filler (D) and an additive (I).

[0477] In the resin film, the content of the polymer component (A) is 5 to 25% by mass relative to the total mass of the resin film.

[0478] In the resin film, the content of the thermosetting agent (B2) is 0.1 to 500 parts by mass based on 100 parts by mass of the epoxy resin (B1).

[0479] In the resin film, the total content of the epoxy resin (B1) and the thermosetting agent (B2) is 600 to 1000 parts by mass relative to 100 parts by mass of the polymer component (A).

[0480] In the resin film, the content of the filler (D) is 5 to 45% by mass relative to the total mass of the resin film.

[0481] In the resin film, the content of the additive (I) is 0.5 to 10% by mass relative to the total mass of the resin film.

[0482] In the resin film, the total content of the polymer component (A), epoxy resin (B1), thermosetting agent (B2), filler (D) and additive (I) is not greater than 100% by mass relative to the total mass of the resin film.

[0483] ◇Manufacturing method of composite sheet

[0484] The composite sheet can be manufactured by stacking the above-mentioned layers in a corresponding positional relationship. The formation method of each layer is as described above.

[0485] For example, a composite sheet formed by laminating a substrate, a buffer layer, and a resin film in this order in their thickness directions can be produced by the method described below.

[0486] That is, the buffer layer is laminated on the substrate by extruding the buffer layer forming composition against the substrate. In addition, the resin film is laminated by applying the above-mentioned resin film forming composition on the release treatment surface of the release film and drying it as needed. And, by laminating the resin film on the release film with the buffer layer on the substrate, a composite sheet consisting of a substrate, a buffer layer, a resin film and a release film is obtained. The release film on the resin film only needs to be removed when the composite sheet is used.

[0487] A composite sheet including other layers in addition to the above-mentioned layers can be produced by adding one or both of the step of forming the other layers and the step of laminating the other layers so that the lamination positions of the other layers are at appropriate positions to the above-mentioned production method.

[0488] For example, a composite sheet in which a substrate, an adhesion layer, a buffer layer, and a resin film are laminated in this order in their thickness directions can be produced by the method described below.

[0489] That is, by coextruding the adhesive layer forming composition and the buffer layer forming composition against the substrate, the adhesive layer and the buffer layer are sequentially stacked on the substrate. In addition, a resin film is stacked on the release film in the same manner as described above. Next, the resin film on the release film is laminated to the substrate and the buffer layer on the adhesive layer to obtain a composite sheet consisting of a substrate, an adhesive layer, a buffer layer, a resin film and a release film stacked in sequence. The release film on the resin film only needs to be removed when the composite sheet is used.

[0490] ◇Method for manufacturing semiconductor device (method for using resin film and composite sheet)

[0491] As described above, the resin film of this embodiment has extremely excellent properties in that the convex portion penetrates through the convex portion to expose the upper portion thereof and can cover the entire convex surface when attached to the convex surface of the attached object. That is, the resin film of this embodiment is suitable for being attached to the convex surface of the attached object having a convex surface.

[0492] The resin film of this embodiment is particularly suitable for use in, for example, manufacturing a semiconductor chip with a first protective film, which includes a semiconductor chip and a first protective film provided on a surface (bump forming surface) of the semiconductor chip having bumps. In this case, the concavo-convex surface is the bump forming surface of the semiconductor chip, and the convex portion is the bump. Furthermore, the semiconductor chip with the first protective film is flip-chip bonded to a substrate at the bumps, thereby being suitable for use in manufacturing semiconductor devices.

[0493] The resin film of the present embodiment is suitably used in the form of the above-mentioned composite sheet.

[0494] Next, a method for manufacturing a semiconductor device using the composite sheet will be described.

[0495] A method for manufacturing a semiconductor device according to one embodiment of the present invention includes:

[0496] The curable resin film in the composite sheet of one embodiment of the present invention is attached to the surface with bumps (bump forming surface) of the semiconductor wafer so that the top of the bump protrudes from the resin film, thereby providing the composite sheet on the semiconductor wafer. After the attaching process, a removal process is performed to remove the layers in the composite sheet other than the resin film from the resin film. After the removal process, a curing process is performed to cure the resin film to form a first protective film. After the curing process, the semiconductor wafer is divided to produce a semiconductor chip. After the curing process, the first protective film is cut off after the curing process. And a mounting process is performed by flip-chip bonding the semiconductor chip with the first protective film provided on the surface with bumps (bump forming surface) of the semiconductor chip obtained after the division process and the cutting process, and the top of the bump protrudes from the first protective film, to the substrate at the top of the bump.

[0497] Figure 5A to Figure 5D For schematic illustration, use Figure 3 1 is a cross-sectional view of an example of a method for manufacturing a semiconductor device using the composite sheet 1 shown in FIG.

[0498] Since the curable resin film is used to form the first protective film, the “composite sheet 1 ” is referred to as a “first protective film forming sheet 1 ” and the “substrate 11 ” is referred to as a “first substrate 11 ”.

[0499] <Attachment process>

[0500] In the attachment process, Figure 5A to Figure 5B As shown, the curable resin film 12 in the first protective film forming sheet 1 is attached to the bump forming surface 9a of the semiconductor wafer 9, and the top end 9101 of the bump 91 is made to protrude from the curable resin film 12, thereby setting the first protective film forming sheet 1 on the semiconductor wafer 9.

[0501] In the attaching process, for example, first Figure 5A As shown, the first protective film forming sheet 1 is arranged so that the curable resin film 12 of the first protective film forming sheet 1 faces the bump formation surface 9 a of the semiconductor wafer 9 .

[0502] The height of the bump 91 is not particularly limited, but is preferably 120 to 300 μm, more preferably 150 to 270 μm, and particularly preferably 180 to 240 μm. By making the height of the bump 91 greater than or equal to the lower limit, the function of the bump 91 can be further improved. By making the height of the bump 91 less than or equal to the upper limit, the effect of suppressing the curable resin film 12 from remaining on the bump 91 is further enhanced.

[0503] In this specification, the "height of a bump" refers to the height of a portion of the bump that is located at the highest position from the bump formation surface.

[0504] The width of the bump 91 is not particularly limited, but is preferably 170 to 350 μm, more preferably 200 to 320 μm, and particularly preferably 230 to 290 μm. By making the width of the bump 91 equal to or greater than the lower limit, the function of the bump 91 can be further improved. By making the width of the bump 91 equal to or less than the upper limit, the effect of suppressing the curable resin film 12 from remaining on the bump 91 is further enhanced.

[0505] In this specification, the "bump width" refers to the maximum value of the length of a line segment connecting two different points on the bump surface with a straight line when the bump is viewed downward from a direction perpendicular to the bump formation surface.

[0506] The distance between adjacent bumps 91 is not particularly limited, but is preferably 250 to 800 μm, more preferably 300 to 600 μm, and particularly preferably 350 to 500 μm. By making the distance equal to or greater than the lower limit, the function of the bump 91 can be further improved. By making the distance equal to or less than the upper limit, the effect of suppressing the curable resin film 12 from remaining on the bump 91 is further enhanced.

[0507] In this specification, "the distance between adjacent bumps" refers to the minimum value of the distance between the surfaces of adjacent bumps.

[0508] Next, in the attaching step, the curable resin film 12 is brought into contact with the bumps 91 on the semiconductor wafer 9, and the first protective film forming sheet 1 is pressed onto the semiconductor wafer 9. Thus, the first surface 12a of the curable resin film 12 is pressed and bonded to the surface 91a of the bump 91 and the bump forming surface 9a of the semiconductor wafer 9 in sequence. At this time, by heating the curable resin film 12, the curable resin film 12 softens and covers the bumps 91 and spreads between the bumps 91, thereby adhering to the bump forming surface 9a and covering the surface 91a of the bump 91, especially the surface 91a of the portion near the bump forming surface 9a, thereby filling the bottom of the bump 91.

[0509] Above, such as Figure 5B As shown, the curable resin film 12 in the first protective film forming sheet 1 is attached to the bump formation surface 9 a of the semiconductor wafer 9 .

[0510] As described above, as a method of pressing the first protective film forming sheet 1 onto the semiconductor wafer 9 , a known method of pressing various sheets onto an object for attachment can be applied, for example, a method using a laminating roll.

[0511] The heating temperature of the first protective film forming sheet 1 (curable resin film 12 ) when being pressure-bonded to the semiconductor wafer 9 may be a temperature at which the curable resin film 12 is incompletely or excessively cured, and may be, for example, 80 to 100° C.

[0512] Among them, the heating temperature is more preferably 85 to 95°C, considering that the effect of suppressing the residual curable resin film 12 on the upper part of the bump 91, the effect of suppressing the overflow of the curable resin film 12 on the bump forming surface 9a, and the effect of suppressing the shrinkage of the curable resin film 12 on the bump forming surface 9a are further increased.

[0513] The pressure at which the first protective film-forming sheet 1 (curable resin film 12 ) is pressed onto the semiconductor wafer 9 is not particularly limited, and may be, for example, 0.1 to 1.5 MPa.

[0514] Among them, the pressure is more preferably 0.3 to 1 MPa, considering that the effect of suppressing the residual curable resin film 12 on the upper part of the bump 91, the effect of suppressing the overflow of the curable resin film 12 on the bump forming surface 9a, and the effect of suppressing the shrinkage of the curable resin film 12 on the bump forming surface 9a are further increased.

[0515] As described above, when the first protective film forming sheet 1 is pressed onto the semiconductor wafer 9, the curable resin film 12 and the buffer layer 13 in the first protective film forming sheet 1 are subjected to pressure from the bumps 91, and initially, the first surface 12a of the curable resin film 12 and the first surface 13a of the buffer layer 13 are deformed into a concave shape. In addition, cracks are generated in the curable resin film 12 subjected to pressure from the bumps 91 in this state. Finally, at the stage of pressing the first surface 12a of the curable resin film 12 onto the bump forming surface 9a of the semiconductor wafer 9, the upper portion 910 of the bump 91 including the top portion 9101 is formed to protrude through the curable resin film 12. In addition, at this final stage, the upper portion 910 of the bump 91 does not usually penetrate the buffer layer 13. This is because the buffer layer 13 has a buffering effect on the pressure applied from the bump 91.

[0516] like Figure 5B As shown, at the stage where the attachment process is finished, no or almost no curable resin film 12 remains on the upper portion 910 including the top portion 9101 of the bump 91, and the curable resin film 12 is suppressed from remaining on the upper portion 910 of the bump 91. In addition, in this specification, unless otherwise specified, "almost no curable resin film remains on the upper portion of the bump" means that although a small amount of curable resin film remains on the upper portion of the bump, the remaining amount is an amount that does not hinder the electrical connection between the semiconductor chip and the substrate when the semiconductor chip having the bump is flip-chip bonded to the substrate.

[0517] Furthermore, at the stage where the attaching step is completed, the curable resin film 12 is suppressed from overflowing beyond the initial size, and thus the curable resin film 12 is suppressed from overflowing from the bump formation surface 9 a of the semiconductor wafer 9 .

[0518] Furthermore, at the stage where the attaching process is finished, the curable resin film 12 is suppressed from shrinking on the bump forming surface 9a. More specifically, in a state where the curable resin film 12 is provided on the bump forming surface 9a, the phenomenon that the area other than the upper part 910 of the bump 91 (for example, the bottom near the bump forming surface 9a) or the area near the bump 91 of the bump forming surface 9a is accidentally not covered by the curable resin film 12 and exposed is suppressed.

[0519] Therefore, as described above, the reason why the curable resin film 12 is prevented from remaining on the upper part 910 of the bump 91, the overflow of the curable resin film 12 on the bump forming surface 9a, and the shrinkage of the curable resin film 12 on the bump forming surface 9a are suppressed is that the curable resin film 12 satisfies the X value condition (19≤X value<10000).

[0520] After the above-mentioned attaching step, the surface (back surface) 9b of the semiconductor wafer 9 opposite to the bump formation surface 9a is further polished as necessary, and then a second protective film forming sheet (not shown) is attached to the back surface 9b.

[0521] <Removal process>

[0522] After the attaching process, in the removing process, if Figure 5C As shown, the layers other than the curable resin film 12 in the first protective film-forming sheet 1 are removed from the curable resin film 12. The removed layers are more specifically the first base material 11 and the buffer layer 13.

[0523] By performing the removal step, a semiconductor wafer with a resin film including the semiconductor wafer 9 and the curable resin film 12 provided on the bump formation surface 9 a of the semiconductor wafer 9 is obtained.

[0524] <Curing process>

[0525] After the removal step, the curable resin film 12 is cured in the curing step, thereby forming a first protective film.

[0526] In the curing step, when the curable resin film 12 is thermosetting, the curable resin film 12 is cured by heating, and when the curable resin film 12 is energy ray curable, the curable resin film 12 is cured by irradiating energy rays. The heating conditions and energy ray irradiation conditions at this time are as described above.

[0527] <Splitting process, cutting process>

[0528] After the curing step, in the dividing step, the semiconductor wafer 9 is divided to produce semiconductor chips 9 ′, and in the cutting step, the first protective film is cut.

[0529] The dividing step and the cutting step can be performed by a known method.

[0530] The order of performing the splitting step and the cutting step is not particularly limited, but it is preferred that the splitting step and the cutting step are performed simultaneously, or in the order of the splitting step and the cutting step. When the splitting step and the cutting step are performed sequentially, for example, the splitting step can be performed by known dicing, and then the cutting step can be performed immediately and continuously.

[0531] In the cutting step, the first protective film is cut along the pre-divided position or the divided position of the semiconductor wafer 9 (in other words, the outer periphery of the semiconductor chip 9 ′).

[0532] By performing the curing process, the dividing process and the cutting process, Figure 5D As shown, a semiconductor chip 9120' with a first protective film is obtained, which includes a semiconductor chip 9' and a cut first protective film (sometimes simply referred to as "first protective film" in this specification) 120' provided on the bump formation surface 9a' of the semiconductor chip 9'.

[0533] In the semiconductor chip 9120' with the first protective film, the top portion 9101 of the bump 91 protrudes from the first protective film 120', and the first protective film is completely or almost not attached to the upper portion 910 of the bump 91 including the top portion 9101, thereby suppressing the attachment of the first protective film to the upper portion 910 of the bump 91.

[0534] Furthermore, in the semiconductor chip 9120' with the first protective film, the overflow of the first protective film 120' on the bump formation surface 9a' of the semiconductor chip 9' is suppressed.

[0535] Furthermore, the shrinkage of the first protective film 120' on the bump forming surface 9a' of the semiconductor chip 9' is suppressed. More specifically, in a state where the first protective film 120' is provided on the bump forming surface 9a', the phenomenon that the area other than the upper portion 910 of the bump 91 (for example, the bottom near the bump forming surface 9a') or the area near the bump 91 of the bump forming surface 9a' is accidentally not covered by the first protective film 120' and exposed is suppressed.

[0536] <Installation process>

[0537] After the dividing and cutting steps, in the mounting step, the semiconductor chip 9120' with the first protective film is flip-chip bonded to the substrate (not shown) at the top end 9101 of the bump 91. At this time, the semiconductor chip 9120' with the first protective film is bonded to the circuit formation surface of the substrate.

[0538] Since the adhesion of the first protective film to the upper portion 910 of the bump 91 in the semiconductor chip 9120' with the first protective film is suppressed, the electrical connection between the semiconductor chip 9' and the substrate is high in this process.

[0539] When the second protective film forming sheet is used, the semiconductor chip 9120' with the first protective film is pulled away from a dicing sheet (not shown) in the second protective film forming sheet and picked up before flip chip bonding.

[0540] The semiconductor chip 9120 ′ with the first protective film can be picked up by a known method.

[0541] When the second protective film forming sheet is used, the cut second protective film (not shown) is provided on the back surface 9 b of the semiconductor chip 9 ′ in the semiconductor chip 9120 ′ with the first protective film.

[0542] When the second protective film forming film in the second protective film forming sheet is curable, the second protective film is formed by curing the second protective film forming film at an appropriate timing according to its type. Furthermore, the second protective film is cut at an appropriate timing according to its type.

[0543] The second protective film-forming film can be cured by the same method as when curing the curable resin film 12 , and may be cured simultaneously with the curable resin film 12 , or may be cured separately from the curable resin film 12 .

[0544] The second protective film can be cut by the same method as when the first protective film is cut.

[0545] The order of performing the splitting step and cutting the second protective film is not particularly limited, but it is preferred that the splitting step and cutting the second protective film are performed simultaneously, or the second protective film is cut after the splitting step. When the splitting step and cutting the second protective film are performed sequentially, for example, the splitting step can be performed by known dicing, and then the second protective film can be cut immediately and continuously.

[0546] The second protective film is cut along the pre-divided position or the divided position of the semiconductor wafer 9 (in other words, the outer periphery of the semiconductor chip 9 ′).

[0547] Then, a semiconductor package is produced by a known method using the circuit board on which the semiconductor chip 9 ′ is mounted, and a target semiconductor device (not shown) can be manufactured by using the semiconductor package.

[0548] Among them, the use of Figure 3 The composite sheet (first protective film forming sheet) 1 shown in FIG. Figure 4 When a composite sheet of another embodiment such as the composite sheet 2 shown in FIG. 1 is used, the composite sheet has the same effect as when the composite sheet 1 is used.

[0549] Figure 6A to Figure 6D To illustrate the schematic, the Figure 4 1 is a cross-sectional view of an example of a method for manufacturing a semiconductor device when the composite sheet (first protective film forming sheet) 2 shown in FIG. 1 is used.

[0550] The same is true when the first protective film forming sheet 2 is used. Figure 6A to Figure 6B As shown, in the attaching process, the curable resin film 12 in the first protective film forming sheet 2 is attached to the bump forming surface 9a of the semiconductor wafer 9, so that the top end 9101 of the bump 91 protrudes from the curable resin film 12, thereby setting the first protective film forming sheet 2 on the semiconductor wafer 9.

[0551] In the attaching process, for example, first Fig. 6A As shown in FIG. 1 , the first protective film forming sheet 2 is arranged so that the curable resin film 12 of the first protective film forming sheet 2 faces the bump formation surface 9 a of the semiconductor wafer 9 .

[0552] Next, in the attaching step, the curable resin film 12 is brought into contact with the bumps 91 on the semiconductor wafer 9, and the first protective film forming sheet 2 is pressed onto the semiconductor wafer 9. Thus, the first surface 12a of the curable resin film 12 is pressed against the surface 91a of the bump 91 and the bump forming surface 9a of the semiconductor wafer 9 in sequence. Figure 6B As shown above, the curable resin film 12 in the first protective film forming sheet 2 is attached to the bump formation surface 9 a of the semiconductor wafer 9 .

[0553] At this time, the first protective film forming sheet 2 can be pressure-bonded onto the semiconductor wafer 9 by the same method as when the first protective film forming sheet 1 is used.

[0554] As described above, when the first protective film forming sheet 2 is pressed onto the semiconductor wafer 9, the curable resin film 12 and the buffer layer 13 in the first protective film forming sheet 2 are subjected to pressure from the bumps 91, and initially, the first surface 12a of the curable resin film 12 and the first surface 13a of the buffer layer 13 are deformed into a concave shape. In addition, cracks are generated in the curable resin film 12 subjected to pressure from the bumps 91 in this state. Finally, at the stage of pressing the first surface 12a of the curable resin film 12 onto the bump forming surface 9a of the semiconductor wafer 9, the upper portion 910 of the bump 91 including the top portion 9101 is formed to protrude through the curable resin film 12. At this final stage, the upper portion 910 of the bump 91 usually does not penetrate the buffer layer 13.

[0555] In addition, as described above, by using the first protective film forming sheet 2, during the process of bonding the curable resin film 12 to the bump forming surface 9a of the semiconductor wafer 9, the adhesive layer 14 highly suppresses the peeling of the first substrate 11 and the buffer layer 13, and more stably maintains the stacking structure of the first substrate 11, the adhesive layer 14 and the buffer layer 13.

[0556] like Figure 6B As shown, at the stage where the attaching step is completed, due to the same action as the first protective film forming sheet 1 , the curable resin film 12 is not left at all or almost not left on the upper portion 910 including the tip portion 9101 of the bump 91 .

[0557] Furthermore, at the stage where the attaching step is completed, the curable resin film 12 is prevented from overflowing beyond the initial size by the same action as the first protective film forming sheet 1 , thereby preventing the curable resin film 12 from overflowing from the bump formation surface 9 a of the semiconductor wafer 9 .

[0558] Furthermore, at the stage where the attaching step is completed, the shrinkage of the curable resin film 12 is suppressed on the bump forming surface 9a by the same action as that of the first protective film forming sheet 1.

[0559] After the above-mentioned attaching step, the surface (back surface) 9b of the semiconductor wafer 9 opposite to the bump formation surface 9a is further polished as necessary, and then a second protective film forming sheet (not shown) is attached to the back surface 9b.

[0560] The same is true when the first protective film forming sheet 2 is used. After the above-mentioned attaching step, Figure 6C As shown, in the removal step, the layers other than the curable resin film 12 in the first protective film-forming sheet 2 are removed from the curable resin film 12. More specifically, the layers removed are the first base material 11, the adhesion layer 14, and the buffer layer 13.

[0561] By performing the removal step, a semiconductor wafer with a resin film can be obtained, which is the same as the semiconductor wafer with a resin film obtained when the first protective film forming sheet 1 is used.

[0562] Thereafter, a semiconductor device can be manufactured by the same method as when the first protective film-forming sheet 1 is used.

[0563] That is, after the removal step, the curable resin film 12 is cured in the curing step to form the first protective film by the same method as when the first protective film forming sheet 1 is used. After the curing step, the semiconductor wafer 9 is divided in the dividing step to produce semiconductor chips 9' by the same method as when the first protective film forming sheet 1 is used, and the first protective film is cut in the cutting step.

[0564] like Fig.6D As shown, by performing the curing step and the dividing step, a semiconductor chip 9120' with a first protective film can be obtained. The semiconductor chip 9120' with a first protective film obtained here is the same as the semiconductor chip obtained when the sheet 1 for forming the first protective film is used.

[0565] Furthermore, the mounting step is performed in the same manner as when the first protective film forming sheet 1 is used, and a semiconductor package is produced using the circuit board on which the semiconductor chip 9 ′ is mounted, thereby manufacturing a target semiconductor device (not shown).

[0566] In the method for manufacturing a semiconductor device of the present embodiment, for example, by acquiring SEM imaging data of the bumps, it can be confirmed whether or not a curable resin film or a protective film remains on the top of the bumps.

[0567] In addition, whether the curable resin film has overflowed on the bump forming surface of the semiconductor wafer and whether the curable resin film has shrunk on the bump forming surface can be confirmed by, for example, obtaining SEM imaging data of the corresponding portion on the bump forming surface of the semiconductor wafer.

[0568] Example

[0569] The present invention is further described in detail below through specific examples, but the present invention is not limited to the following examples.

[0570] <Raw materials for preparing the resin film-forming composition>

[0571] The raw materials used for preparing the resin film-forming composition are shown below.

[0572] [Polymer component (A)]

[0573] (A)-1: Polyvinyl butyral having structural units represented by the following formulae (i)-1, (i)-2 and (i)-3 ("S-LEC BL-10" manufactured by SEKISUI CHEMICAL CO., LTD., weight average molecular weight: 25,000, glass transition temperature: 59°C)

[0574] (A)-2: an acrylic resin (weight average molecular weight: 800,000, glass transition temperature: -28°C) obtained by copolymerizing butyl acrylate (55 parts by mass), methyl acrylate (10 parts by mass), glycidyl methacrylate (20 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass).

[0575] [Chemical formula 2]

[0576]

[0577] In the formula, l1 is approximately 28, m1 is 1 to 3, and n1 is an integer from 68 to 74.

[0578] [Epoxy resin (B1)]

[0579] (B1)-1: Liquid modified bisphenol A type epoxy resin ("EPICLON EXA-4850-150" manufactured by DIC CORPORATION, molecular weight 900, epoxy equivalent 450 g / eq)

[0580] (B1)-2: Liquid bisphenol F type epoxy resin ("YL983U" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 165 to 175 g / eq)

[0581] (B1)-3: Polyfunctional aromatic epoxy resin ("EPPN-502H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 158 to 178 g / eq)

[0582] (B1)-4: dicyclopentadiene type epoxy resin ("EPICLON HP-7200HH" manufactured by DIC CORPORATION, epoxy equivalent of 254 to 264 g / eq)

[0583] [Thermosetting agent (B2)]

[0584] (B2)-1: o-cresol type novolac resin ("PHENOLITE KA-1160" manufactured by DIC CORPORATION)

[0585] (B2)-2: Novolac type phenolic resin ("BRG-556" manufactured by Showa Denko KK)

[0586] [Filling material (D)]

[0587] (D)-1: Epoxy-modified spherical silica ("ADMANANO YA050C-MKK" manufactured by ADMATECHS, average particle size 50 nm)

[0588] [Additive (I)]

[0589] (I)-1: Rheology control agent (polyhydroxycarboxylate, BYK-R606)

[0590] (I)-2: Surfactant (acrylic acid polymer, "BYK-361N" manufactured by BYK)

[0591] (I)-3: Silicone oil (aralkyl-modified silicone oil, "XF42-334" manufactured by Momentive Performance Materials Japan Inc.)

[0592] [Curing accelerator (C)]

[0593] (C)-1: 2-phenyl-4,5-dihydroxymethylimidazole ("CUREZOL 2PHZ-PW" manufactured by SHIKOKU CHEMICALS CORPORATION)

[0594] [Example 1]

[0595] <<Manufacturing of the First Protective Film-Forming Sheet>>

[0596] <Preparation of Thermosetting Resin Film-Forming Composition>

[0597] The polymer component (A)-1 (100 parts by mass), epoxy resin (B1)-1 (350 parts by mass), epoxy resin (B1)-4 (270 parts by mass), epoxy resin (B2)-1 (190 parts by mass), curing accelerator (C)-1 (2 parts by mass), filler (D)-1 (90 parts by mass) and additive (I)-1 (9 parts by mass) were dissolved or dispersed in methyl ethyl ketone and stirred at 23° C. to obtain a composition (III) as a composition for forming a thermosetting resin film, in which the total concentration of all components other than the solvent was 45% by mass. In addition, the blending amounts of the components other than the solvent shown here are all blending amounts of the target product without the solvent.

[0598] <Manufacturing of the First Protective Film-Forming Sheet>

[0599] A release film ("SP-PET381031" manufactured by LINTEC Corporation, 38 μm thick) having one surface of a polyethylene terephthalate film subjected to a release treatment by silicone treatment was used, and the composition (III) obtained above was applied to the release-treated surface thereof, followed by heating and drying at 120° C. for 2 minutes to form a thermosetting resin film having a thickness of 30 μm.

[0600] A laminate sheet ("E-9485" manufactured by LINTEC Corporation, 485 μm thick) corresponding to the laminate of the first substrate, the adhesion layer, and the buffer layer was used, and the buffer layer in the laminate sheet was bonded to the thermosetting resin film on the release film obtained above. Thus, a laminated film was obtained in which the first substrate, the adhesion layer, the buffer layer, the thermosetting resin film, and the release film were laminated in order in their thickness direction. Figure 4 The first protective film forming sheet having the structure shown.

[0601] <<Evaluation of the first protective film-forming sheet>>

[0602] <Measurement of Gc1 and Gc300 of Thermosetting Resin Film, and Calculation of X Value>

[0603] Except for changing the coating amount of composition (III), 20 thermosetting resin films with a thickness of 50 μm were prepared by the same method as above. Then, these thermosetting resin films were stacked and the obtained stacked film was cut into a disk shape with a diameter of 25 mm, thereby preparing a test piece of thermosetting resin film with a thickness of 1 mm.

[0604] The test piece of the thermosetting resin film obtained above was placed at the test piece setting position in a viscoelasticity measuring device ("MCR301" manufactured by Anton Paar) preheated to 90°C, and a measuring jig was pressed against the upper surface of the test piece to fix the test piece at the setting position.

[0605] Next, the strain generated on the test piece was gradually increased in the range of 0.01% to 1000% under the conditions of a temperature of 90°C and a measurement frequency of 1 Hz, and the storage modulus Gc of the test piece was measured. The X value was calculated from the measured values ​​of Gc1 and Gc300. The results are shown in Table 1.

[0606] <Measurement of the amount of overflow of thermosetting resin film>

[0607] A release film ("SP-PET381031" manufactured by LINTEC Corporation, 38 μm thick) having one surface of a polyethylene terephthalate film subjected to a release treatment by silicone treatment was used, and the composition (III) obtained above was applied to the release-treated surface thereof, followed by heating and drying at 120°C for 2 minutes to form a thermosetting resin film having a thickness of 30 μm.

[0608] Next, this thermosetting resin film was processed into a circular shape with a diameter of 170 mm together with the release film, thereby preparing a test piece with a release film.

[0609] The entire exposed surface of the obtained test piece (in other words, the surface opposite to the side provided with the release film) was bonded to the surface of a transparent tape-shaped back grinding tape ("E-8180" manufactured by LINTEC Corporation) to obtain a Figure 7 The stack shown. Figure 7 It is a top view schematically showing a state when the obtained laminated body is looked down from above the back grinding tape side.

[0610] As shown in the figure, the obtained laminated body 101 is constituted by laminating the back grinding tape 7, the test piece 120 (thermosetting resin film 12), and the release film in this order in the thickness direction thereof.

[0611] Next, the release film was removed from the obtained laminate, and the exposed surface of the newly generated test piece (in other words, the surface of the test piece on the opposite side to the side having the back grinding tape) was pressed against one surface of a silicon wafer having a diameter of 12 inches, thereby attaching the test piece to the surface of the silicon wafer. At this time, the test piece was attached while heating the thermosetting resin film using an attaching device (roll laminator, "RAD-3510F / 12" manufactured by LINTEC Corporation) under the conditions of a table temperature of 90°C, an attaching speed of 2 mm / sec, an attaching pressure of 0.5 MPa, and a roller attaching height of -200 μm.

[0612] Next, for the test piece with back grinding tape attached to the silicon wafer, the maximum value of the length of the line segment connecting two different points on the outer circumference is measured, and the measured value (the maximum value of the length of the line segment) is used to calculate the maximum value of the length of the line segment using the reference Figure 2 The method described above calculates the overflow amount (mm) of the test piece (in other words, the thermosetting resin film).

[0613] <Confirm whether there is any residual thermosetting resin film on the top of the bump>

[0614] For the first protective film forming sheet obtained above, the release film is removed, and the surface (exposed surface) of the thermosetting resin film thus exposed is pressed onto the bump forming surface of a semiconductor wafer having a diameter of 8 inches and having bumps, thereby attaching the first protective film forming sheet with the release film removed to the bump forming surface of the semiconductor wafer. At this time, as a semiconductor wafer, a semiconductor wafer with a bump height of 210 μm, a bump width of 250 μm, and a distance between bumps of 400 μm is used. In addition, using an attaching device (roll laminator, "RAD-3510F / 12" manufactured by LINTEC Corporation), the first protective film forming sheet is attached while being heated under the conditions of a workbench temperature of 90°C, an attaching speed of 2 mm / sec, an attaching pressure of 0.5 MPa, and a roller attaching height of -200 μm.

[0615] Next, using a multi-wafer mounter ("RAD-2700F / 12" manufactured by LINTEC Corporation), the first base material, the adhesion layer, and the buffer layer were removed from the thermosetting resin film to expose the thermosetting resin film.

[0616] Next, a scanning electron microscope (SEM, "VE-9700" manufactured by KEYENCE CORPORATION) was used to observe the surface of the bumps of the semiconductor wafer from a direction perpendicular to the bump formation surface of the semiconductor wafer at an angle of 60° to confirm whether there was a residual thermosetting resin film on the top of the bumps. The results are shown in Table 1.

[0617] <Confirmation of shrinkage of the thermosetting resin film on the bump formation surface>

[0618] Using the same method as the above-mentioned "confirming whether there is residual thermosetting resin film on the upper part of the bump", use the same semiconductor wafer, attach the first protective film forming sheet on its bump forming surface, and remove the first substrate, the sealing layer and the buffer layer from the thermosetting resin film.

[0619] Next, the thermosetting resin film attached to the semiconductor wafer was heat-treated using a pressurized oven ("RAD-9100" manufactured by LINTEC Corporation) under heating conditions of a temperature of 130° C., a time of 2 hours, and a furnace pressure of 0.5 MPa, thereby thermally curing the thermosetting resin film.

[0620] Next, a scanning electron microscope (SEM, "VE-9700" manufactured by KEYENCE CORPORATION) was used to observe the entire laminate of the cured product of the thermosetting resin film (in other words, the first protective film) and the semiconductor wafer from the cured product side. In addition, the presence of an area where the bottom of the bump or the bump forming surface of the semiconductor wafer can be directly confirmed is judged as "shrinkage", and the absence of an area where the bottom of the bump or the bump forming surface of the semiconductor wafer can be directly confirmed is judged as "no shrinkage".

[0621] [Example 2, Comparative Examples 1 to 3]

[0622] <<Manufacturing and evaluation of first protective film-forming sheet>>

[0623] The first protective film-forming sheet was manufactured and evaluated in the same manner as in Example 1 except that either or both of the types and amounts of the components blended when preparing the thermosetting resin film-forming composition were changed so that the types and contents of the components in the thermosetting resin film-forming composition were as shown in Table 1. The results are shown in Table 1.

[0624] In addition, "-" described in the column of contained components in Table 1 means that the thermosetting resin film-forming composition does not contain the component.

[0625] [Table 1]

[0626]

[0627] From the above results, it can be seen that in Examples 1 and 2, the overflow amount of the thermosetting resin film was 0 mm (no overflow of the thermosetting resin film was found), and no thermosetting resin film was found to remain on the upper part of the bump.

[0628] Furthermore, in Examples 1 and 2, no shrinkage of the thermosetting resin film on the bump formation surface was found, and the basic properties of the thermosetting resin film were good. In addition, at the same time, the result of observing the upper part of the bump was that no thermosetting resin film was found.

[0629] In Examples 1 and 2, the value of X is 29-65.

[0630] On the other hand, in Comparative Example 1, the overflow of the thermosetting resin film could not be suppressed.

[0631] In Comparative Example 1, the X value is 18, which is significantly smaller than those in Examples 1 and 2. This is because Gc1 in Comparative Example 1 is too low.

[0632] In Comparative Example 2, it was found that the thermosetting resin film's heat-cured product shrunk on the bump formation surface, and the basic characteristics of the thermosetting resin film were inferior.

[0633] In Comparative Example 2, the X value is 10000 or more, which is significantly greater than Examples 1 and 2. This is because Gc300 is too low in Comparative Example 2. In Comparative Example 2, since Gc300 is below the detection threshold, it cannot be determined, and only the X value of 10000 or more can be determined.

[0634] In Comparative Example 3, the thermosetting resin film was found to remain on the top of the bumps. When confirming whether the thermosetting product of the thermosetting resin film had shrunk, the top of the bumps was simultaneously observed, and the thermosetting product of the thermosetting resin film was found.

[0635] In Comparative Example 3, the X value is 18, which is significantly smaller than those in Examples 1 and 2. This is because Gc300 in Comparative Example 3 is too high.

[0636] In addition, in Examples 1 to 2, for the buffer layer in the laminated sheet, a test piece (a circular plate with a diameter of 25 mm and a thickness of 1 mm) identical to the test piece of the thermosetting resin film described above was prepared, and the strain generated on the test piece of the buffer layer was gradually increased within the range of 0.01% to 1000% using the same method as that for the test piece of the thermosetting resin film, and the storage modulus Gb of the test piece of the buffer layer was measured.

[0637] As a result, when Gb and Gc were compared when the strains were the same, Gb was greater than or equal to Gc (Gb ≥ Gc) in the entire range of the strains from 0.01% to 1000%.

[0638] Industrial Applicability

[0639] The present invention can be used to manufacture a semiconductor chip having bumps on a connection pad portion that can be used in a flip chip bonding method.

[0640] Description of Reference Numerals

[0641] 1, 2: composite sheet (sheet for forming the first protective film); 11: substrate (first substrate); 12: resin film (curable resin film); 12a: first surface of the resin film (curable resin film); 120': first protective film (first protective film after cutting); 13: buffer layer; 13a: first surface of the buffer layer; 14:

[0642] Adhesive layer; 9: semiconductor wafer; 9a: bump forming surface of semiconductor wafer; 9': semiconductor chip; 9a': bump forming surface of semiconductor chip; 91: bump; 91a: bump surface; 910:

[0643] The upper part of the bump; 9101: the top part of the bump.

Claims

1. A resin film, wherein Under the conditions of a temperature of 90° C. and a frequency of 1 Hz, a test piece of the resin film having a diameter of 25 mm and a thickness of 1 mm is strained and the storage modulus of the test piece is measured. When the storage modulus of the test piece when the strain of the test piece is 1% is Gc1 and the storage modulus of the test piece when the strain of the test piece is 300% is Gc300, the value of X calculated by the following formula is 19 or more and less than 10000, X = Gc1 / Gc300, The resin film contains a polymer component (A), a thermosetting component (B), a curing accelerator (C), a filler (D) and an additive (I). The polymer component (A) is polyvinyl butyral, The thermosetting component (B) is composed of an epoxy resin (B1) and a thermosetting agent (B2). The epoxy resin (B1) is a liquid modified bisphenol A type epoxy resin with an epoxy equivalent of 450 g / eq and a dicyclopentadiene type epoxy resin with an epoxy equivalent of 254 to 264 g / eq. The thermal curing agent (B2) is an o-cresol type novolac resin, The filler material (D) is epoxy-modified spherical silica, The additive (I) is an acrylic polymer and an aralkyl-modified silicone oil, or a polyhydroxycarboxylate. The content of the additive (I) in the resin film is 0.5 to 5% by mass based on the total mass of the resin film.

2. The resin film according to claim 1, wherein The additive (I) is a surfactant composed of acrylic polymer and aralkyl modified silicone oil, or a rheology control agent composed of polyhydroxycarboxylate.

3. The resin film according to claim 1, wherein The resin film is used to be attached to the concave and convex surface.

4. The resin film according to claim 1, wherein The resin film is thermosetting.

5. A composite sheet comprising a substrate, a buffer layer provided on the substrate, and a resin film provided on the buffer layer, The resin film is the resin film according to any one of claims 1 to 4.

6. A method for manufacturing a semiconductor device, comprising: The thermosetting resin film in the composite sheet according to claim 5 is attached to the surface of the semiconductor wafer having bumps so that the top of the bumps protrude from the resin film, thereby providing the composite sheet on the semiconductor wafer. After the attaching step, a removing step of removing layers other than the resin film in the composite sheet from the resin film; After the removing step, the resin film is thermally cured to form a first protective film; After the curing step, the semiconductor wafer is divided to thereby produce semiconductor chips; After the curing step, a cutting step of cutting the first protective film; and A mounting process in which the semiconductor chip with a first protective film obtained after the splitting process and the cutting process, which comprises the semiconductor chip and a first protective film arranged on the surface of the semiconductor chip having bumps and the top end of the bumps protruding from the first protective film, is flip-chip bonded to a substrate at the top end of the bumps.

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