Resin film, composite sheet, and method for manufacturing semiconductor chip with first protective film

Abstract

The present invention provides a resin film, which is a curable resin film. A cured product of the resin film with a thickness of 0.5 mm and a width of 4.5 mm is used as a first test piece. The first test piece is subjected to thermomechanical analysis. When the linear expansion coefficient α1 of the first test piece is measured from the temperature of the first test piece from ‑75°C to the temperature equal to the glass transition temperature, the α1 is 65 ppm / K or less. In the thermomechanical analysis, the first test piece is heated at a heating rate of 5°C / min, thereby increasing the temperature of the first test piece from room temperature to 100°C, then the first test piece is cooled at a cooling rate of 5°C / min, thereby decreasing the temperature of the first test piece to ‑75°C, then the first test piece is heated at a heating rate of 5°C / min, thereby increasing the temperature of the first test piece to 260°C.

Description

Technical Field

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

[0002] This application claims priority based on Japanese Patent Application No. 2020-031717 filed in Japan on February 27, 2020, the contents of which are incorporated herein by reference. Background Art

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

[0004] The semiconductor chip used in the mounting method is obtained, for example, by grinding or cutting the surface of a semiconductor wafer having bumps formed on the circuit surface, which is opposite to the circuit surface (in other words, the bump forming surface), and singulating it. In the process of obtaining such a semiconductor chip, for the purpose of protecting the bump forming surface and the bumps of the semiconductor wafer, a curable resin film is usually 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, semiconductor devices are expected to have higher functions, so the size of semiconductor chips tends to increase. However, the semiconductor chip with an increased size will be warped when mounted on a substrate, so the bumps are easily deformed, and in particular, the bumps located at the ends of the semiconductor chip or near the ends are easily broken. It is also desired that the protective film formed on the bump formation surface suppresses the breakage of such bumps.

[0006] Reference Figures 8A to 8D A method of forming a protective film on the bump formation surface of a semiconductor wafer will be described.

[0007] When forming a protective film, use Fig. 8A The protective film forming sheet 8 is shown. The protective film forming sheet 8 is formed by laminating an adhesive layer 83 and a curable resin film 82 on a base material 81 in this order.

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

[0009] Next, the protective film forming sheet 8 is pressed onto the semiconductor wafer 9, as shown in FIG. Figure 8BAs shown, 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 closely 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, the adhesive layer 83 is also closely bonded to a part of the surface 91a of the bump 91.

[0010] After the curable resin film 82 is thus bonded, 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 further 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 substrate 81 and the adhesive layer 83 are removed from the curable resin film 82 .

[0012] Then, if Fig.8D As shown, the curable resin film 82 is cured to form a protective film 82'.

[0013] Thus, as a protective film forming sheet capable of forming a protective film on the bump forming surface of a semiconductor wafer, a protective film forming sheet is disclosed, in which the curable resin film is thermosetting and has a melt viscosity in a specific range, and the adhesive layer has a shear modulus in a specific range within a specific temperature range (see patent document 1).

[0014] Prior art literature

[0015] Patent Literature

[0016] Patent Document 1: Japanese Patent Application Publication No. 2015-092594 Summary of the invention

[0017] Technical Problems to be Solved by the Invention

[0018] On the other hand, various methods are known as methods for dividing a semiconductor wafer into semiconductor chips. As an example, the following method is known: a semiconductor wafer is further provided with a groove as a dividing position on the bump forming surface of the semiconductor wafer, and as described above, the surface (back side) of the semiconductor wafer opposite to the bump forming surface is ground so that the ground surface (back side) reaches the groove, thereby dividing the semiconductor wafer into semiconductor chips. In the case of adopting this method, when the curable resin film in the protective film forming sheet is attached to the bump forming surface of the semiconductor wafer before dividing the semiconductor wafer, if the curable resin film can be fully filled in the groove, the protective film can be cut into the size of the semiconductor chip by dividing the semiconductor wafer and cutting the curable resin film or the protective film into the size of the semiconductor chip, so that the protective film not only covers the bump forming surface of the semiconductor chip, but also covers its side. Fig. 9 This semiconductor chip is shown which includes a protective film not only on the bump formation surface but also on the side surfaces thereof. Fig. 9 This is a cross-sectional view schematically showing an example of a semiconductor chip having a protective film on the bump formation surface and the side surface (semiconductor chip with a protective film) assuming that the protective film forming sheet 8 described above can be normally obtained.

[0019] The semiconductor chip 909 with a protective film shown here comprises a semiconductor chip 9' and a first protective film 820' provided on the side surface 9c' and the bump forming surface 9a' of the semiconductor chip 9'. The side surface 9c' and the bump forming surface 9a' of the semiconductor chip 9' are respectively protected by the cut first protective film 820', and the protection effect obtained by the semiconductor chip 9' is significantly higher.

[0020] In the manufacturing process of such a multi-sided protected semiconductor chip having a protective film on the bump forming surface and the side of the semiconductor chip, when the back of the semiconductor wafer is ground with the grooves filled with a protective film or a curable resin film, the semiconductor wafer becomes hot due to the friction between the grinding device such as a grinder and the semiconductor wafer, and a load is applied to the interface between the semiconductor wafer including the grooves and the protective film or the curable resin film. Therefore, part of the protective film or the curable resin film may be peeled off from the semiconductor wafer. In addition, even during the process of flip-chip bonding the multi-sided protected semiconductor chip to the substrate by reflow soldering or after flip-chip bonding, part of the protective film may be peeled off from the semiconductor chip because the protective film and the semiconductor chip are placed under high temperature conditions, and further because a load is applied to the interface between the protective film and the semiconductor chip.

[0021] On the other hand, it is not clear whether the protective film-forming sheet (protective film-forming film) disclosed in Patent Document 1 can solve such problems.

[0022] So far, the case where the curable resin film is attached to the bump forming surface of the semiconductor wafer has been described as an example, but it is not limited to this. The resin film can also be attached to the concave-convex surface of the semiconductor wafer other than the bump forming surface. In addition, like the semiconductor wafer, it is sometimes required to fully fill the fine grooves on the concave-convex surface with the resin film and to prevent the protective film from peeling off from the concave-convex surface. In this regard, such attachment to the concave-convex surface may cause poor filling of the fine grooves with the resin film and peeling of the protective film from the concave-convex surface.

[0023] The object of the present invention is to provide a resin film and a composite sheet having the resin film for use when attaching the resin film to a concave-convex surface, wherein the resin film can be suitable for attachment to the concave-convex surface and can form a protective film, and the resin film can fully fill the fine grooves on the concave-convex surface and can inhibit the protective film from peeling off from the concave-convex surface.

[0024] Technical means to solve technical problems

[0025] The present invention provides a resin film, which is a curable resin film. When the resin film is thermosetting, the resin film is pressurized at a pressure of 0.5 MPa and heated at 130° C. for 4 hours, thereby the resin film is thermally cured. When the resin film is energy ray curable, the resin film is heated at an illuminance of 230 mW / cm 2 , light intensity is 560mJ / cm 2 The resin film is irradiated with energy rays under the conditions of, thereby curing the resin film with energy rays, and the obtained cured product with a thickness of 0.5 mm and a width of 4.5 mm is used as a first test piece. A thermomechanical analysis is performed on a portion of the first test piece having a length of 15 mm. When the linear expansion coefficient α1 of the first test piece is measured from the temperature of the first test piece from -75°C to the temperature equal to the glass transition temperature, the α1 is 65 ppm / K or less. In the thermomechanical analysis, the first test piece is heated at a heating rate of 5°C / min, thereby increasing the temperature of the first test piece from room temperature to 100°C, and then the first test piece is cooled at a cooling rate of 5°C / min, thereby decreasing the temperature of the first test piece to -75°C, and then the first test piece is heated at a heating rate of 5°C / min, thereby increasing the temperature of the first test piece to 260°C.

[0026] For the resin film of the present invention, when the linear expansion coefficient α2 of the first test piece is measured from the same temperature as the glass transition temperature to 260° C. during the thermomechanical analysis, the α2 may be 165 ppm / K or less.

[0027] The resin film of the present invention having a diameter of 25 mm and a thickness of 1 mm is used as a second test piece, and the second test piece is strained under the conditions of a temperature of 90° C. and a frequency of 1 Hz, and the storage modulus of the second test piece is measured, and the storage modulus of the second test piece when the strain of the second test piece is 1% is set to Gc1, and the storage modulus of the second test piece when the strain of the second test piece is 300% is set to Gc300, the value of X calculated by the following formula can be 19 or more and less than 10000,

[0028] X=Gc1 / Gc300.

[0029] The resin film of the present invention can be used for attachment to a concave-convex surface.

[0030] The resin film of the present invention can be used to protect the uneven surface and side surfaces of a semiconductor chip.

[0031] Furthermore, the present invention provides a composite sheet including a support sheet and a resin film provided on one surface of the support sheet, wherein the resin film is the resin film of the present invention.

[0032] In the composite sheet of the present invention, the support sheet may include a base material and an adhesive layer provided on one surface of the base material, and the adhesive layer may be arranged between the base material and the resin film.

[0033] In the composite sheet of the present invention, the support sheet may include a substrate and a buffer layer provided on one surface of the substrate, and the buffer layer may be arranged between the substrate and the resin film.

[0034] In addition, the present invention provides a method for manufacturing a semiconductor chip with a first protective film, which is a method for manufacturing a semiconductor chip with a first protective film using a semiconductor wafer, wherein the semiconductor chip with the first protective film comprises a semiconductor chip and a first protective film arranged on the side surface and the surface having a bump of the semiconductor chip, and the semiconductor wafer has bumps and grooves serving as dividing positions of the semiconductor wafer on one surface thereof, and the manufacturing method comprises an attaching step, in which the resin film in the composite sheet of the present invention is attached to the one surface of the semiconductor wafer, thereby producing a semiconductor wafer with a resin film having the resin film on the one surface and the grooves filled with the resin film. The manufacturing method further comprises: after the attaching step, curing the resin film to form the first protective film, thereby producing a semiconductor wafer with a first protective film having the semiconductor wafer and the first protective film arranged on the one surface of the semiconductor wafer and filling the groove; after the curing step (1), dividing the semiconductor wafer, thereby producing a semiconductor chip group with a first protective film having a plurality of semiconductor chips and the first protective film arranged on the surfaces having the bumps of the plurality of semiconductor chips and the gaps between the semiconductor chips; and after the dividing step (1), dividing the semiconductor wafer along the semiconductor chip group with the first protective film The method further comprises the steps of: cutting the first protective film through the gap between the semiconductor chips to produce the semiconductor chip with the first protective film by cutting the first protective film, or cutting the first protective film along the groove in the semiconductor wafer with the first protective film after the attaching step and after the curing step (1), thereby producing a semiconductor wafer with the cut first protective film; and dividing the semiconductor wafer after the cutting step (2), thereby producing a semiconductor chip with the first protective film by dividing the semiconductor wafer, or dividing the semiconductor wafer after the attaching step, thereby producing a semiconductor wafer having a plurality of semiconductor chips and a plurality of semiconductor chips arranged on the plurality of semiconductor chips. A step (3) of dividing a semiconductor chip group with a resin film, wherein the resin film has a surface with the bumps and a gap between the semiconductor chips; a step (3) of curing the resin film to form the first protective film after the dividing step (3), thereby producing a semiconductor chip group with a first protective film, wherein the first protective film has a surface with the bumps and a gap between the semiconductor chips and is arranged on the surface of the plurality of semiconductor chips; and a step (3) of cutting the first protective film along the gap between the semiconductor chips in the semiconductor chip group with the first protective film after the curing step (3), thereby obtaining the semiconductor chip with the first protective film.

[0035] Effects of the Invention

[0036] According to the present invention, a resin film and a composite sheet having the resin film used when attaching the resin film to a concave-convex surface can be provided. The resin film can be suitable for attachment to the concave-convex surface and can form a protective film. The resin film can fully fill the fine grooves on the concave-convex surface and can inhibit the protective film from peeling off from the concave-convex surface. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 It is a cross-sectional view schematically showing an example of a resin film according to an embodiment of the present invention.

[0038] Figure 2 It is a top view for schematically explaining the amount of protrusion of the resin film when the planar shape of the resin film is circular.

[0039] Figure 3 This is a cross-sectional view schematically showing an example of a composite sheet according to an embodiment of the present invention.

[0040] Figure 4A To schematically illustrate the use Figure 3 sectional view of an example of a method for manufacturing a semiconductor chip with a first protective film when a composite sheet is shown.

[0041] Figure 4B To schematically illustrate the use Figure 3 sectional view of an example of a method for manufacturing a semiconductor chip with a first protective film when a composite sheet is shown.

[0042] Figure 4C To schematically illustrate the use Figure 3 sectional view of an example of a method for manufacturing a semiconductor chip with a first protective film when a composite sheet is shown.

[0043] Figure 4D To schematically illustrate the use Figure 3 sectional view of an example of a method for manufacturing a semiconductor chip with a first protective film when a composite sheet is shown.

[0044] Figure 4E To schematically illustrate the use Figure 3 sectional view of an example of a method for manufacturing a semiconductor chip with a first protective film when a composite sheet is shown.

[0045] Figure 5A To schematically illustrate the use Figure 3 2 is a cross-sectional view of another example of a method for manufacturing a semiconductor chip with a first protective film when a composite sheet is shown.

[0046] Figure 5B To schematically illustrate the use Figure 32 is a cross-sectional view of another example of a method for manufacturing a semiconductor chip with a first protective film when a composite sheet is shown.

[0047] Figure 5C To schematically illustrate the use Figure 3 2 is a cross-sectional view of another example of a method for manufacturing a semiconductor chip with a first protective film when a composite sheet is shown.

[0048] Figure 5D To schematically illustrate the use Figure 3 2 is a cross-sectional view of another example of a method for manufacturing a semiconductor chip with a first protective film when a composite sheet is shown.

[0049] Figure 5E To schematically illustrate the use Figure 3 2 is a cross-sectional view of another example of a method for manufacturing a semiconductor chip with a first protective film when a composite sheet is shown.

[0050] Fig. 6A To schematically illustrate the use Figure 3 2 is a cross-sectional view of another example of a method for manufacturing a semiconductor chip with a first protective film when a composite sheet is shown.

[0051] Figure 6B To schematically illustrate the use Figure 3 2 is a cross-sectional view of another example of a method for manufacturing a semiconductor chip with a first protective film when a composite sheet is shown.

[0052] Figure 6C To schematically illustrate the use Figure 3 2 is a cross-sectional view of another example of a method for manufacturing a semiconductor chip with a first protective film when a composite sheet is shown.

[0053] Fig.6D To schematically illustrate the use Figure 3 2 is a cross-sectional view of another example of a method for manufacturing a semiconductor chip with a first protective film when a composite sheet is shown.

[0054] Fig. 6E To schematically illustrate the use Figure 3 2 is a cross-sectional view of another example of a method for manufacturing a semiconductor chip with a first protective film when a composite sheet is shown.

[0055] Figure 7 This is a top view schematically showing a laminate including a thermosetting resin film produced when measuring the amount of protrusion of the thermosetting resin film in Example 1.

[0056] Fig. 8A It is a cross-sectional view for schematically explaining a method of forming a protective film on a bump formation surface of a semiconductor wafer.

[0057] Figure 8B It is a cross-sectional view for schematically explaining a method of forming a protective film on a bump formation surface of a semiconductor wafer.

[0058] Figure 8C It is a cross-sectional view for schematically explaining a method of forming a protective film on a bump formation surface of a semiconductor wafer.

[0059] Fig.8D It is a cross-sectional view for schematically explaining a method of forming a protective film on a bump formation surface of a semiconductor wafer.

[0060] Fig. 9 The cross-sectional view schematically shows an example of a semiconductor chip having a protective film on the bump formation surface and the side surface. DETAILED DESCRIPTION

[0061] ◇Resin film and method for producing the same

[0062] The resin film of one embodiment of the present invention is a curable resin film. When the resin film is thermosetting, the resin film is heat-cured by heating it at 130° C. for 4 hours while being pressed at a pressure of 0.5 MPa. When the resin film is energy-ray curable, the resin film is heated at an illuminance of 230 mW / cm 2 , light intensity is 560mJ / cm 2 The resin film is irradiated with energy rays under the conditions of , thereby curing the resin film with energy rays, and the obtained cured product having a thickness of 0.5 mm and a width of 4.5 mm is used as a first test piece, and a portion of the first test piece having a length of 15 mm is subjected to a thermomechanical analysis (TMA), and when a linear expansion coefficient α1 (sometimes simply referred to as "α1" in this specification) of the first test piece from -75°C to a temperature equal to the glass transition temperature (Tg) is measured, the α1 is 65 ppm / K or less, and in the thermomechanical analysis, the first test piece is heated at a heating rate of 5°C / min, thereby increasing the temperature of the first test piece from room temperature to 100°C, and then the first test piece is cooled at a cooling rate of 5°C / min, thereby decreasing the temperature of the first test piece to -75°C, and then the first test piece is heated at a heating rate of 5°C / min, thereby increasing the temperature of the first test piece to 260°C.

[0063] The resin film of this embodiment is suitable for attachment to a concavo-convex surface. In addition, the resin film of this embodiment has curability and can form a protective film by curing.

[0064] When the resin film of the present embodiment is attached to the concave-convex surface while being heated, the softened resin film spreads between the convex parts in a manner covering the convex parts, and is in close contact with the concave-convex surface, while covering the surface of the convex parts, especially the surface of the parts near the concave-convex surface, and burying the base of the convex parts. At this time, it is preferred that the convex parts of the concave-convex surface penetrate the resin film, and the upper part of the convex parts protrudes from the resin film. Furthermore, when the concave-convex surface has fine grooves, the resin film can be used to fully fill such grooves, and as a result, the protective film can be used to fully fill the grooves. Furthermore, it is possible to prevent the protective film from peeling off from the concave-convex surface. In this way, the reason why the grooves can be fully filled with the resin film and the protective film and the protective film can be prevented from peeling off from the concave-convex surface is that the α1 of the first test piece made using the resin film is less than 65ppm / K.

[0065] When the resin film of this embodiment is attached to a concave-convex surface, the heating temperature and the attachment pressure of the resin film can be appropriately adjusted according to other attachment conditions and the width and depth of the grooves on the concave-convex surface. For example, it can be set to be the same as when attached to the bump forming surface of a semiconductor wafer described later.

[0066] The degree of filling of the grooves on the uneven surface by the resin film or the protective film (sometimes referred to as "groove filling suitability" in this specification) can be confirmed by observing the uneven surface having the resin film or the protective film using an optical microscope.

[0067] The degree of suppression of peeling of the protective film from the uneven surface can be confirmed by observing the uneven surface provided with the protective film using an optical microscope.

[0068] When the resin film of this embodiment is attached to a concavo-convex surface, a composite sheet including the resin film of this embodiment can be used. The composite sheet will be described in detail below.

[0069] More specifically, as an object having the uneven surface to which the resin film is attached, for example, a semiconductor wafer having bumps can be cited.

[0070] 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.

[0071] In this specification, the surface having bumps of a semiconductor wafer or a semiconductor chip may be referred to as a "bump formation surface".

[0072] By attaching the resin film to the bump forming surface while heating it, the softened resin film spreads between the bumps in a manner that covers the bumps, and is in close contact with the bump forming surface, while covering the surface of the bumps, especially the surface of the parts near the bump forming surface, and burying the base of the bumps. At this time, it is preferred that the bumps of the bump forming surface penetrate the resin film, and the tops of the bumps protrude from the resin film. Furthermore, when the bump forming surface has fine grooves, the resin film can be used to fully fill such grooves, and as a result, the protective film can be used to fully fill the grooves. Furthermore, it is possible to prevent the protective film from peeling off from the uneven surface. The reasons for obtaining these effects are as described above.

[0073] Then, the resin film provided on the bump formation surface and filling the groove is cured in this state, and finally a first protective film is formed.

[0074] In this specification, the protective film provided 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 provided 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".

[0075] The resin film may be either thermosetting or energy-ray-curable, or may have both thermosetting and energy-ray-curable properties.

[0076] 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. Ultraviolet rays can be irradiated by, for example, using a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light lamp, or an LED lamp as an ultraviolet source. Electron beams can be irradiated by using an electron beam accelerator or the like.

[0077] 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.

[0078] Furthermore, the term "non-curable" refers to a property that a substance does not cure even by any means such as heating or irradiation with energy rays.

[0079] The first test piece is in the form of a film, and its planar shape is a rectangle.

[0080] The first test piece may be a cured product of a single-layer resin film having a thickness of 0.5 mm, but is preferably a cured product of a laminated film composed of a plurality of laminated single-layer resin films having a thickness of less than 0.5 mm from the viewpoint of ease of production.

[0081] The thicknesses of the multiple single-layer resin films constituting the laminated film (in other words, the cured products of the multiple single-layer resin films) may be the same, different, or only partially the same, but are preferably the same from the perspective of ease of production.

[0082] The TMA of the first test piece is performed on a portion of the first test piece having a length of 15 mm. Therefore, the length of the first test piece is preferably 18 mm or more.

[0083] The temperature of the first test piece is raised from normal temperature (eg, room temperature) to 100° C. before TMA is performed. The reason for this is to eliminate the inherent stress in the first test piece before starting TMA. This allows α1 to be measured with higher accuracy.

[0084] The temperature increase rate when the temperature of the first test piece is increased to 100° C. is preferably 4 to 6° C. / min, and may be, for example, 5° C. / min.

[0085] The first test piece is heated to 100°C and then cooled to -75°C. At this time, it is preferred that the temperature of the first test piece is heated to 100°C and then immediately cooled without maintaining the temperature (100°C). The cooling rate when cooling the first test piece is preferably 4 to 6°C / min, for example, 5°C / min.

[0086] The first test piece is heated after its temperature is lowered to -75°C to raise its temperature to 260°C. At this time, it is preferred that the temperature of the first test piece is lowered to -75°C and then immediately heated without maintaining the temperature (-75°C). The heating rate when heating the first test piece is preferably 4 to 6°C / min, for example, 5°C / min.

[0087] In the TMA of the first test piece, when the data of the temperature and heating time of the first test piece are graphed, an inflection point can be observed. The temperature of the first test piece when the inflection point is observed is the glass transition temperature (Tg). In this embodiment, the linear expansion coefficient of the first test piece determined during the period from the temperature of the first test piece starting from -75°C to the temperature equal to the glass transition temperature is used as α1. In addition, the linear expansion coefficient of the first test piece determined during the period from the temperature equal to the glass transition temperature to 260°C is used as α2 described later.

[0088] α1 is 65 ppm / K or less, preferably 62 ppm / K or less, and can be, for example, any range of 55 ppm / K or less and 48 ppm / K or less.

[0089] The lower limit of α1 is not particularly limited. For example, when α1 is 20 ppm / K or more, the production of the resin film is easier.

[0090] α1 can be set within a numerical range formed by appropriately combining the lower limit value and the upper limit value, preferably 20 to 65 ppm / K, more preferably 20 to 62 ppm / K, for example, any of 20 to 55 ppm / K and 20 to 48 ppm / K.

[0091] In the TMA of the first test piece, when the linear expansion coefficient α2 of the first test piece is measured from the temperature equal to the glass transition temperature to 260° C., the α2 is preferably 165 ppm / K or less. By satisfying the conditions of α1 and the above α2, a higher effect can be obtained in that the fine grooves on the concavo-convex surface can be fully filled and the peeling of the protective film from the concavo-convex surface can be suppressed.

[0092] α2 is 165 ppm / K or less, preferably 162 ppm / K or less, and can be, for example, any range of 140 ppm / K or less and 120 ppm / K or less.

[0093] The lower limit of α2 is not particularly limited. For example, when α2 is 90 ppm / K or more, the resin film can be produced more easily.

[0094] α2 can be set within a numerical range formed by appropriately combining the lower limit value and the upper limit value, preferably 90 to 165 ppm / K, more preferably 90 to 162 ppm / K, for example, it can be any range of 90 to 140 ppm / K and 90 to 120 ppm / K.

[0095] As a preferred resin film, for example, a resin film can be listed, wherein α1 of the resin film is below 65 ppm / K, preferably below 62 ppm / K, or in any range between 55 ppm / K and 48 ppm / K, and α2 is below 165 ppm / K, preferably below 162 ppm / K, or in any range between 140 ppm / K and 120 ppm / K.

[0096] By adjusting the type or content of the components contained in the resin film, α1 and α2 can be easily adjusted. To this end, it is sufficient to adjust the type or content of the components contained in the composition used to form the resin film. For example, when using the thermosetting resin film forming composition (III) described later, by adjusting the type or content of the main components contained in the composition, such as the thermosetting component (B) (for example, epoxy resin (B1) and thermosetting agent (B2)), filler (D), etc., α1 and α2 can be easily adjusted.

[0097] For example, if the content of the thermosetting component (B) of the thermosetting resin film and the composition (III) is reduced (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)), α1 and α2 are likely to become smaller. In addition, if the content of the filler (D) is increased, α1 and α2 are likely to become smaller.

[0098] In this embodiment, the resin film having a diameter of 25 mm and a thickness of 1 mm is used as a second test piece, and the second test piece is strained under the conditions of a temperature of 90°C and a frequency of 1 Hz, and the storage modulus of the second test piece is measured. When the storage modulus of the second test piece when the strain of the second test piece is 1% is set to Gc1, and the storage modulus of the second test piece when the strain of the second test piece is 300% is set to Gc300, the X value calculated by the following formula is preferably greater than 19 and less than 10000 (19≤X value<10000).

[0099] X=Gc1 / Gc300

[0100] When such a resin film is attached to a concave-convex surface, when 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, the resin film can be suppressed from remaining on the upper portion of the convex portion. And, of course, the solidified product of the resin film in this state can be suppressed from adhering to the upper portion of the convex portion. Furthermore, since the sticking of the resin film from its initial size can be suppressed, for example, the sticking of the resin film from the concave-convex surface can be suppressed. Furthermore, when the resin film and its solidified product are set on the concave-convex surface, the area of ​​the convex portion of the concave-convex surface other than its upper portion (for example, the base near the concave-convex surface) or the area near the convex portion of the concave-convex surface is not covered by the resin film and its solidified product and is inadvertently exposed, i.e., the so-called unevenness can be suppressed.

[0101] Thus, by setting the X value to be 19 or more and less than 10000, the resin film has more excellent characteristics in that the convex portions can be exposed and the entire concavo-convex surface can be covered with the resin film itself and its cured product.

[0102] The second test piece for the strain dispersion measurement was in the form of a film, and its planar shape was circular.

[0103] The second 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.

[0104] The thicknesses of the plurality of single-layer resin films constituting the laminated film may be the same or different, or only partially the same. However, from the viewpoint of easy production, the thicknesses of the resin films are preferably the same.

[0105] In this specification, not limited to Gc1 and Gc300, "storage modulus of the second test piece" refers to "when the second test piece of the resin film with a diameter of 25 mm and a thickness of 1 mm is strained under the conditions of temperature of 90°C and frequency of 1 Hz, the storage modulus of the second test piece corresponding to the strain."

[0106] When a resin film is attached to a concave-convex surface of an attached object, the strain degree of the resin film is greatly different in the intermediate stage where 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) tries to penetrate the resin film and protrude, and in the final stage where the resin film fills the base of the convex part after penetrating the resin film and protruding from the upper part of the convex part. More specifically, the strain of the resin film is large in the intermediate stage, and the strain of the resin film is small in the final stage.

[0107] The resin film of this embodiment adopts Gc1 as the storage modulus of the resin film when the strain is small, and adopts Gc300 as the storage modulus of the resin film when the strain is large. By limiting the X value (= Gc1 / Gc300) to a specific range in a manner that makes Gc1 high and Gc300 low, the excellent effect described above is exerted.

[0108] Whether or not the resin film remains on the upper part of the convex part of the uneven surface can be confirmed by, for example, obtaining SEM image data of the upper part of the convex part.

[0109] In addition, whether the resin film protrudes from the concavo-convex surface or whether the resin film is uneven on the concavo-convex surface can be confirmed by, for example, obtaining SEM image data of corresponding parts on the concavo-convex surface.

[0110] In the resin film, the X value may be, for example, in any range of 5000 or less, 2000 or less, 1000 or less, 500 or less, 300 or less, 100 or less, and 70 or less.

[0111] On the other hand, from the viewpoint of further improving the effect of fully filling the fine grooves on the concavo-convex surface with the resin film, the X value may be, for example, any range of 25 or more, 30 or more, 35 or more, 40 or more, 45 or more, and 50 or more.

[0112] 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, or in any range of 25-70, 30-70, 35-70, 40-70, 45-70, and 50-70.

[0113] For other resin films with an X value of 10,000 or more, even if they were attached to the uneven surface and the upper part of the convex part protruded from the other resin film, the effect of suppressing unevenness was not observed, and the cured product of the other resin film still had unevenness.

[0114] In the resin film, Gc1 is preferably a value such that the X value is 19 or more and less than 10,000.

[0115] As described above, from the viewpoint of achieving the effect of suppressing the resin film from remaining on the convex portion, the effect of suppressing the bulging of the resin film, and the effect of suppressing the unevenness of the resin film and its cured product at a high level, Gc1 is preferably 1×10 4 ~1×10 6 Pa, more preferably 1×10 5 ~7×10 5 Pa.

[0116] In the resin film, Gc300 is preferably a value such that the X value is 19 or more and less than 10,000.

[0117] Furthermore, for the same reason as that of Gc1 described above, Gc300 is preferably 1 to 30000 Pa, and may be, for example, 1 to 5000 Pa, or 5000 to 30000 Pa.

[0118] In the resin film, it is preferred that the above conditions are satisfied simultaneously, that is, it is preferred that: Gc1 is 1×10 4 ~1×10 6 Pa, preferably 1×10 5 ~7×10 5 Pa, and Gc300 is 1-30000Pa, 1-5000Pa or 5000-30000Pa.

[0119] The storage modulus of the resin film is not limited to Gc1 and Gc300, and can be easily adjusted by adjusting the type or content of the components contained in the resin film. To this end, 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 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.

[0120] 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.

[0121] As described later, the resin film of the present embodiment can be formed into a composite sheet by, for example, laminating it with a supporting sheet.

[0122] Figure 1 It is a cross-sectional view schematically showing an example of a resin film according to an embodiment of the present invention.

[0123] In order to facilitate understanding of the features of the present invention, important parts of the drawings used in the following description may be enlarged for convenience, and the dimensional ratios of the components may not necessarily be the same as the actual ones.

[0124] 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 which is opposite to the first surface 12a.

[0125] Such a resin film 12 is preferably stored in a roll shape, for example.

[0126] The α1 of the first test piece of the resin film 12 was 65 ppm / K or less.

[0127] The α2 of the first test piece of the resin film 12 is preferably 165 ppm / K or less.

[0128] The X value of the second test piece of the resin film 12 is preferably 19 or more and less than 10,000.

[0129] Both the first release film 151 and the second release film 152 may be known release films.

[0130] The first release film 151 and the second release film 152 may be the same release films or different release films, for example, release films having different release forces required when being released from the resin film 12 .

[0131] for Figure 1 The resin film 12 shown in the figure has an exposed surface formed by removing any one of the first release film 151 and the second release film 152, which is attached to the concave-convex surface. Then, the exposed surface formed by removing the other release film remaining in the first release film 151 and the second release film 152 is attached to the surface of other layers (e.g., a buffer layer, an adhesive layer, etc.) used to constitute the composite sheet described later.

[0132] Figure 1 , an example in which the release film is provided on both sides (the first side 12a and the second side 12b) of the resin film 12 is shown, but the release film may be provided on only one side of the resin film 12, that is, only on the first side 12a or only on the second side 12b.

[0133] The resin film of the present embodiment contains a resin component, and may or may not contain components other than the resin component.

[0134] Preferred resin films include, for example, resin films containing a resin component, a thermosetting component and a filler, and, if necessary, various additives that are not any of these components (resin component, thermosetting component and filler) and have the effect of adjusting the storage modulus of the resin film.

[0135] 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.

[0136] When a resin film is attached to an attachment object such as a concave or convex surface, and the resin film protrudes from its initial size, the resin film is looked down at from above the resin film in a protruding state, and the maximum value of the length of the line segment connecting two different points on the periphery of the resin film at this time is calculated. Further, the value of the initial (i.e., before protrusion) width of the resin film at the position overlapping with the line segment showing the maximum value is calculated, and the value of the width of the resin film is subtracted from the maximum value of the length of the line segment, thereby calculating the amount of resin film protrusion.

[0137] Figure 2 It is a top view for schematically explaining the amount of protrusion of the resin film when the planar shape of the resin film is circular.

[0138] 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.

[0139] The resin film 101 shown here is in a state of protruding from the initial size when attached to the attachment object 102. The reference numeral 101' represents the resin film of the initial size, and is simply shown for the sake of understanding the protruding amount. Although the plane shape of the initial resin film 101' is circular here, the plane shape of the resin film 101 in the protruding state is not circular. However, this is only an example, and the plane shape of the resin film 101 in the protruding state is not limited to the shape shown here.

[0140] In order to find the amount of the resin film 101 protruding, 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 from the point, and further find the initial (i.e., before the protrusion) width D0 of the resin film 101' at the position overlapping with the line segment showing the maximum value. The difference (D1-D0) between D1 and D0 is the amount of the protruding.

[0141] When looking down at the line segment showing the maximum value in the resin film 101, the line segment sometimes passes through the center of the initial resin film 101'. At this time, the width value of the initial resin film 101' at the position overlapping with the line segment showing the maximum value is the diameter of the resin film 101'.

[0142] Here, the bulging 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 bulging amount of the resin film can be calculated by the same method.

[0143] Regardless of whether the resin film 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, the multiple layers may be the same or different from each other, and there is no particular limitation on the combination of the multiple layers.

[0144] 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 the layers may be the same, all the layers may be different, or only some of the layers may be the same", and further "multiple layers may be different from each other" means "at least one of the constituent materials and thicknesses of each layer is different from each other".

[0145] Regardless of whether the resin film is thermosetting or energy-ray curable, the thickness of the resin film is preferably 1 to 100 μm, more preferably 5 to 80 μm, and particularly preferably 5 to 60 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 ability can be formed. On the other hand, by making the thickness of the resin film below the upper limit, the thickness can be suppressed from being too thick.

[0146] 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.

[0147] <<Resin film forming composition>>

[0148] 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 to be formed and drying it as needed. The content ratio of the components that do not vaporize at room temperature in the resin film-forming composition is usually the same as the content ratio of the components in the resin film.

[0149] In this specification, "normal temperature" means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25°C.

[0150] Thermosetting resin film can be formed using a thermosetting resin film-forming composition, and energy-ray curable resin film can be formed using an energy-ray curable resin film-forming composition. In addition, in this specification, when the resin film has both thermosetting and energy-ray curing properties, if the contribution of thermal curing of the resin film to its curing (e.g., formation of a protective film) is greater than the contribution of energy-ray curing to its curing, the resin film is considered to be a thermosetting resin film. On the contrary, if 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 is considered to be an energy-ray curable resin film.

[0151] In the resin film, the total content of one or two or more components described below contained in the resin film is not more than 100% by mass based on the total mass of the resin film.

[0152] 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.

[0153] 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.

[0154] Regardless of whether the resin film is thermosetting or energy-ray curable, the drying conditions of the resin film-forming composition are not particularly limited. However, when the resin film-forming composition contains a solvent described later, it is preferably heated and dried. In addition, the resin film-forming composition containing a solvent is preferably heated and dried at 70 to 130° C. for 10 seconds to 5 minutes. Among them, the thermosetting resin film-forming composition is preferably heated and dried in a manner that does not thermally cure the composition itself and the thermosetting resin film formed by the composition.

[0155] Hereinafter, the thermosetting resin film and the energy ray curable resin film will be described in further detail.

[0156] ◎Thermosetting resin film

[0157] The curing conditions when curing the thermosetting resin film to form a cured product, especially the curing conditions when forming a protective film, are not particularly limited as long as the cured product has a degree of curing that allows it to fully exert its functions, and may be appropriately selected depending on the type of thermosetting resin film, the purpose of the cured product, etc.

[0158] For example, when 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 4 hours. In addition, the thermosetting resin film can be cured while being pressurized, and the pressurization pressure at this time is preferably 0.1 to 1 MPa.

[0159] <Thermosetting resin film-forming composition>

[0160] Examples of the thermosetting resin film-forming composition include a thermosetting resin film-forming composition (III) (sometimes referred to simply as “composition (III)” in this specification) containing a polymer component (A), a thermosetting component (B) and a filler (D).

[0161] [Polymer component (A)]

[0162] 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 products of polycondensation reactions.

[0163] 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.

[0164] Examples of the polymer component (A) include polyvinyl acetal, acrylic resin, urethane resin, phenoxy resin, silicone resin, and saturated polyester resin.

[0165] Among them, the polymer component (A) is preferably polyvinyl acetal.

[0166] Examples of the polyvinyl acetal in the polymer component (A) include known polyvinyl acetals.

[0167] Among these, examples of preferred polyvinyl acetals include polyvinyl formal and polyvinyl butyral, and polyvinyl butyral is more preferred.

[0168] Examples of the polyvinyl butyral include polyvinyl butyrals having structural units represented by the following formulae (i)-1, (i)-2, and (i)-3.

[0169] [Chemical formula 1]

[0170]

[0171] In the formula, l, m and n are each independently an integer of 1 or more.

[0172] The weight average molecular weight (Mw) of polyvinyl acetal is preferably 5000 to 200000, more preferably 8000 to 100000. By making the weight average molecular weight of polyvinyl acetal in such a range, the following effects become higher: when the thermosetting resin film is attached to the concave-convex surface, the thermosetting resin film fully fills the fine grooves on the concave-convex surface and inhibits the protective film from peeling off from the concave-convex surface (for example, when the thermosetting resin film is attached to the convex point forming surface, the thermosetting resin film fully fills the fine grooves on the convex point forming surface and inhibits the protective film from peeling off from the convex point forming surface; the same below); when the thermosetting resin film is attached to the concave-convex surface, the effect of inhibiting the thermosetting resin film from remaining on the upper part of the convex part of the concave-convex surface (for example, when the thermosetting resin film is attached to the convex point forming surface, the thermosetting resin film fully fills the fine grooves on the convex point forming surface and inhibits the protective film from peeling off from the convex point forming surface; the same below); The present invention relates to an effect of suppressing the residual of the thermosetting resin film on the upper part of the bump when the film is attached to the bump forming surface; the same below); an effect of suppressing the thermosetting resin film from sticking out from the initial size on the bump forming surface (for example, when the thermosetting resin film is attached to the bump forming surface, the effect of suppressing the thermosetting resin film from sticking out from the initial size on the bump forming surface; the same below); and an effect of suppressing the unevenness of the thermosetting resin film and its cured product on the bump forming surface (for example, when the thermosetting resin film is attached to the bump forming surface, the effect of suppressing the unevenness of the thermosetting resin film and its cured product on the bump forming surface; the same below).

[0173] In this specification, unless otherwise specified, the "weight average molecular weight" means a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0174] 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 such a range, when the thermosetting resin film is attached to the concavo-convex surface, the following effects become higher: the effect of fully filling the fine grooves on the concavo-convex surface and suppressing the peeling of the protective film from the concavo-convex surface; the effect of suppressing the residue of the thermosetting resin film on the upper part of the convex part of the concavo-convex surface; the effect of suppressing the emergence of the thermosetting resin film on the concavo-convex surface; and the effect of suppressing the unevenness of the thermosetting resin film and its cured product on the concavo-convex surface.

[0175] The ratio of three or more monomers constituting polyvinyl acetal can be arbitrarily selected.

[0176] Examples of the acrylic resin in the polymer component (A) include known acrylic polymers.

[0177] The weight average molecular weight (Mw) of the acrylic resin is preferably 5000 to 1000000, more preferably 8000 to 800000. By setting the weight average molecular weight of the acrylic resin to be within such a range, when the thermosetting resin film is attached to the concavo-convex surface, the following effects become higher: the effect of fully filling the fine grooves on the concavo-convex surface and suppressing the peeling of the protective film from the concavo-convex surface; the effect of suppressing the residue of the thermosetting resin film on the upper part of the convex part of the concavo-convex surface; the effect of suppressing the emergence of the thermosetting resin film on the concavo-convex surface; and the effect of suppressing the unevenness of the thermosetting resin film and its cured product on the concavo-convex surface.

[0178] 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 to be within such a range, when the thermosetting resin film is attached to the concavo-convex surface, the following effects become higher: the effect of fully filling the fine grooves on the concavo-convex surface and suppressing the peeling of the protective film from the concavo-convex surface; the effect of suppressing the residue of the thermosetting resin film on the upper part of the convex part of the concavo-convex surface; the effect of suppressing the emergence of the thermosetting resin film on the concavo-convex surface; and the effect of suppressing the unevenness of the thermosetting resin film and its cured product on the concavo-convex surface.

[0179] 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.

[0180] 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.

[0181] Examples of the acrylic resin include polymers of one or more (meth)acrylates;

[0182] A copolymer of two or more monomers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene and N-hydroxymethyl acrylamide;

[0183] Copolymers of one or more (meth)acrylates and one or more monomers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene and N-hydroxymethyl acrylamide, etc.

[0184] In this specification, "(meth)acrylic acid" is a concept including "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid, for example, "(meth)acrylate" is a concept including "acrylate" and "methacrylate", and "(meth)acryloyl" is a concept including "acryloyl" and "methacryloyl".

[0185] Examples of the (meth)acrylate 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, and isononyl (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), etc.;

[0186] Cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate;

[0187] Aralkyl (meth)acrylates such as benzyl (meth)acrylate;

[0188] Cycloalkenyl (meth)acrylates such as dicyclopentenyl (meth)acrylate;

[0189] Cycloalkenyloxyalkyl (meth)acrylates such as dicyclopentenyloxyethyl (meth)acrylate;

[0190] (Meth)acrylic acid imide;

[0191] Glycidyl (meth)acrylates such as glycidyl (meth)acrylate;

[0192] (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;

[0193] (Meth)acrylates containing a substituted amino group such as N-methylaminoethyl (meth)acrylate, etc. Here, the "substituted amino group" refers to a group in which one or two hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom.

[0194] 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, thereby tending to improve the reliability of the package obtained by, for example, using a thermosetting resin film.

[0195] In composition (III), regardless of the type of 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 35% by mass, and more preferably 5 to 27% by mass.

[0196] [Thermosetting component (B)]

[0197] The thermosetting component (B) is a component having thermosetting properties and used to thermally cure the thermosetting resin film to form a hard cured product.

[0198] The thermosetting component (B) 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.

[0199] Examples of the thermosetting component (B) include epoxy-based thermosetting resins, polyimide resins, and unsaturated polyester resins.

[0200] Among them, the thermosetting component (B) is preferably an epoxy-based thermosetting resin.

[0201] (Epoxy thermosetting resin)

[0202] The epoxy thermosetting resin is formed of an epoxy resin (B1) and a thermosetting agent (B2).

[0203] The epoxy thermosetting resin contained in the composition (III) and the thermosetting resin film may be only one type or two or more types. When there are two or more types, the combination and ratio thereof may be arbitrarily selected.

[0204] Epoxy resin (B1)

[0205] 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.

[0206] The epoxy resin (B1) may be an epoxy resin having an unsaturated hydrocarbon group. The compatibility of an epoxy resin having an unsaturated hydrocarbon group with an acrylic resin is higher than that of an epoxy resin not having an unsaturated hydrocarbon group with an acrylic resin. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, there is a tendency that the reliability of a package obtained by, for example, using a thermosetting resin film is improved.

[0207] Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which part of the epoxy groups of a polyfunctional epoxy resin are 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.

[0208] 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 constituting the epoxy resin.

[0209] 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.

[0210] 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).

[0211] The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000 g / eq, more preferably 100 to 600 g / eq.

[0212] The epoxy resin (B1) may be used alone or in combination of two or more. When two or more epoxy resins are used in combination, the combination and ratio thereof may be arbitrarily selected.

[0213] Thermal curing agent (B2)

[0214] The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).

[0215] Examples of the thermosetting agent (B2) include compounds having two or more functional groups that can react with epoxy groups in one molecule. Examples of the functional group include phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, and groups formed by anhydriding acid groups. Phenolic hydroxyl groups, amino groups, or groups formed by anhydriding acid groups are preferred, and phenolic hydroxyl groups or amino groups are more preferred.

[0216] 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.

[0217] Examples of the amine curing agent having an amino group in the thermosetting agent (B2) include dicyandiamide (hereinafter, sometimes abbreviated as "DICY") and the like.

[0218] The heat curing agent (B2) may have an unsaturated hydrocarbon group.

[0219] Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include compounds in which part of the hydroxyl groups of a phenol 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 phenol resin.

[0220] 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.

[0221] The number average molecular weight of the resin component such as polyfunctional phenol resin, novolac phenol resin, dicyclopentadiene phenol resin, aralkyl phenol resin in the thermosetting agent (B2) is preferably 300 to 30,000, more preferably 400 to 10,000, particularly preferably 500 to 3,000.

[0222] The molecular weight of non-resin components such as biphenol and dicyandiamide in the thermosetting agent (B2) is not particularly limited, but is preferably 60 to 500, for example.

[0223] 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.

[0224] 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 is reduced, for example, the reliability of the package obtained using the thermosetting resin film is further improved.

[0225] In the composition (III), the ratio of the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) to the total content of all components other than the solvent (that is, the ratio of the content of the thermosetting component (B) in the thermosetting resin film to the total mass of the thermosetting resin film) is preferably 10 to 75% by mass, more preferably 15 to 70% by mass, for example, it can be any range of 15 to 50% by mass and 15 to 30% by mass, and can also be any range of 35 to 70% by mass and 55 to 70% by mass. By making the ratio within such a range, when the thermosetting resin film is attached to the concavo-convex surface, the following effects become higher, and a hard cured product (for example, a protective film) can be formed: the effect of fully filling the fine grooves on the concavo-convex surface and suppressing the peeling of the protective film from the concavo-convex surface; the effect of suppressing the thermosetting resin film from remaining on the convex part of the concavo-convex surface; the effect of suppressing the emergence of the thermosetting resin film on the concavo-convex surface; and the effect of suppressing the unevenness of the thermosetting resin film and its cured product on the concavo-convex surface. In particular, the lower the ratio, the easier it is to reduce the α1 and α2.

[0226] Furthermore, from the viewpoint of being able 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).

[0227] [Filling material (D)]

[0228] By adjusting the amount of the filler (D) in the composition (III) and the thermosetting resin film, the α1, α2 and X values ​​can be more easily adjusted. For example, by adjusting the amount of the filler (D) in the composition (III) and the thermosetting resin film, the linear expansion coefficient of the cured product (e.g., protective film) of the thermosetting resin film can be more easily adjusted. For example, by optimizing the linear expansion coefficient of the protective film (e.g., the first protective film) for the object of forming 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, or the heat dissipation can be improved.

[0229] The filler (D) may be any of an organic filler and an inorganic filler, but is preferably an inorganic filler.

[0230] Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium dioxide, red iron oxide (bengala), 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.

[0231] Among them, the inorganic filler is preferably silicon dioxide or aluminum oxide.

[0232] 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.

[0233] 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 10 to 65% by mass, more preferably 15 to 55% by mass, for example, it can be any range of 15 to 40% by mass and 15 to 30% by mass, or any range of 30 to 55% by mass and 40 to 55% by mass. By making the ratio in such a range, when the thermosetting resin film is attached to the concave-convex surface, the following effects become higher, and the above-mentioned linear expansion coefficient can be further easily adjusted, and the effects are: fully filling the fine grooves on the concave-convex surface, inhibiting the peeling of the protective film from the concave-convex surface; inhibiting the residue of the thermosetting resin film on the convex part of the concave-convex surface; inhibiting the emergence of the thermosetting resin film on the concave-convex surface; and inhibiting the unevenness of the thermosetting resin film and its cured product on the concave-convex surface. In particular, the higher the ratio, the easier it is to reduce the α1 and α2.

[0234] [Additive (I)]

[0235] The composition (III) and the thermosetting resin film may contain an additive (I). Examples of the additive (I) include components for adjusting the X value.

[0236] Among them, examples of the additive (I) that is preferred because it can more easily adjust the X value include rheology control agents, surfactants, silicone oils, and the like.

[0237] More specifically, examples of the rheology control agent include polyhydroxycarboxylate, polycarboxylic acid, and polyamide resin.

[0238] Examples of the surfactant include modified silicone and acrylic polymer.

[0239] 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.

[0240] Examples of the additive (I) include, in addition to the above-mentioned additives, various other general-purpose additives such as a plasticizer, an antistatic agent, an antioxidant, a gettering agent, an ultraviolet absorber, and a thickener.

[0241] 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.

[0242] 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.

[0243] 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 further preferably 0.5 to 5% by mass.

[0244] [Curing accelerator (C)]

[0245] 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).

[0246] 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 tetraphenylphosphoniumtetraphenylborate and triphenylphosphinetetraphenylborate, and the like.

[0247] 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.

[0248] When a curing accelerator (C) is used, 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, and 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 interface 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.

[0249] [Coupling agent (E)]

[0250] The composition (III) and the thermosetting resin film may contain a coupling agent (E). By using a coupling agent having a functional group that can react 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 water resistance of the cured product (e.g., protective film) of the thermosetting resin film is improved without impairing the heat resistance.

[0251] 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.

[0252] 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, Methoxysilane, 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.

[0253] 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.

[0254] When a coupling agent (E) is used, the content of the coupling agent (E) is preferably 0.03 to 10 parts by mass, more preferably 0.05 to 6 parts by mass, and particularly preferably 0.1 to 3 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 effect of using the coupling agent (E) can be more significantly obtained, that is, improving the dispersibility of the filler (D) in the resin, improving the adhesion between the thermosetting resin film and the adherend, etc. By making the content of the coupling agent (E) below the upper limit, the generation of outgas can be further suppressed.

[0255] [Crosslinking agent (F)]

[0256] 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 be bonded to 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 for bonding the functional group in the polymer component (A) to other compounds to crosslink, and by crosslinking in this manner, the initial adhesive force and cohesive force of the thermosetting resin film can be adjusted.

[0257] 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).

[0258] As the organic polyisocyanate compound, for example, aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds and alicyclic polyisocyanate compounds (hereinafter, these compounds are sometimes 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 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 part of the molecule.

[0259] More specifically, the organic polyisocyanate compound includes, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylylene 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 in which any one or two or more of toluene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or part of the hydroxyl groups of a polyol such as trimethylolpropane; lysine diisocyanate, etc.

[0260] 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.

[0261] 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).

[0262] 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.

[0263] When a crosslinking agent (F) is used, 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 polymer component (A) in the composition (III). 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.

[0264] [Other ingredients]

[0265] 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).

[0266] Examples of the other components include energy-ray-curable resins and photopolymerization initiators.

[0267] 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.

[0268] 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.

[0269] [Solvent]

[0270] The composition (III) preferably further contains a solvent. The composition (III) containing a solvent has good handleability.

[0271] 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.

[0272] 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.

[0273] From the viewpoint of being able to more uniformly mix the components contained in the composition (III), examples of more preferred solvents among the solvents contained in the composition (III) include methyl ethyl ketone and the like.

[0274] The content of the solvent in the composition (III) is not particularly limited and may be appropriately selected according to the types of components other than the solvent, for example.

[0275] <Method for preparing thermosetting resin film-forming composition>

[0276] The thermosetting resin film-forming composition such as the composition (III) can be obtained by blending the respective components constituting the composition.

[0277] The order of adding the components when blending them is not particularly limited, and two or more components may be added simultaneously.

[0278] When blending, the method for mixing the components 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.

[0279] 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 to 30°C.

[0280] ◎Energy ray curable resin film

[0281] 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 as long as the cured product has a degree of curing to a degree that allows it to fully exert its functions, and can be appropriately selected depending on the type of energy-ray-curable resin film, the purpose of the cured product, etc.

[0282] 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 .

[0283] <Energy beam curable resin film forming composition>

[0284] Examples of the energy-curable resin film-forming composition include an energy-curable resin film-forming composition (IV) (sometimes simply referred to as “composition (IV)” in this specification) containing an energy-curable component (a).

[0285] The energy-ray-curable component (a) is a component that is cured by irradiation with energy rays, and is a component for imparting film-forming properties, flexibility, and the like to the energy-ray-curable resin film.

[0286] The energy ray-curable component (a) is preferably uncured and preferably has adhesiveness, and more preferably is uncured and has adhesiveness.

[0287] The composition (IV) and the energy-ray-curable resin film may contain other components that do not belong to the energy-ray-curable component (a) within a range not impairing the effects of the present invention.

[0288] The energy-curable component (a) and the other components contained in the composition (IV) and the energy-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.

[0289] The contents of the energy-ray curable component (a) and the other components in the composition (IV) and the energy-ray curable resin film are not particularly limited and may be appropriately selected according to the types of these components, for example.

[0290] The composition (IV) preferably further contains a solvent. The composition (IV) containing a solvent has good handleability.

[0291] Examples of the solvent contained in the composition (IV) include the same solvents as those contained in the composition (III) described above.

[0292] 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.

[0293] The content of the solvent in the composition (IV) is not particularly limited and may be appropriately selected according to the types of components other than the solvent, for example.

[0294] <Method for preparing energy-beam-curable resin film-forming composition>

[0295] The energy-ray-curable resin film-forming composition such as the composition (IV) can be obtained by blending the respective components constituting the composition.

[0296] The energy-ray-curable resin film-forming composition can be prepared by the same method as the thermosetting resin film-forming composition described above, except that the types of the blended components are different, for example.

[0297] As an example of a preferred resin film of this embodiment, there can be cited a resin film which is a thermosetting resin film, wherein:

[0298] The α1 is any one of 65 ppm / K or less, 62 ppm / K or less, 55 ppm / K or less, and 48 ppm / K or less.

[0299] The α2 is any one of 165 ppm / K or less, 162 ppm / K or less, 140 ppm / K or less, and 120 ppm / K or less.

[0300] The resin film contains a polymer component (A), a thermosetting component (B) and a filler (D).

[0301] The content of the thermosetting component (B) in the resin film is in any range of 10 to 75% by mass and 15 to 70% by mass relative to the total mass of the resin film.

[0302] The content of the filler (D) in the resin film is in any range of 10 to 65% by mass and 15 to 55% by mass relative to the total mass of the resin film.

[0303] However, in the resin film, the total content of the polymer component (A), the thermosetting component (B) and the filler (D) is not more than 100% by mass relative to the total mass of the resin film.

[0304] As another example of a preferred resin film of the present embodiment, there can be cited a resin film which is a thermosetting resin film, wherein:

[0305] The α1 is any one of 65 ppm / K or less, 62 ppm / K or less, 55 ppm / K or less, and 48 ppm / K or less.

[0306] The X value is 19 or more and less than any one of 10000, 19 to 5000, 19 to 2000, 19 to 1000, 19 to 500, 19 to 300, 19 to 100 and 19 to 70,

[0307] The resin film contains a polymer component (A), a thermosetting component (B), a filler (D) and an additive (I),

[0308] The content of the thermosetting component (B) in the resin film is in any range of 10 to 75% by mass and 15 to 70% by mass relative to the total mass of the resin film.

[0309] The content of the additive (I) in the resin film is in any range of 0.5 to 10% by mass, 0.5 to 7% by mass, and 0.5 to 5% by mass relative to the total mass of the resin film.

[0310] However, in the resin film, the total content of the polymer component (A), the thermosetting component (B), the filler (D) and the additive (I) is not more than 100% by mass relative to the total mass of the resin film.

[0311] As another example of a preferred resin film of the present embodiment, there can be cited a resin film which is a thermosetting resin film, wherein:

[0312] The α1 is any one of 65 ppm / K or less, 62 ppm / K or less, 55 ppm / K or less, and 48 ppm / K or less.

[0313] The α2 is any one of 165 ppm / K or less, 162 ppm / K or less, 140 ppm / K or less, and 120 ppm / K or less.

[0314] The X value is 19 or more and less than any one of 10000, 19 to 5000, 19 to 2000, 19 to 1000, 19 to 500, 19 to 300, 19 to 100 and 19 to 70,

[0315] The resin film contains a polymer component (A), a thermosetting component (B), a filler (D) and an additive (I),

[0316] The content of the thermosetting component (B) in the resin film is in any range of 10 to 75% by mass and 15 to 70% by mass relative to the total mass of the resin film.

[0317] The content of the filler (D) in the resin film is in any range of 10 to 65% by mass and 15 to 55% by mass relative to the total mass of the resin film.

[0318] The content of the additive (I) in the resin film is in any range of 0.5 to 10% by mass, 0.5 to 7% by mass, and 0.5 to 5% by mass relative to the total mass of the resin film.

[0319] However, in the resin film, the total content of the polymer component (A), the thermosetting component (B), the filler (D) and the additive (I) is not more than 100% by mass relative to the total mass of the resin film.

[0320] ◇Composite film

[0321] A composite sheet according to one embodiment of the present invention includes a support sheet and a resin film provided on one surface of the support sheet, and the resin film is the resin film according to the above-mentioned one embodiment of the present invention.

[0322] As described above, by using the composite sheet of this embodiment, the resin film can be well attached to the uneven surface of the object to be attached. In this case, the fine grooves on the uneven surface can be fully filled, and the protective film can be prevented from peeling off from the uneven surface.

[0323] In this specification, when the resin film is used for forming the first protective film, the composite sheet is referred to as a "first protective film forming sheet", and the support sheet in the first protective film forming sheet is referred to as a "first support sheet".

[0324] On the other hand, in order to provide a second protective film on the surface (back side) opposite to the bump forming surface of a semiconductor wafer or a semiconductor chip, a second protective film forming sheet is used which is provided with a second protective film forming film for forming a second protective film. As the second protective film forming sheet, for example, a sheet which is provided with a cutting sheet and a second protective film forming film provided on the cutting sheet can be cited. When the cutting sheet has a supporting sheet identical to the supporting sheet, the supporting sheet is referred to as a "second supporting sheet".

[0325] Similarly, for example, when the first support sheet includes a substrate and an adhesive layer, they are referred to as "first substrate" and "first adhesive layer", and when the second support sheet includes a substrate and an adhesive layer, they are referred to as "second substrate" and "second adhesive layer".

[0326] Figure 3 It is a cross-sectional view schematically showing an example of the composite sheet according to the present embodiment.

[0327] The composite sheet 1 shown here is configured to include a support sheet 10 and a resin film 12 provided on one surface (sometimes referred to as “first surface” in this specification) 10 a of the support sheet 10 .

[0328] The support sheet 10 is composed of a substrate 11, a buffer layer 13 arranged on a surface 11a of the substrate 11 (sometimes referred to as the "first surface" in this specification), and an adhesive layer 14 arranged on a surface 13a of the buffer layer 13 opposite to the substrate 11 side (sometimes referred to as the "first surface" in this specification).

[0329] That is, the composite sheet 1 is formed by sequentially stacking the substrate 11, the buffer layer 13, the adhesive layer 14, and the resin film 12 in their thickness direction. The adhesive layer 14 is the outermost layer on one side (resin film 12 side) of the support sheet 10, and the surface (sometimes referred to as "first surface" in this specification) 14a of the adhesive layer 14 on the opposite side to the buffer layer 13 side is the same as the first surface 10a of the support sheet 10.

[0330] In the composite sheet 1 , the buffer layer 13 and the adhesive layer 14 are both disposed between the base material 11 and the resin film 12 .

[0331] The resin film 12 is the resin film of one embodiment of the present invention described above.

[0332] The surface (first surface) 12 a of the resin film 12 opposite to the buffer layer 13 side is a surface of the resin film 12 (in other words, the composite sheet 1 ) to be attached to the concavo-convex surface.

[0333] The composite sheet of this embodiment is not limited to Figure 3 The composite sheet shown in the figure can be used without damaging the effect of the present invention. Figure 3 Part of the structure of the composite sheet shown is changed, deleted or added.

[0334] For example, as the support sheet in the composite sheet of this embodiment, in addition to the above-mentioned support sheet composed of a substrate, a buffer layer and an adhesive layer, there can also be listed: a support sheet composed only of a substrate; a support sheet composed of a substrate and an adhesive layer arranged on one surface of the substrate; a support sheet composed of a substrate and a buffer layer arranged on one surface of the substrate.

[0335] When the support sheet includes a substrate and an adhesive layer, the adhesive layer is disposed between the substrate and the resin film in the composite sheet. When the support sheet includes a substrate and a buffer layer, the buffer layer is disposed between the substrate and the resin film in the composite sheet.

[0336] Among them, as the support sheet, the support sheet including the base material, the cushion layer and the adhesive layer as described above is more preferable.

[0337] For example, in the composite sheet of the present embodiment, the support sheet ( Figure 3 The support sheet 10 in the composite sheet 1 shown can also be on the substrate ( Figure 3 The substrate 11) and the buffer layer ( Figure 3 The composite sheet 1 shown has adhesion layers between the buffer layers 13).

[0338] The adhesion layer improves the adhesion between the substrate and the buffer layer and highly suppresses the peeling of the substrate and the buffer layer in the composite sheet. Therefore, when a composite sheet having an adhesion layer is used, the laminated structure of the substrate, the adhesion layer and the buffer layer can be more stably maintained.

[0339] The sealing layer is in the form of a sheet or a film.

[0340] As a preferable adhesion layer, the adhesion layer containing ethylene-vinyl acetate copolymer resin (EVA) etc. is mentioned, for example.

[0341] For example, the composite sheet of this embodiment may also have an outermost layer ( Figure 3 The composite sheet 1 shown has a release film on the resin film 12).

[0342] Next, each layer constituting the composite sheet of the present embodiment will be described.

[0343] ◎Base material

[0344] The substrate is in a sheet or film shape, and examples of its constituent material include various resins.

[0345] 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 by using ethylene as a monomer); and vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers. (resin obtained by 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.

[0346] In addition, the resin may include, for example, a polymer alloy such as a mixture of the polyester and other resins. The amount of the resin other than polyester in the polymer alloy of the polyester and other resins is preferably relatively small.

[0347] 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.

[0348] 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.

[0349] 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.

[0350] 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 180 μm.

[0351] 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 the layers constituting the substrate.

[0352] The substrate is preferably a substrate with high thickness accuracy, that is, a substrate in which the thickness deviation is suppressed at any position. Among the above-mentioned constituent materials, materials that can be used to constitute such a substrate with high thickness accuracy include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, etc.

[0353] In addition to the 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).

[0354] The substrate may be transparent or opaque, may be colored according to the purpose, and may have other layers deposited thereon.

[0355] When the resin film is energy ray-curable, it is preferred that the substrate transmits energy rays.

[0356] The substrate can be produced by a known method. For example, a substrate containing a resin can be produced by molding a resin composition containing the resin.

[0357] ◎Buffer layer

[0358] The buffer layer is in sheet or film form and has a buffering effect on the force applied to the buffer layer and the layer adjacent thereto. Here, as the "layer adjacent to the buffer layer", for example, the resin film, a layer equivalent to a cured product of the resin film (for example, a protective film such as the first protective film) and an adhesive layer can be listed.

[0359] The constituent material of the buffer layer is not particularly limited.

[0360] As a preferable buffer layer, the buffer layer containing urethane (meth)acrylate etc. is mentioned, for example.

[0361] In the same manner as the above-mentioned resin film, a test piece of a buffer layer with 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, and 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) is more likely to penetrate the resin film.

[0362] 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. 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 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 further easily penetrate the resin film.

[0363] The buffer layer may be composed of one layer (single layer) or two or more layers. When the buffer layer is composed of multiple layers, the multiple layers may be the same as or different from each other, and the combination of the multiple layers is not particularly limited.

[0364] 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.

[0365] 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.

[0366] <<Composition for forming buffer layer>>

[0367] The buffer layer can be formed using a buffer layer forming composition containing the constituent material of the buffer layer such as the resin. For example, the buffer layer can be formed at the target site by extruding the buffer layer forming composition onto the formation target surface of the buffer layer. 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 of the components that do not vaporize at room temperature in the buffer layer forming composition is usually the same as the content ratio of the components of the buffer layer.

[0368] <Buffer layer forming composition (V)>

[0369] As a buffer layer forming composition, the buffer layer forming composition (V) containing urethane (meth)acrylate etc. are mentioned, for example.

[0370] 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.

[0371] [Other ingredients]

[0372] 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.

[0373] There is no particular restriction on the other components, and they can be appropriately selected depending on the purpose.

[0374] 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 can be arbitrarily selected.

[0375] 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.

[0376] ◎Adhesive layer

[0377] The adhesive layer is in a sheet or film shape and contains an adhesive.

[0378] Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber-based resins, silicone resins, epoxy-based resins, polyvinyl ethers, polycarbonates, and ester-based resins, and acrylic resins are preferred.

[0379] In this specification, "adhesive resin" includes resins having adhesive properties and resins having adhesive properties. For example, the adhesive resin includes not only resins having adhesive properties per se, but also resins that exhibit adhesive properties by being used together with other components such as additives, resins that exhibit adhesive properties due to the presence of triggers such as heat or water, and the like.

[0380] The adhesive layer may consist of one layer (single layer) or two or more layers. When the adhesive layer consists of multiple layers, the multiple layers may be the same as or different from each other, and the combination of the multiple layers is not particularly limited.

[0381] The thickness of the adhesive layer is preferably 10 to 180 μm, more preferably 30 to 120 μm, and particularly preferably 40 to 80 μm. By making the thickness of the adhesive layer above the lower limit, the effect of providing the adhesive layer can be more significantly obtained. By making the thickness of the adhesive layer below the upper limit, the support sheet can be thinned.

[0382] Here, “the thickness of the adhesive layer” refers to the thickness of the entire adhesive layer. For example, the thickness of an adhesive layer composed of a plurality of layers refers to the total thickness of all the layers constituting the adhesive layer.

[0383] The adhesive layer can be formed using an energy-ray-curable adhesive or a non-energy-ray-curable adhesive. That is, the adhesive layer can be either energy-ray-curable or non-energy-ray-curable. The energy-ray-curable adhesive layer can easily adjust the physical properties before and after curing. For example, by curing the energy-ray-curable adhesive layer before picking up the semiconductor chip with the first protective film described later, the semiconductor chip with the first protective film can be picked up more easily.

[0384] <<Adhesive composition>>

[0385] The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the adhesive composition is applied to the surface of the adhesive layer and dried as needed, thereby forming the adhesive layer at the target site. The content ratio of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the content ratio of the components in the adhesive layer.

[0386] The adhesive composition can be applied by, for example, the same method as the above-mentioned application of the resin film-forming composition.

[0387] The drying conditions of the adhesive composition are not particularly limited. When the adhesive composition contains a solvent described below, it is preferably dried by heating. The adhesive composition containing a solvent is preferably dried at 70 to 130° C. for 10 seconds to 5 minutes, for example.

[0388] When an adhesive layer is provided on a substrate or a buffer layer, for example, an adhesive composition is applied on the substrate or the buffer layer and dried as required, thereby laminating an adhesive layer on the substrate or the buffer layer. In addition, when an adhesive layer is provided on a substrate or a buffer layer, for example, an adhesive composition can also be applied on a release film and dried as required, thereby pre-forming an adhesive layer on the release film, and the exposed surface of the adhesive layer is laminated to a surface of the substrate or the buffer layer, thereby laminating an adhesive layer on the substrate or the buffer layer. At this time, the release film can be removed at any time during the manufacturing process or use of the composite sheet.

[0389] When the adhesive layer is energy-ray-curable, examples of energy-ray-curable adhesive compositions include: an adhesive composition (I-1) containing a non-energy-ray-curable adhesive resin (I-1a) (hereinafter, sometimes abbreviated as "adhesive resin (I-1a)") and an energy-ray-curable compound; an adhesive composition (I-2) containing an energy-ray-curable adhesive resin (I-2a) (hereinafter, sometimes abbreviated as "adhesive resin (I-2a)") having an unsaturated group introduced into the side chain of the adhesive resin (I-1a); an adhesive composition (I-3) containing the adhesive resin (I-2a) and an energy-ray-curable low molecular weight compound, etc.

[0390] Examples of the adhesive composition (I-1), the adhesive composition (I-2), and the adhesive composition (I-3) include the first adhesive composition (I-1), the first adhesive composition (I-2), and the first adhesive composition (I-3) described in paragraphs 0045 to 0105 of International Publication No. 2017 / 078047.

[0391] When the adhesive layer is non-energy ray-curable, examples of the non-energy ray-curable adhesive composition include an adhesive composition (I-4) containing the above-mentioned adhesive resin (I-1a).

[0392] <<Method for preparing adhesive composition>>

[0393] The adhesive compositions such as the adhesive compositions (I-1) to (I-4) can be obtained by blending the above-mentioned adhesive with various components other than the above-mentioned adhesive as required to constitute the adhesive composition.

[0394] The order of adding the components when blending them is not particularly limited, and two or more components may be added simultaneously.

[0395] When blending, the method for mixing the components 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.

[0396] 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 to 30°C.

[0397] ◎Resin film

[0398] Since the resin film in the composite sheet of the present embodiment is the same as the resin film described above, a detailed description thereof will be omitted here.

[0399] As an example of a preferred composite sheet of the present embodiment, there can be cited a composite sheet comprising a support sheet and a resin film provided on one surface of the support sheet, wherein:

[0400] The support sheet includes a substrate, a buffer layer provided on one surface of the substrate, and an adhesive layer provided on a surface of the buffer layer opposite to the substrate side, wherein the buffer layer and the adhesive layer are arranged between the substrate and the resin film.

[0401] The resin film is a thermosetting resin film,

[0402] The α1 is any one of 65 ppm / K or less, 62 ppm / K or less, 55 ppm / K or less, and 48 ppm / K or less.

[0403] The α2 is any one of 165 ppm / K or less, 162 ppm / K or less, 140 ppm / K or less, and 120 ppm / K or less.

[0404] The resin film contains a polymer component (A), a thermosetting component (B) and a filler (D), and the content of the thermosetting component (B) in the resin film is in any range of 10 to 75% by mass and 15 to 70% by mass relative to the total mass of the resin film.

[0405] The content of the filler (D) in the resin film is in any one of a range of 10 to 65% by mass and a range of 15 to 55% by mass relative to the total mass of the resin film.

[0406] As another example of a preferred composite sheet of the present embodiment, there can be cited a composite sheet comprising a support sheet and a resin film provided on one surface of the support sheet, wherein:

[0407] The support sheet includes a substrate, a buffer layer provided on one surface of the substrate, and an adhesive layer provided on a surface of the buffer layer opposite to the substrate side, wherein the buffer layer and the adhesive layer are arranged between the substrate and the resin film.

[0408] The resin film is a thermosetting resin film,

[0409] The α1 is any one of 65 ppm / K or less, 62 ppm / K or less, 55 ppm / K or less, and 48 ppm / K or less.

[0410] The X value is 19 or more and less than any one of 10000, 19 to 5000, 19 to 2000, 19 to 1000, 19 to 500, 19 to 300, 19 to 100 and 19 to 70,

[0411] The resin film contains a polymer component (A), a thermosetting component (B), a filler (D) and an additive (I),

[0412] The content of the thermosetting component (B) in the resin film is in any range of 10 to 75% by mass and 15 to 70% by mass relative to the total mass of the resin film.

[0413] The content of the additive (I) in the resin film is in any range of 0.5 to 10% by mass, 0.5 to 7% by mass, and 0.5 to 5% by mass relative to the total mass of the resin film.

[0414] As another example of a preferred composite sheet of the present embodiment, there can be cited a composite sheet comprising a support sheet and a resin film provided on one surface of the support sheet, wherein:

[0415] The support sheet includes a substrate, a buffer layer provided on one surface of the substrate, and an adhesive layer provided on a surface of the buffer layer opposite to the substrate side, wherein the buffer layer and the adhesive layer are arranged between the substrate and the resin film.

[0416] The resin film is a thermosetting resin film,

[0417] The α1 is any one of 65 ppm / K or less, 62 ppm / K or less, 55 ppm / K or less, and 48 ppm / K or less.

[0418] The α2 is any one of 165 ppm / K or less, 162 ppm / K or less, 140 ppm / K or less, and 120 ppm / K or less.

[0419] The X value is 19 or more and less than any one of 10000, 19 to 5000, 19 to 2000, 19 to 1000, 19 to 500, 19 to 300, 19 to 100 and 19 to 70,

[0420] The resin film contains a polymer component (A), a thermosetting component (B), a filler (D) and an additive (I),

[0421] The content of the thermosetting component (B) in the resin film is in any range of 10 to 75% by mass and 15 to 70% by mass relative to the total mass of the resin film.

[0422] The content of the filler (D) in the resin film is in any range of 10 to 65% by mass and 15 to 55% by mass relative to the total mass of the resin film.

[0423] The content of the additive (I) in the resin film is in any range of 0.5 to 10% by mass, 0.5 to 7% by mass, and 0.5 to 5% by mass relative to the total mass of the resin film.

[0424] ◇Manufacturing method of composite sheet

[0425] The composite sheet can be manufactured by sequentially stacking the above-mentioned layers in a corresponding positional relationship. The method of forming each layer is the same as described above.

[0426] For example, a composite sheet in which a base material, a cushion layer, an adhesive layer, and a resin film are sequentially laminated in their thickness direction can be produced by the following method.

[0427] That is, the buffer layer forming composition is extruded onto the substrate, thereby laminating the buffer layer on the substrate. In addition, the above-mentioned adhesive composition is applied to the peeling treatment surface of the release film and dried as needed, thereby laminating the adhesive layer. Then, the adhesive layer on the release film is laminated with the buffer layer on the substrate, thereby obtaining a laminated sheet with a release film in which the substrate, the buffer layer, the adhesive layer and the release film are sequentially laminated along their thickness directions.

[0428] Furthermore, the resin film is laminated by applying the resin film-forming composition onto the release-treated surface of the release film and drying it as necessary.

[0429] Then, the release film is removed from the laminated sheet obtained above, and the exposed surface of the newly generated adhesive layer is bonded to the exposed surface of the resin film on the release film, thereby obtaining a composite sheet composed of a substrate, a buffer layer, an adhesive layer, a resin film and a release film laminated in sequence along their thickness direction. The release film on the resin film can be removed when the composite sheet is used.

[0430] A composite sheet having other layers in addition to the above-mentioned layers can be produced by appropriately adding one or both of the steps of forming and laminating the other layers in the above-mentioned production method so that the lamination positions of the other layers are at appropriate positions.

[0431] ◇Method for manufacturing semiconductor chip with first protective film (method for using resin film and composite sheet)

[0432] As described above, when the resin film of the present embodiment is attached to the concavo-convex surface of the object to be attached, the resin film of the present embodiment has extremely excellent characteristics in that the convex portion is penetrated to expose the upper portion thereof and the entire concavo-convex surface can be covered. That is, the resin film of the present embodiment is suitable for being attached to the concavo-convex surface of the object to be attached having a concavo-convex surface. Furthermore, when the concavo-convex surface has fine grooves, the resin film can be used to fully fill such grooves, and as a result, the protective film can be used to fully fill the grooves. Furthermore, it is possible to suppress the protective film from peeling off from the concavo-convex surface.

[0433] The resin film of this embodiment is suitable for protecting the concavoconvex surface and side of the semiconductor chip, for example, it is particularly suitable for manufacturing a semiconductor chip with a first protective film having a semiconductor chip and a first protective film arranged on the side of the semiconductor chip and a surface with bumps (bump forming surface). At this time, the concavoconvex surface is the bump forming surface of the semiconductor chip, and the convex portion is the bump. In addition, the concave portion includes a groove on the bump forming surface. And the semiconductor chip with the first protective film is suitable for flip-chip bonding to a substrate through the bumps therein, thereby being used in the manufacture of semiconductor devices.

[0434] The resin film of the present embodiment is suitably used in the form of the above-mentioned composite sheet.

[0435] Hereinafter, a method for manufacturing a semiconductor chip with a first protective film when the composite sheet is used will be described.

[0436] A method for manufacturing a semiconductor chip with a first protective film according to an embodiment of the present invention is a method for manufacturing a semiconductor chip with a first protective film using a semiconductor wafer, wherein the semiconductor chip with the first protective film comprises a semiconductor chip and a first protective film arranged on the side surface and the surface having a bump of the semiconductor chip, the semiconductor wafer having a bump and a groove as a dividing position of the semiconductor wafer on one surface thereof, and the manufacturing method comprises an attaching step, in which the resin film in the composite sheet according to an embodiment of the present invention is attached to the one surface of the semiconductor wafer, thereby producing a semiconductor chip having the resin film on the one surface and the groove filled with the resin film. A semiconductor wafer with a resin film, the manufacturing method further comprising: after the attaching step, curing the resin film to form the first protective film, thereby producing a semiconductor wafer with a first protective film having the semiconductor wafer and the first protective film arranged on the one surface of the semiconductor wafer and filling the groove; after the curing step (1), dividing the semiconductor wafer, thereby producing a semiconductor chip group with a first protective film having a plurality of semiconductor chips and the first protective film arranged on the surfaces with the bumps of the plurality of semiconductor chips and the gaps between the semiconductor chips; and after the dividing step (1), The method further comprises the steps of: cutting the first protective film in the gaps between the semiconductor chips in the semiconductor chip group with the first protective film, thereby producing the semiconductor chip with the first protective film (in this specification, the manufacturing method at this time is sometimes referred to as "manufacturing method (1)"), or comprising: after the attaching step and after the curing step (1), cutting the first protective film along the groove in the semiconductor wafer with the first protective film, thereby producing a semiconductor wafer with the cut first protective film; and after the cutting step (2), dividing the semiconductor wafer, thereby producing the semiconductor chip with the first protective film. In the method, the manufacturing method at this time is sometimes referred to as "manufacturing method (2)"), or it comprises: after the attaching step, dividing the semiconductor wafer, thereby producing a semiconductor chip group with a resin film, which has a plurality of semiconductor chips and the resin film provided on the surfaces with the bumps of the plurality of semiconductor chips and the gaps between the semiconductor chips; after the dividing step (3), curing the resin film to form the first protective film, thereby producing a semiconductor chip group with a first protective film, which has a plurality of semiconductor chips and the first protective film provided on the surfaces with the bumps of the plurality of semiconductor chips and the gaps between the semiconductor chips.and a cutting step (3) of cutting the first protective film along the gaps between the semiconductor chips in the semiconductor chip group with the first protective film to obtain the semiconductor chip with the first protective film (in this specification, the manufacturing method at this time is sometimes referred to as "manufacturing method (3)");

[0437] These production methods are described below.

[0438] <<Manufacturing method (1)>>

[0439] Figure 4A to Figure 4E A cross-sectional view schematically shows a manufacturing method (1) using Figure 3 The composite sheet 1 shown is an example of a method for manufacturing a semiconductor chip with a first protective film.

[0440] Here, since the resin film is used for forming 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 ”.

[0441] <Attachment process>

[0442] In the attaching step of the manufacturing method (1), if Figure 4A to Figure 4B As shown, the resin film 12 in the first protective film forming sheet 1 is attached to one surface (hereinafter sometimes referred to as a “bump formation surface”) 9 a of a semiconductor wafer 9 .

[0443] The semiconductor wafer 9 has a plurality of bumps 91 on its bump formation surface 9 a and a plurality of grooves 90 as division positions of the semiconductor wafer 9 .

[0444] In this step, the first protective film forming sheet 1 is placed on the semiconductor wafer 9 , thereby manufacturing a semiconductor wafer 901 with a resin film in which the bump formation surface 9 a of the semiconductor wafer 9 has the resin film 12 and the grooves 90 are filled with the resin film 12 .

[0445] Here, the top 9101 of the bump 91 is in a state of protruding from the resin film 12. The degree to which the top 9101 of the bump 91 protrudes from the resin film 12 can be adjusted by adjusting the composition and thickness of the resin film 12 or the bonding conditions of the resin film 12.

[0446] In the attaching step of the manufacturing method (1), if Figure 4A As shown, for example, first, the first protective film forming sheet 1 is arranged so that its resin film 12 faces the bump formation surface 9 a of the semiconductor wafer 9 .

[0447] The thickness of the semiconductor wafer 9 to which the resin film 12 is attached is not particularly limited, but is preferably 100 to 1000 μm, more preferably 200 to 900 μm, and further preferably 300 to 800 μm. By making the thickness of the semiconductor wafer 9 greater than or equal to the lower limit, it is easy to suppress the warping caused by the shrinkage of the resin film 12 during curing. By making the thickness of the semiconductor wafer 9 less than or equal to the upper limit, the time for dividing the semiconductor wafer 9 described later can be further shortened.

[0448] In this specification, “the thickness of the semiconductor wafer” refers to the thickness of the semiconductor wafer in a region without the trench when the semiconductor wafer has the trench.

[0449] 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 residue of the resin film 12 on the top of the bump 91 becomes higher.

[0450] In this specification, the "height of a bump" refers to the height of a portion of the bump that exists at the highest position from the bump formation surface.

[0451] 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 greater than or equal to the lower limit, the function of the bump 91 can be further improved. By making the width of the bump 91 less than or equal to the upper limit, the effect of suppressing the residue of the resin film 12 on the upper part of the bump 91 becomes higher.

[0452] 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.

[0453] 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 residue of the resin film 12 on the upper part of the bump 91 becomes higher.

[0454] In this specification, "the distance between adjacent bumps" refers to the minimum value of the distance between the surfaces of adjacent bumps.

[0455] If the depth of the groove 90 is greater than the thickness of the semiconductor chip as the final target and less than the thickness of the semiconductor wafer 9 before grinding described later, it is not particularly limited, but is preferably 30 to 700 μm, more preferably 60 to 600 μm, and further preferably 100 to 500 μm. By making the depth of the groove 90 greater than the lower limit, the division of the semiconductor wafer 9 described later becomes easier. By making the depth of the groove 90 less than the upper limit, the strength of the semiconductor wafer 9 becomes higher.

[0456] In this specification, when the depth of a groove is not a constant value, the maximum value of the depth of the groove is used as the “depth of the groove”.

[0457] The width of the groove 90 is not particularly limited, but is preferably 10 to 2000 μm, more preferably 30 to 1000 μm, further preferably 40 to 500 μm, and particularly preferably 50 to 300 μm. By making the width of the groove 90 greater than the lower limit, the effect of preventing contact between adjacent semiconductor chips is increased when the semiconductor wafer 9 is divided as described later. By making the width of the groove 90 less than the upper limit, the strength of the semiconductor wafer 9 becomes higher.

[0458] In this specification, when the width of a groove is not a constant value, the maximum value of the width of the groove is used as the “width of the groove”.

[0459] Next, in the attaching step of the manufacturing method (1), the 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 .

[0460] Thus, the first surface 12a of the 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. At this time, the resin film 12 is softened by heating the resin film 12, and the resin film 12 spreads between the bumps 91 in a manner covering the bumps 91, closely adheres to the bump forming surface 9a, and covers the surface 91a of the bump 91, especially the surface 91a near the bump forming surface 9a, and fills the base of the bump 91. Therefore, the resin film 12 is fully closely adhered to the bump forming surface 9a and the base of the bump 91, and further, the resin film 12 fully fills the groove 90 on the semiconductor wafer 9.

[0461] Through the above methods, such as Figure 4B As shown, a semiconductor wafer 901 with a resin film is obtained.

[0462] As described above, as a method of press-bonding the first protective film forming sheet 1 to the semiconductor wafer 9 , a known method of press-bonding and attaching various sheets to an object can be applied, for example, a method using a laminating roll.

[0463] The heating temperature of the first protective film forming sheet 1 (resin film 12 ) when being pressure-bonded to the semiconductor wafer 9 may be a temperature at which the resin film 12 is not completely cured or is not excessively cured, and may be, for example, 80° C. to 100° C.

[0464] The heating temperature is preferably 85 to 95° C. from the viewpoint that the resin film 12 is sufficiently in close contact with the bump forming surface 9 a and the base of the bump 91 and the effect of the resin film 12 sufficiently filling the groove 90 is further enhanced.

[0465] The pressure at which the first protective film-forming sheet 1 (resin film 12 ) is pressed against the semiconductor wafer 9 is not particularly limited, and may be, for example, 0.1 to 1.5 MPa.

[0466] The pressure is preferably 0.3 to 1 MPa from the viewpoint that the resin film 12 is sufficiently in close contact with the bump forming surface 9a and the base of the bump 91 and the effect of the resin film 12 sufficiently filling the groove 90 is further enhanced.

[0467] As described above, when the first protective film forming sheet 1 is pressed against the semiconductor wafer 9, the resin film 12, the adhesive layer 14 and the buffer layer 13 in the first protective film forming sheet 1 are subjected to pressure from the bump 91, and initially, the first surface 12a of the resin film 12, the first surface 14a of the adhesive layer 14 and the first surface 13a of the buffer layer 13 are deformed into a concave shape. Then, the resin film 12 subjected to pressure from the bump 91 in this state sometimes breaks. If the X value is greater than 19 and less than 10000 (19≤X value<10000), such a break in the resin film 12 will occur. At this time, at the stage where the first surface 12a of the resin film 12 is finally pressed against the bump forming surface 9a of the semiconductor wafer 9, the upper portion 910 including the top 9101 of the bump 91 is in a state of penetrating the resin film 12 and protruding. In addition, at this final stage, the upper portion 910 of the bump 91 usually does not penetrate the buffer layer 13. This is because the buffer layer 13 has a buffering effect on the pressure applied by the bump 91 .

[0468] Figure 4B It is shown that at the stage where the attaching process is completed, the resin film 12 does not remain at all or hardly remains on the upper portion 910 including the top 9101 of the bump 91, and the resin film 12 is suppressed from remaining on the upper portion 910 of the bump 91.

[0469] In addition, in this specification, unless otherwise specified, "almost no resin film remains on the upper part of the bump" means that a small amount of resin film remains on the upper part of the bump, but 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.

[0470] When the X value is 19 or more and less than 10000, the resin film 12 can be suppressed from protruding from the initial size at the stage where the attaching step is completed, and thus the resin film 12 can be suppressed from protruding from the bump formation surface 9 a of the semiconductor wafer 9 .

[0471] When the X value is 19 or more and less than 10000, the unevenness of the resin film 12 on the bump forming surface 9a can be suppressed at the stage of completing the attaching process. More specifically, the phenomenon that the area other than the upper part 910 of the bump 91 (for example, the base near the bump forming surface 9a) or the area near the bump 91 of the bump forming surface 9a is not covered by the resin film 12 and is accidentally exposed can be suppressed.

[0472] <Curing process (1)>

[0473] In the curing step (1) after the attaching step of the manufacturing method (1), the first support sheet 10 is removed from the semiconductor wafer 901 with the resin film, and then Figure 4C As shown, the resin film 12 is cured to form a first protective film 12 ′, thereby manufacturing a semiconductor wafer 902 with a first protective film including the semiconductor wafer 9 and the first protective film 12 ′ provided on the bump formation surface 9 a of the semiconductor wafer 9 and filling the groove 90 .

[0474] In the curing step (1), when the resin film 12 is thermosetting, the resin film 12 is cured by heating, and when the resin film 12 is energy-ray curable, the resin film 12 is cured by irradiating energy rays. The heating conditions and energy-ray irradiation conditions at this time are as described above.

[0475] Reference numeral 9 b denotes the surface (back surface) of the semiconductor wafer 9 which is opposite to the bump formation surface 9 a .

[0476] When the adhesive layer 14 in the support sheet 10 is energy ray-curable, the support sheet 10 can be removed more easily from the semiconductor wafer 901 with a resin film by curing the adhesive layer 14 .

[0477] In the semiconductor wafer 901 with a resin film, since the resin film 12 is fully filled in the groove 90 on the semiconductor wafer 9, the curing step (1) can obtain a semiconductor wafer 902 with a first protective film in which the first protective film 12' is fully filled in the groove 90. In addition, in the semiconductor wafer 902 with a first protective film, the first protective film 12' is sufficiently in close contact with the bump forming surface 9a and the base of the bump 91, and the peeling of the first protective film 12' from these parts is suppressed.

[0478] <Division process (1)>

[0479] In the dividing step (1) after the curing step (1), the semiconductor wafer 9 is divided, such as Figure 4D As shown, a semiconductor chip group 903 with a first protective film is prepared, which includes multiple semiconductor chips 9' and a first protective film 12'. The first protective film 12' is set on the surface with bumps (hereinafter sometimes referred to as "bump formation surface") 9a' of the multiple semiconductor chips 9' and the gaps 90' between the semiconductor chips 9'.

[0480] The gap 90 ′ between the semiconductor chips 9 ′ refers to a region sandwiched by the side surfaces 9 c ′ of the adjacent semiconductor chips 9 ′.

[0481] The division of the semiconductor wafer 9 can be performed by a known method. In the present embodiment, for example, the back side 9b of the semiconductor wafer 9 can be ground using a grinding device such as a grinder. At this time, the semiconductor wafer 9 is ground along the direction from the back side 9b of the semiconductor wafer 9 toward the bump forming surface 9a until the ground surface (back side 9b) reaches the groove 90 (in other words, until the groove 90 appears, and in other words, until the gap 90' is formed). As a result, the thickness of the semiconductor wafer 9 becomes thinner and the groove 90 becomes the division position, the semiconductor wafer 9 is divided, and the gap 90' is formed by the groove 90. The back side 9b of the semiconductor wafer 9 is ground until the thickness of the semiconductor chip 9' reaches the target value. For example, the grinding can be stopped at the stage where the grinding surface reaches the groove 90, or after the grinding surface reaches the groove 90, the first protective film 12' and the back side 9b present in the gap 90' can be further ground simultaneously.

[0482] In the dividing step (1), a back grinding tape may be attached to the surface of the semiconductor wafer 902 with the first protective film on the bump formation surface 9a side to grind the back surface 9b of the semiconductor wafer 9 as needed.

[0483] For convenience, in this specification, the back surface of the semiconductor wafer 9 being ground is also denoted by reference numeral 9 b .

[0484] Reference numeral 9b' denotes a surface (back surface) of the semiconductor chip 9' that is opposite to the bump formation surface 9a'.

[0485] In the semiconductor chip group 903 with the first protective film, all the semiconductor chips 9' are held together by a first protective film 12'. When the back grinding tape is used as described above, all the semiconductor chips 9' are held together by a first protective film 12' and the back grinding tape attached to the surface of the semiconductor chip group 903 with the first protective film on the side of the bump forming surface 9a'.

[0486] <Cutting process (1)>

[0487] In the cutting step (1) after the dividing step (1), the first protective film 12' is cut along the gaps 90' between the semiconductor chips 9' in the semiconductor chip group 903 with the first protective film, thereby Figure 4E As shown, a semiconductor chip 900 with a first protective film is manufactured.

[0488] The semiconductor chip 900 with the first protective film comprises a semiconductor chip 9' and a first protective film 120' provided on the side surface 9c' and the bump forming surface 9a' of the semiconductor chip 9'. The side surface 9c' and the bump forming surface 9a' of the semiconductor chip 9' are respectively protected by the cut first protective film 120', and the protection effect obtained by the semiconductor chip 9' is very high.

[0489] When the semiconductor chip 9' is viewed downward from the top of the bump forming surface 9a' side of the semiconductor chip 9' and the planar shape of the semiconductor chip 9' is a square, one semiconductor chip 9' has four side surfaces 9c'. Therefore, in the semiconductor chip 900 with the first protective film, the first protective film 120' after being cut is integrally provided on all (i.e., four) side surfaces 9c' and one bump forming surface 9a' of the semiconductor chip 9'. In this specification, the "first protective film after being cut" is sometimes referred to as the "first protective film".

[0490] In the cutting step (1), the first protective film 12' is cut along the outer periphery (in other words, the side 9c') of the semiconductor chip 9'. At this time, it is preferred to cut the first protective film 12' filling the gap 90' between adjacent semiconductor chips 9' along the outer periphery (in other words, the side 9c') of the semiconductor chip 9' and divide it into two. As a result, the cut first protective film 120' with a more uniform shape can be provided on each side 9c' of the semiconductor chip 9'.

[0491] The first protective film 12 ′ can be cut by a known method such as blade cutting or laser cutting.

[0492] The first protective film 12' can be cut, for example, by attaching a known dicing sheet to the back surface 9b' of the semiconductor chip 9' in the semiconductor chip group 903 with the first protective film and removing the back grinding tape. When the back grinding tape has an energy ray-curable adhesive layer, the adhesive layer is cured by irradiating energy rays, thereby making it easier to remove the back grinding tape from the semiconductor chip group 903 with the first protective film.

[0493] In the semiconductor chip 900 with the first protective film, the first protective film 120' is sufficiently closely attached to the bump forming surface 9a' of the semiconductor chip 9', the base of the bump 91 and the side surface 9c', and the peeling of the first protective film 120' from these parts is suppressed. In addition, the first protective film 120' with a sufficient thickness is provided on the side surface 9c' of the semiconductor chip 9'.

[0494] In addition, when the X value is greater than 19 and less than 10000, further, in the semiconductor chip 900 with the first protective film, the top 9101 of the bump 91 protrudes from the first protective film 120', the first protective film 120' is completely or almost not attached to the upper part 910 of the bump 91 including the top 9101, and the adhesion of the first protective film 120' to the upper part 910 of the bump 91 is suppressed.

[0495] Furthermore, in the semiconductor chip 900 with the first protective film, the protrusion of the first protective film 120 ′ on the bump formation surface 9 a ′ of the semiconductor chip 9 ′ is suppressed.

[0496] Furthermore, the unevenness of the first protective film 120' on the bump forming surface 9a' of the semiconductor chip 9' is suppressed. More specifically, when the first protective film 120' is provided on the bump forming surface 9a', the region other than the upper portion 910 of the bump 91 (for example, the base near the bump forming surface 9a') or the region near the bump 91 on the bump forming surface 9a' is not covered by the first protective film 120' and is inadvertently exposed.

[0497] <<Manufacturing method (2)>>

[0498] Figure 5A to Figure 5E A cross-sectional view schematically showing a manufacturing method (2) using Figure 3 The composite sheet 1 shown is another example of a method for manufacturing a semiconductor chip with a first protective film.

[0499] <Attachment process, curing process (1)>

[0500] like Figure 5A to Figure 5C As shown, in the manufacturing method (2), the attaching step and the curing step (1) are performed in the same manner as the manufacturing method (1) to manufacture the semiconductor wafer 902 with the first protective film.

[0501] <Cutting process (2)>

[0502] In the cutting step (2) after the curing step (1) of the manufacturing method (2), the first protective film 12' is cut along the groove 90 in the semiconductor wafer 902 with the first protective film, thereby Figure 5DAs shown, a semiconductor wafer 904 with a first protection film that has been cut is manufactured.

[0503] In this step, the first protection film 12' filled in the trench 90 is preferably cut along the side surface 90c of the trench 90. Thus, the first protection film having a more uniform shape after cutting can be provided on each side surface of the semiconductor chip.

[0504] In the cutting step (2), the first protective film 12' is cut from the surface 12b' of the first protective film 12' on the opposite side to the semiconductor wafer 9 side toward the surface 12a' on the semiconductor wafer 9 side. At this time, the cut of the first protective film 12' may not reach the front end of the first protective film 12' in the depth direction of the groove 90, but from the viewpoint of making it easier to divide the semiconductor wafer 9 described later, the closer the cut reaches the front end, the better, and it is more preferable that the cut reaches the front end, that is, the first protective film 12' is cut. Figure 5D The case where the cut of the first protective film 12 ′ is made to reach the front end portion and the first protective film 12 ′ is cut (the first protective film 120 ′ after cutting is produced) is shown.

[0505] On the other hand, when the semiconductor wafer 9 is divided into semiconductor chips by grinding the back side 9b of the semiconductor wafer 9 described later, from the viewpoint of suppressing the cracking or defect of the corner of the semiconductor chip and suppressing the cracking or defect of the first protective film 12' present near the corner of the semiconductor chip, it is preferred that the reaching position of the cut of the first protective film 12' coincides with the position where the back side of the semiconductor chip is estimated to be finally formed, or is located near such a position.

[0506] Similar to the above-mentioned cutting step (1), the first protective film 12 ′ can be cut by a known method such as blade cutting or laser cutting.

[0507] <Division process (2)>

[0508] In the dividing step (2) after the cutting step (2), the semiconductor wafer 9 is divided, thereby Figure 5E As shown, a semiconductor chip 900 with a first protective film is manufactured.

[0509] The semiconductor chip 900 with the first protective film obtained in the dividing step (2) is the same as the semiconductor chip 900 with the first protective film obtained in the cutting step (1).

[0510] Similar to the above-mentioned dividing step (1), the semiconductor wafer 9 can be divided by a known method.

[0511] For example, when the back side 9b of the semiconductor wafer 9 is ground using a grinding device such as a grinder, the back side 9b is ground in a direction from the back side 9b toward the bump forming surface 9a until the ground surface (back side 9b) reaches the groove 90. In the cutting step (2), when the cut of the first protective film 12' does not reach the front end of the first protective film 12' in the depth direction of the groove 90, the back side 9b and the first protective film 12' are further ground simultaneously until the ground surface reaches the cut of the first protective film 12'.

[0512] Similar to the manufacturing method (1), in the semiconductor chip 900 with the first protective film obtained in the dividing step (2), the peeling of the first protective film 120' from the bump forming surface 9a' of the semiconductor chip 9', the base of the bump 91, and the side surface 9c' is suppressed. In addition, the first protective film 120' having a sufficient thickness is provided on the side surface 9c' of the semiconductor chip 9'.

[0513] In addition, when the X value is greater than 19 and less than 10000, the semiconductor chip 900 with the first protective film obtained in the segmentation step (2) can obtain the effect of suppressing the first protective film 120' from adhering to the upper part 910 of the above-mentioned bump 91, the effect of suppressing the first protective film 120' from sticking out on the bump forming surface 9a', and the effect of suppressing the unevenness of the first protective film 120' on the bump forming surface 9a', as in the manufacturing method (1).

[0514] <<Manufacturing method (3)>>

[0515] Figure 6A to Figure 6E A cross-sectional view schematically showing a manufacturing method (3) using Figure 3 The composite sheet 1 shown is another example of a method for manufacturing a semiconductor chip with a first protective film.

[0516] <Attachment process>

[0517] like Figure 6A to Figure 6B As shown, in the manufacturing method (3), the attaching step is performed by the same method as the manufacturing method (1) to produce the semiconductor wafer 901 with the resin film.

[0518] <Division process (3)>

[0519] In the dividing step (3) after the attaching step of the manufacturing method (3), the semiconductor wafer 9 is divided, thereby Figure 6C As shown, a semiconductor chip group 905 with a resin film is prepared, which includes a plurality of semiconductor chips 9' and a resin film 12 provided on bump formation surfaces 9a' of the plurality of semiconductor chips 9' and gaps 90' between the semiconductor chips 9'.

[0520] Similar to the above-mentioned dividing step (1), the semiconductor wafer 9 can be divided by a known method.

[0521] In the semiconductor chip group 905 with a resin film, all the semiconductor chips 9 ′ are held integrally with the support sheet 10 by a single resin film 12 .

[0522] <Curing process (3)>

[0523] In the curing step (3) after the dividing step (3), the first support sheet 10 is removed from the semiconductor chip group 905, and then the resin film 12 is cured to form a first protective film. Fig.6D As shown, a semiconductor chip group 903 with a first protective film is prepared, which includes a plurality of semiconductor chips 9' and a first protective film 12'. The first protective film 12' is provided on the bump formation surfaces 9a' of the plurality of semiconductor chips 9' and in the gaps 90' between the semiconductor chips 9'.

[0524] The semiconductor chip group 903 with the first protective film obtained in the curing step (3) is the same as the semiconductor chip group 903 with the first protective film obtained in the above-mentioned dividing step (1).

[0525] Similar to the curing step (1), the resin film 12 can be cured by a known method.

[0526] <Cutting process (3)>

[0527] In the cutting step (3) after the curing step (3), the first protective film 12' is cut along the gaps 90' between the semiconductor chips 9' in the semiconductor chip group 903 with the first protective film, thereby manufacturing the semiconductor chip 900 with the first protective film.

[0528] The semiconductor chip 900 with the first protective film obtained in the cutting step (3) is the same as the semiconductor chip 900 with the first protective film obtained in the cutting step (1).

[0529] Similar to the above-mentioned cutting step (1), the first protective film 12 ′ can be cut by a known method.

[0530] Similar to the manufacturing method (1), in the semiconductor chip 900 with the first protective film obtained in the cutting step (3), the peeling of the first protective film 120' from the bump forming surface 9a' of the semiconductor chip 9', the base of the bump 91, and the side surface 9c' is suppressed. In addition, the first protective film 120' having a sufficient thickness is provided on the side surface 9c' of the semiconductor chip 9'.

[0531] In addition, when the X value is greater than 19 and less than 10000, the semiconductor chip 900 with the first protective film obtained in the cutting step (3) can obtain the effect of suppressing the first protective film 120' from adhering to the upper part 910 of the above-mentioned bump 91, the effect of suppressing the first protective film 120' from sticking out on the bump forming surface 9a', and the effect of suppressing the unevenness of the first protective film 120' on the bump forming surface 9a', as in the manufacturing method (1).

[0532] So far, the use of Figure 3 Although the case of the composite sheet (first protective film forming sheet) 1 shown has been described, when the composite sheets of other embodiments described above are used, the composite sheets can also achieve the same effects as when the composite sheet 1 is used.

[0533] The above-mentioned production methods (1) to (3) may have other steps different from the steps described above without departing from the scope of the present invention.

[0534] For example, when a second protective film is provided on the back side of a semiconductor chip, manufacturing methods (1) to (3) may include, at any time, the following steps: a step of attaching the second protective film forming film in the second protective film forming sheet to the back side of the semiconductor chip; a step of curing the second protective film forming film to form a second protective film when the second protective film forming film is curable; a step of cutting the second protective film forming film or the second protective film along the periphery (side) of the semiconductor chip, etc.

[0535] For example, when the resin film 12, the first protective film 12' or the first protective film 120' after being cut off remains on the upper part 910 of the bump 91 including the top 9101 at any stage after the attaching process, the manufacturing method (1) to the manufacturing method (3) may include a removal step of removing the residues of the resin film 12, the first protective film 12' or the first protective film 120' after being cut off from the upper part 910 of the bump 91 at any time after the attaching process.

[0536] The residue of the resin film 12 , the first protection film 12 ′, or the first protection film 120 ′ after being cut off on the upper portion 910 of the bump 91 may be removed by a known method such as plasma irradiation.

[0537] So far, the case where a support sheet or a back grinding tape is provided on the bump forming surface of a semiconductor wafer or a bump forming surface of a semiconductor chip group via a resin film or a first protective film, and the back side of the semiconductor wafer or the back side of the semiconductor chip group is ground, etc. has been described. However, in the present embodiment, a resin sheet other than the support sheet or the back grinding tape may be provided to replace these support sheets or the back grinding tape, and the back side of the semiconductor wafer or the back side of the semiconductor chip group may be ground, etc. Here, the resin sheet may be formed by filling the resin film or the first protective film on the bump forming surface of the semiconductor wafer or the bump forming surface of the semiconductor chip group with a resin having fluidity, and further filling the surface of the bump and then curing it. When such a resin sheet is provided, it is also possible to use other resins that can follow the resin film or the first protective film on the bump forming surface and the surface of the bump and have flexibility before using the resin having fluidity, and pre-form a resin film that covers the resin film or the first protective film and the surface of the bump on the bump forming surface, and provide the resin sheet via the resin film. By providing the resin film in this manner, it is possible to easily remove the unnecessary resin sheet after polishing the back surface of the semiconductor wafer or the back surface of the semiconductor chip group.

[0538] ◇How to use the semiconductor chip with the first protective film

[0539] By using the semiconductor chip with the first protective film, a semiconductor device can be manufactured. For example, the semiconductor chip with the first protective film is flip-chip bonded (mounted) on the circuit formation surface of the circuit substrate through the top of the bumps therein.

[0540] When the second protective film forming sheet is used, before flip chip bonding of the semiconductor chip with the first protective film is performed, the semiconductor chip with the first protective film having the second protective film is separated from the dicing sheet in the second protective film forming sheet and picked up.

[0541] The semiconductor chip with the first protective film and the second protective film can be picked up by a known method.

[0542] Thereafter, a semiconductor package can be fabricated by a known method using the circuit substrate on which the semiconductor chip is mounted, and a target semiconductor device can be manufactured using the semiconductor package.

[0543] Example

[0544] The present invention will be described in more detail below using specific examples, but the present invention is not limited to the following examples.

[0545] <Raw materials for preparing the resin film-forming composition>

[0546] The raw materials used for preparing the resin film-forming composition are shown below.

[0547] [Polymer component (A)]

[0548] (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).

[0549] [Chemical formula 2]

[0550]

[0551] In the formula, l1 is approximately 28, m1 is 1 to 3, and n1 is an integer from 68 to 74.

[0552] [Epoxy resin (B1)]

[0553] (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)

[0554] (B1)-2: dicyclopentadiene type epoxy resin ("EPICLON HP-7200HH" manufactured by DIC CORPORATION, epoxy equivalent 254 to 264 g / eq)

[0555] (B1)-3: Bisphenol A type epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184 to 194 g / eq)

[0556] [Thermosetting agent (B2)]

[0557] (B2)-1: o-cresol novolac resin ("PHENOLITE KA-1160" manufactured by DIC CORPORATION, softening point 80°C, hydroxyl equivalent 117 g / eq)

[0558] (B2)-2: Biphenyl aralkyl type phenolic resin ("MEHC-7851-H" manufactured by MEIWA PLASTIC INDUSTRIES, LTD., solid dispersion type latent curing agent, hydroxyl equivalent 218 g / eq)

[0559] [Curing accelerator (C)]

[0560] (C)-1: 2-phenyl-4,5-dihydroxymethylimidazole ("CUREZOL 2PHZ-PW" manufactured by SHIKOKU CHEMICALS CORPORATION)

[0561] [Filling material (D)]

[0562] (D)-1: Epoxy-modified spherical silica ("ADMANANO YA050C-MKK" manufactured by Admatechs, average particle size 50 nm)

[0563] (D)-2: Epoxy-modified spherical silica (“5SE-CH1” manufactured by Admatechs, average particle size 500 nm)

[0564] [Coupling agent (E)]

[0565] (E)-1: 3-glycidyloxypropyltrimethoxysilane (silane coupling agent, "KBM-403" manufactured by Shin-Etsu Silicone Co., Ltd.)

[0566] [Additive (I)]

[0567] (I)-1: Surfactant (acrylic acid polymer, "BYK-361N" manufactured by BYK Chemical Co., Ltd.)

[0568] (I)-2: Silicone oil (aralkyl-modified silicone oil, "XF42-334" manufactured by Momentive Performance Materials Japan)

[0569] (I)-3: Rheology control agent (polyhydroxycarboxylate, BYK-R606 manufactured by BYK Chemicals)

[0570] [Example 1]

[0571] <<Manufacturing of the First Protective Film-Forming Sheet>>

[0572] <Preparation of Thermosetting Resin Film-Forming Composition>

[0573] The polymer component (A)-1 (100 parts by mass), epoxy resin (B1)-1 (290 parts by mass), epoxy resin (B1)-2 (220 parts by mass), (B2)-1 (160 parts by mass), curing accelerator (C)-1 (2 parts by mass), filler (D)-1 (200 parts by mass), additive (I)-1 (25 parts by mass) and additive (I)-2 (3 parts by mass) were dissolved or dispersed in methyl ethyl ketone and stirred at 23° C. to obtain a composition (III) as a thermosetting resin film-forming composition having a total concentration of all components other than the solvent of 45% by mass. The blending amounts of the components other than the solvent shown here are all blending amounts of the target product excluding the solvent.

[0574] <Manufacturing of thermosetting resin film>

[0575] A release film ("SP-PET381031" manufactured by LINTEC Corporation, thickness 38 μm) obtained by subjecting one side of a polyethylene terephthalate film to a release treatment by silicone treatment was used, and the composition (III) obtained above was applied to the release-treated surface of the release film, followed by heating and drying at 120°C for 2 minutes to form a thermosetting resin film with a thickness of 45 μm.

[0576] <Manufacturing of the First Protective Film-Forming Sheet>

[0577] A laminate sheet (back grinding tape, "E-8510HR" manufactured by LINTEC Corporation, also corresponding to the support sheet) corresponding to the laminate of the first substrate, the buffer layer and the first adhesive layer is used, and the first adhesive layer in the laminate sheet is bonded to the thermosetting resin film on the release film obtained above. Thus, a structure in which the first substrate, the buffer layer, the first adhesive layer, the thermosetting resin film and the release film are sequentially laminated in their thickness direction is obtained. Figure 3 The first protective film forming sheet shown.

[0578] <<Evaluation of thermosetting resin film>>

[0579] <Measurement of α1 and α2>

[0580] [Manufacturing of Thermosetting Resin Film and First Test Specimen]

[0581] Except for changing the coating amount of composition (III), 20 thermosetting resin films with a thickness of 25 μm were prepared by the same method as above. Next, a laminated body obtained by laminating the thermosetting resin films was heat-treated using a pressure oven ("RAD-9100" manufactured by LINTEC Corporation) under heating conditions of a temperature of 130° C., a time of 4 hours, and a furnace pressure of 0.5 MPa, thereby thermally curing it. The obtained cured product was cut into a rectangle with a width of 4.5 mm and a length of 20 mm, thereby preparing a first test piece formed by the cured product with a thickness of 0.5 mm.

[0582] [Determination of α1 and α2]

[0583] Thermomechanical analysis (TMA) was performed on the first test piece obtained above using a thermomechanical analyzer ("TMA4000SA" manufactured by PerkinElmer Co., Ltd.) according to the following procedure.

[0584] That is, the first test piece was heated at a temperature increase rate of 5°C / min, thereby raising the temperature of the first test piece from room temperature to 100°C. Then, the first test piece was immediately cooled at a temperature decrease rate of 5°C / min, thereby lowering the temperature of the first test piece to -75°C. Next, the first test piece was immediately heated at a temperature increase rate of 5°C / min, thereby raising the temperature of the first test piece to 260°C. This thermomechanical analysis was performed on a 15 mm long portion of the first test piece having a length of 20 mm. Then, the linear expansion coefficient α1 of the first test piece was measured from -75°C to the temperature equal to the glass transition temperature (Tg). Furthermore, the linear expansion coefficient α2 of the first test piece was measured from the temperature equal to Tg to 260°C. The results are shown in Table 1. In addition, Tg of the first test piece is the temperature indicated by the inflection point in the graph of the temperature of the first test piece and the heating time obtained when the above-mentioned thermomechanical analysis is performed, which is about 60°C here.

[0585] <Evaluation of the filling suitability of thermosetting resin films for trenches on wafer surfaces>

[0586] [Fabrication of Silicon Wafer with First Protective Film]

[0587] A plurality of grooves 60 μm wide and 230 μm deep were formed in a grid pattern on the surface of a silicon wafer (12 inches in diameter, 750 μm thick) using a half-cut dicing machine ("DFD6361" manufactured by DISCO CORPORATION) so as to obtain chips of 6 mm×6 mm in size.

[0588] Using a bonding device (roller laminator, "RAD-3510 F / 12" manufactured by LINTEC Corporation), under the conditions of a workbench temperature of 90°C, a bonding speed of 2 mm / s, a bonding pressure of 0.5 MPa, and a roller bonding height of -200 μm, the first protective film forming sheet obtained above was bonded to the surface of the silicon wafer where the grooves were formed through the thermosetting resin film therein.

[0589] Next, the laminate sheet (support sheet) is removed from the thermosetting resin film.

[0590] Next, the thermosetting resin film was heat-treated and thermally cured in a pressurized oven ("RAD-9100" manufactured by LINTEC Corporation) at 130°C for 4 hours and at a furnace pressure of 0.5 MPa to form a first protective film.

[0591] By the above method, a silicon wafer with a first protective film is manufactured.

[0592] [Evaluation of the filling suitability of thermosetting resin films for trenches on wafer surfaces]

[0593] The silicon wafer with the first protective film obtained above was observed using an optical microscope. Then, the filling suitability of the first protective film (i.e., the thermosetting resin film) for the groove on the surface of the wafer was evaluated according to the following criteria. The results are shown in the column "Groove Filling Suitability" in Table 1.

[0594] (Evaluation Criteria)

[0595] A: No deformation of the shape of the first protective film was observed, and the filling suitability of the groove was high.

[0596] B: Although slight deformation of the shape of the first protective film was observed in the area corresponding to the vicinity of the groove opening, the filling suitability of the groove was good.

[0597] C: Although there are gaps in some parts, the grooves can be mostly filled and the grooves have filling suitability.

[0598] D: It does not belong to any of the above A, B, and C, and the groove filling suitability is poor.

[0599] <Evaluation of the effect of suppressing peeling of the first protective film from the side surface of the chip>

[0600] [Manufacturing of Silicon Chip with First Protective Film]

[0601] Using a laminating device (roller laminator, "RAD-3510 F / 12" manufactured by LINTEC Corporation), the same laminating sheet as above (back grinding tape, "E-8510HR" manufactured by LINTEC Corporation), and a silicon wafer with a first protective film that has been evaluated for the filling suitability, the first adhesive layer in the laminating sheet is attached to the surface on the first protective film side of the silicon wafer with the first protective film, thereby obtaining a silicon wafer with a first protective film having a laminating sheet.

[0602] Next, the back surface of the silicon wafer with the first protective film having the laminated sheet was polished so that the polished surface reached the grooves, thereby dividing the silicon wafer into silicon chips, and the silicon chips were polished until the thickness of the silicon chips reached 200 μm.

[0603] Next, a dicing tape ("D-686H" manufactured by LINTEC Corporation) was attached to the back side (grinding surface) of all the silicon chips obtained above using a sticking device (roller laminator, "RAD-3510F / 12" manufactured by LINTEC Corporation). Then, a blade cutter ("DFD6362" manufactured by DISCO CORPORATION) was used to cut the first protective film along the periphery of the obtained silicon chip. At this time, the moving speed of the blade was set to 10 mm / s, the rotation speed of the blade was set to 50,000 rpm, and the base material of the dicing tape was cut by the blade until a depth of 20 μm from the surface on the silicon chip side.

[0604] By the above method, a plurality of silicon chips with first protective films are obtained, which have a silicon chip with a size of 6mm×6mm and a first protective film integrally arranged on the four sides and one surface (the surface of the silicon wafer that once had the groove) of the silicon chip and are fixed on a dicing tape.

[0605] [Evaluation of the Effect of Suppressing Peeling of the First Protective Film from the Sides of the Chip]

[0606] Next, the silicon chip with the first protective film is peeled off from the dicing tape and picked up at four positions corresponding to the position that was once the central part of the silicon wafer and the position that was once located at approximately the same distance from the central part and equidistant from each other near the peripheral part of the silicon wafer. The five silicon chips with the first protective film obtained in this way are observed using an optical microscope. Then, the number of silicon chips with the first protective film in which peeling of the first protective film is observed on any one of the four side surfaces (the number of defective products) is confirmed. The result of "number of defective products / number of evaluations (=5)" at this time is shown in the "Effect of Suppressing Peeling" column in Table 1.

[0607] <Measurement of Gc1 and Gc300 of Thermosetting Resin Film and Calculation of X Value>

[0608] [Manufacturing of Thermosetting Resin Film and Second Test Specimen]

[0609] 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 second test piece of thermosetting resin film with a thickness of 1 mm.

[0610] [Measurement of Gc1 and Gc300 of Thermosetting Resin Film and Calculation of X Value]

[0611] The setting position of the test piece in the viscoelasticity measuring device ("MCR301" manufactured by Anton Paar) is pre-heated at 90°C, the second test piece of the thermosetting resin film obtained above is placed on the setting position, and the measuring fixture is pressed on the upper surface of the second test piece, thereby fixing the second test piece at the setting position.

[0612] Next, under the conditions of a temperature of 90°C and a measurement frequency of 1 Hz, the strain generated in the second test piece was gradually increased in the range of 0.01% to 1000%, and the storage modulus Gc of the second test piece was measured. Then, the X value was calculated from the measured values ​​of Gc1 and Gc300. The results are shown in Table 1.

[0613] <Measurement of the amount of bubbling of thermosetting resin film>

[0614] [Manufacturing of Thermosetting Resin Film and Third Test Specimen]

[0615] A release film ("SP-PET381031" manufactured by LINTEC Corporation, thickness 38 μm) obtained by subjecting one side of a polyethylene terephthalate film to a release treatment by silicone treatment was used, and the composition (III) obtained above was applied to the release-treated surface of the release film, and heated and dried at 120°C for 2 minutes to form a thermosetting resin film with a thickness of 30 μm.

[0616] Next, the thermosetting resin film was processed together with the release film into a circular shape having a diameter of 170 mm, thereby preparing a third test piece with a release film.

[0617] [Measurement of the amount of bubbling of thermosetting resin film]

[0618] The entire exposed surface of the obtained third test piece (in other words, the surface opposite to the side provided with the release film) was bonded to the surface of a transparent belt-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.

[0619] As shown here, the obtained laminated body 101 is constituted by laminating the back grinding tape 7, the third test piece 120 (thermosetting resin film 12), and the release film in this order in the thickness direction thereof.

[0620] Next, the release film was removed from the obtained laminate, and the exposed surface of the newly produced third test piece (in other words, the surface of the third test piece opposite to the side provided with the back grinding tape) was pressed against one surface of a silicon wafer having a diameter of 12 inches, thereby attaching the third test piece to the surface of the silicon wafer. At this time, the third test piece was attached to the surface of the silicon wafer 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 / s, an attaching pressure of 0.5 MPa, and a roller attaching height of -200 μm while heating the third test piece.

[0621] Next, for the third 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 was measured, and the maximum value of the length of the line segment connecting two different points on the outer circumference was measured by referring to Figure 2 The method described above was used to calculate the amount (mm) of protrusion of the third test piece (in other words, the thermosetting resin film) using the measured value (the maximum value of the length of the line segment).

[0622] [Example 2, Reference Example 1]

[0623] <<Manufacturing of Thermosetting Resin Film and First Protective Film-Forming Sheet, and Evaluation of Thermosetting Resin Film>>

[0624] A thermosetting resin film and a first protective film-forming sheet were produced by the same method 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 contained in the thermosetting resin film-forming composition were as shown in Table 1. The thermosetting resin film was evaluated. The results are shown in Table 1.

[0625] In addition, "-" in the column of the contained component in Table 1 means that the thermosetting resin film-forming composition does not contain the component.

[0626] [Table 1]

[0627]

[0628] According to the above results, in Examples 1 to 2, the thermosetting resin film has good filling suitability for the grooves on the surface of the silicon wafer. In addition, in Examples 1 to 2, no peeling of the first protective film was observed on the four sides of the semiconductor chip with the first protective film, and of course no falling off of the first protective film was observed, and the peeling of the first protective film from the side of the silicon chip was significantly suppressed. In Examples 1 to 2, no peeling of the first protective film was observed on the surface of the silicon chip (the surface of the silicon wafer that once had the grooves), and of course no falling off of the first protective film was observed, and the peeling of the first protective film from the surface was significantly suppressed. In Examples 1 to 2, α1 is less than 60 ppm / K (40 to 60 ppm / K).

[0629] In addition, in Examples 1 to 2, α2 is below 160 ppm / K (110 to 160 ppm / K). It is speculated that since the thermosetting resin film not only satisfies the conditions of α1 but also α2, it is more preferred in terms of the above-mentioned groove filling suitability and inhibiting the peeling of the first protective film from the side of the silicon chip.

[0630] In particular, in Example 1, the thermosetting resin film has a particularly high filling suitability for the groove. The value of X in Example 1 is greater than that in Example 2.

[0631] In Example 1 (Example 2 was not evaluated), the amount of protrusion of the third test piece was 0 mm (protrusion of the thermosetting resin film was not observed), and the basic characteristics of the thermosetting resin film were good.

[0632] In Examples 1 to 2, the X value is 20 to 65, and it can be determined that when the thermosetting resin films of Examples 1 to 2 are attached to a concave-convex surface (for example, the bump forming surface of a semiconductor wafer), penetration of the convex portion (for example, the bump) can be achieved, residue on the upper portion of the convex portion can be suppressed, and popping out on the concave-convex surface can be suppressed, and unevenness of the thermosetting resin film itself and its cured product on the concave-convex surface can be suppressed.

[0633] In contrast, peeling of the first protective film was observed on all four side surfaces of the semiconductor chip with the first protective film in Reference Example 1. In Reference Example 1, α1 was 70 ppm / K.

[0634] In addition, in Reference Example 1, α2 is 170ppm / K, and it is confirmed that since the thermosetting resin film not only does not satisfy α1 but also α2 does not satisfy the conditions listed above (α1≤65ppm / K, α2≤165ppm / K), it has a less preferred property in suppressing the peeling of the above-mentioned first protective film from the side of the silicon chip.

[0635] Industrial Applicability

[0636] The present invention can be utilized in the production of a semiconductor chip or the like having bumps on a connection pad portion used in a flip chip bonding method.

[0637] Description of Reference Numerals

[0638] 1: composite sheet (sheet for forming the first protective film); 10: support sheet (first support sheet); 10a: one side of the support sheet; 11: substrate (first substrate); 11a: one side of the substrate; 12: resin film; 12a: the first side of the resin film; 12': the first protective film; 120': the first protective film (the first protective film after cutting); 13: buffer layer; 9: semiconductor wafer; 90: groove of semiconductor wafer; 9a: bump forming surface of semiconductor wafer; 9': semiconductor chip; 9a': bump forming surface of semiconductor chip; 9c': side surface of semiconductor chip; 91: bump; 900: semiconductor chip with the first protective film; 901: semiconductor wafer with resin film; 902: semiconductor wafer with the first protective film; 903: semiconductor chip group with the first protective film; 904: semiconductor wafer with the first protective film that has been cut; 905: semiconductor chip group with resin film.

Claims

1. A resin film, which is a curable resin film, wherein: The resin film contains a polymer component (A), an epoxy resin (B1), a thermosetting agent (B2), a curing accelerator (C), a filler (D) and a coupling agent (E). The epoxy resin (B1) is any one or both of bisphenol A epoxy resin and dicyclopentadiene epoxy resin. The thermosetting agent (B2) is any one or both of a novolac type phenolic resin and an aralkyl type phenolic resin, The filler material (D) is any one or two of silicon dioxide and its surface modified product, The coupling agent (E) is a silane coupling agent, The total content of the epoxy resin (B1) and the thermosetting agent (B2) in the resin film is 15 to 30% by mass relative to the total mass of the resin film. The content of the filler (D) in the resin film is 40 to 55% by mass relative to the total mass of the resin film. The resin film was heat-cured at 130° C. for 4 hours while being pressurized at a pressure of 0.5 MPa, and the obtained cured product having a thickness of 0.5 mm and a width of 4.5 mm was used as a first test piece. A thermomechanical analysis was performed on a 15 mm long portion of the first test piece, and when the linear expansion coefficient α1 of the first test piece was measured from −75° C. to a temperature equal to the glass transition temperature, the α1 was 65 ppm / K or less. In the thermomechanical analysis, the first test piece was heated at a heating rate of 5°C / min, thereby increasing the temperature of the first test piece from room temperature to 100°C, then the first test piece was cooled at a cooling rate of 5°C / min, thereby decreasing the temperature of the first test piece to -75°C, and then the first test piece was heated at a heating rate of 5°C / min, thereby increasing the temperature of the first test piece to 260°C.

2. The resin film according to claim 1, wherein The content of the filler (D) in the resin film is 53 to 55% by mass based on the total mass of the resin film.

3. The resin film according to claim 1, wherein When the thermomechanical analysis was performed and the linear expansion coefficient α2 of the first test piece was measured from the same temperature as the glass transition temperature to 260° C., the α2 was 165 ppm / K or less.

4. The resin film according to claim 1, wherein The resin film having a diameter of 25 mm and a thickness of 1 mm is used as a second test piece, and the second test piece is strained under the conditions of a temperature of 90° C. and a frequency of 1 Hz, and the storage modulus of the second test piece is measured, and when the storage modulus of the second test piece when the strain of the second test piece is 1% is set as Gc1, and the storage modulus of the second test piece when the strain of the second test piece is 300% is set as Gc300, the X value calculated by the following formula is 19 or more and less than 10000, X=Gc1 / Gc300.

5. The resin film according to claim 1, wherein The resin film is used for attachment to the concave and convex surface. The resin film according to claim 1 , wherein The resin film is used to protect the concavo-convex surface and side surfaces of the semiconductor chip.

7. A composite sheet comprising a support sheet and a resin film provided on one surface of the support sheet, The resin film is the resin film according to any one of claims 1 to 6.

8. The composite sheet according to claim 7, wherein: The support sheet includes a base material and an adhesive layer provided on one surface of the base material, and the adhesive layer is arranged between the base material and the resin film.

9. The composite sheet according to claim 7, wherein: The support sheet includes a base material and a buffer layer provided on one surface of the base material, and the buffer layer is arranged between the base material and the resin film.

10. A method for manufacturing a semiconductor chip with a first protective film, the method being a method for manufacturing a semiconductor chip with a first protective film using a semiconductor wafer, wherein: The semiconductor chip with the first protective film comprises a semiconductor chip and a first protective film provided on a side surface and a surface having bumps of the semiconductor chip. The semiconductor wafer has bumps and grooves serving as division positions of the semiconductor wafer on one surface thereof. The manufacturing method comprises a bonding step, in which the resin film in the composite sheet according to any one of claims 7 to 9 is bonded to the one surface of the semiconductor wafer, thereby manufacturing a semiconductor wafer with a resin film having the resin film on the one surface and the groove filled with the resin film. The manufacturing method also comprises: After the attaching step, the resin film is thermally cured to form the first protective film, thereby preparing a curing step (1) of a semiconductor wafer with a first protective film, which comprises the semiconductor wafer and the first protective film arranged on the one surface of the semiconductor wafer and filling the groove; after the curing step (1), the semiconductor wafer is divided, thereby preparing a semiconductor chip group with a first protective film, which comprises a plurality of semiconductor chips and the first protective film arranged on the surfaces having the bumps of the plurality of semiconductor chips and the gaps between the semiconductor chips; and after the dividing step (1), the first protective film is cut along the gaps between the semiconductor chips in the semiconductor chip group with the first protective film, thereby preparing a cutting step (1) of the semiconductor chips with the first protective film; or After the attaching step and after the curing step (1), the first protective film is cut along the groove in the semiconductor wafer with the first protective film, thereby producing a cutting step (2) of the semiconductor wafer with the cut first protective film; and after the cutting step (2), the semiconductor wafer is divided, thereby producing the semiconductor chip with the first protective film. Or After the attaching step, the semiconductor wafer is divided to thereby produce a dividing step (3) of a semiconductor chip group with a resin film, which comprises a plurality of semiconductor chips, a surface with the bumps arranged on the plurality of semiconductor chips, and a gap between the semiconductor chips; after the dividing step (3), the resin film is thermally cured to form the first protective film, thereby producing a semiconductor chip group with a first protective film, which comprises a plurality of semiconductor chips, a surface with the bumps arranged on the plurality of semiconductor chips, and a gap between the semiconductor chips; and after the curing step (3), the first protective film is cut along the gap between the semiconductor chips in the semiconductor chip group with the first protective film, thereby obtaining the semiconductor chip with the first protective film.

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