TWI877281B - Method for manufacturing curable resin film, composite sheet and semiconductor chip - Google Patents

Abstract

The subject of the present invention is to provide a curable resin film that can form a protective film with excellent coverage on both the bump-forming surface and the side surface of a semiconductor chip. As a curable resin film for solving this problem, a curable resin film is provided for forming a protective film on both the bump-forming surface and the side surface of a semiconductor chip having a bump-forming surface with bumps; and the curable resin film satisfies the following requirement (I). <Requirement (I)> Under the conditions of a temperature of 90°C and a frequency of 1 Hz, a test piece of the aforementioned curable resin film having a diameter of 25 mm and a thickness of 1 mm is strained, and the storage modulus of the aforementioned test piece is measured, and when the storage modulus of the aforementioned test piece when the strain of the aforementioned test piece is 1% is set as Gc1, and when the storage modulus of the aforementioned test piece when the strain of the aforementioned test piece is 300% is set as Gc300, the value of X calculated by the following formula (i) is 19 or more and less than 10,000.

Description

Method for manufacturing curable resin film, composite sheet and semiconductor chip

The present invention relates to a method for manufacturing a hardening resin film, a composite sheet, and a semiconductor chip. More specifically, the present invention relates to a hardening resin film, a composite sheet having the hardening resin film, and a method for manufacturing a semiconductor chip using the hardening resin film as a protective film.

In recent years, semiconductor devices have been manufactured using a mounting method called a flip-chip (face down) method. In the flip-chip method, a semiconductor chip having bumps on a circuit surface and a substrate for mounting the semiconductor chip are laminated in such a way that the circuit surface of the semiconductor chip faces the substrate, and the semiconductor chip is mounted on the substrate. In addition, the semiconductor chip is usually obtained by singulating a semiconductor wafer having bumps on a circuit surface.

In a semiconductor wafer having a bump, a protective film is sometimes provided for the purpose of protecting the bonding portion between the bump and the semiconductor wafer (hereinafter also referred to as the "bump neck"). For example, in Patent Documents 1 and 2, a laminate formed by laminating a support substrate, an adhesive layer, and a thermosetting resin layer in sequence is pressed and attached to the bump forming surface of a semiconductor wafer having a bump, with the thermosetting resin layer as a bonding surface, and the thermosetting resin layer is heated to harden it, thereby forming a protective film. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2015-092594 [Patent Document 2] Japanese Patent Publication No. 2012-169484

[Problems to be solved by the invention]

In recent years, with the miniaturization and thinning of IC assembly products such as electronic equipment, there has been a further demand for thinning of semiconductor chips. However, if the semiconductor chip becomes thinner, the strength of the semiconductor chip will decrease. Therefore, there is a problem that the semiconductor chip becomes easily damaged when, for example, the semiconductor chip is transported and the subsequent steps of packaging the semiconductor chip are implemented. Therefore, it is thought of forming a protective film on the bump forming surface of the semiconductor wafer to protect the bump neck and improve the strength of the semiconductor chip. However, the strength of the semiconductor chip is not sufficiently improved by only forming a protective film on the bump forming surface of the semiconductor wafer. In addition, the protective film sometimes causes film peeling.

Based on this, the inventors of the present invention have conceived that by providing a protective film for the purpose of protecting the bump neck, not only on the bump forming surface of the semiconductor chip but also on the side surface, the strength of the semiconductor chip can be improved while suppressing the peeling of the protective film, and a very reasonable structure can be constructed. Based on this concept, the inventors of the present invention have devoted themselves to repeated research and have created a curable resin film that can form a protective film with excellent coverage on both the bump forming surface and the side surface of the semiconductor chip.

Therefore, the subject of the present invention is to provide a curable resin film that can form a protective film with excellent coverage on both the bump forming surface and the side surface of a semiconductor chip, a composite sheet having the curable resin film, and a method for manufacturing a semiconductor chip using the curable resin film and the composite sheet. [Means for solving the subject]

As a result of repeated studies, the inventors of the present invention have found that the above-mentioned problems can be solved by focusing on the parameters calculated from the specific physical properties of the curable resin film, thereby achieving the present invention.

That is, the present invention relates to the following [1] to [14]. [1] A curable resin film, which is used to form a curable resin film as a protective film on both the bump forming surface and the side surface of a semiconductor chip having a bump forming surface with bumps; and satisfies the following requirement (I). <Requirement (I)> Under the conditions of a temperature of 90°C and a frequency of 1 Hz, a test piece of the aforementioned curable resin film having a diameter of 25 mm and a thickness of 1 mm is strained, and the storage modulus of the aforementioned test piece is measured, and when the storage modulus of the aforementioned test piece when the strain of the aforementioned test piece is 1% is set as Gc1, and when the storage modulus of the aforementioned test piece when the strain of the aforementioned test piece is 300% is set as Gc300, the value of X calculated by the following formula (i) is 19 or more and less than 10,000. [2] A curable resin film as described in [1] above, wherein in the above requirement (I), Gc300 is less than 15,000. [3] A composite sheet for forming a curable resin film as a protective film on both the bump forming surface and the side surface of a semiconductor chip having a bump forming surface with bumps, and having a laminated structure formed by laminating a support sheet and a curable resin layer, wherein the curable resin is a curable resin film as described in [1] or [2] above. [4] A method of use, which is a method of using the curable resin film described in [1] or [2] above to form a curable resin film as a protective film on both the aforementioned bump forming surface and the side surface of a semiconductor chip having a bump forming surface with bumps. [5] A method of use, which is a method of using the composite sheet described in [3] above to form a curable resin film as a protective film on both the aforementioned bump forming surface and the side surface of a semiconductor chip having a bump forming surface with bumps. [6] A method of manufacturing a semiconductor chip, which comprises the following steps (S1) to (S4) in sequence, ･Step (S1): a step of preparing a semiconductor wafer for manufacturing a working wafer, wherein the semiconductor wafer for manufacturing a working wafer is a semiconductor wafer having a bump forming surface with bumps, and a groove portion serving as a predetermined dividing line is formed on the bump forming surface of the semiconductor wafer so as not to reach the back surface ･Step (S2): a step of pressing and attaching a first curable resin (x1) to the bump forming surface of the semiconductor wafer for manufacturing a working wafer, and while covering the bump forming surface of the semiconductor wafer for manufacturing a working wafer with the first curable resin (x1), burying the first curable resin (x1) in the groove portion formed on the semiconductor wafer for manufacturing a working wafer ･Step (S3): hardening the first curable resin (x1) to obtain a semiconductor wafer with a first curable resin film (r1) ･Step (S4): singulating the semiconductor wafer with the first curable resin film (r1) along the predetermined dividing line to obtain semiconductor wafers at least on which the bump forming surface and the side surface are covered with the first curable resin film (r1) Further, after the step (S2) and before the step (S3), after the step (S3) and before the step (S4), or in the step (S4), the following step (S-BG) is included, ･Step (S-BG): grinding the back side of the semiconductor chip manufacturing wafer; and using the curable resin film described in [1] or [2] as the first curable resin (x1). [7] The method for manufacturing a semiconductor chip as described in [6], wherein the step (S2) is performed by pressing and attaching a first composite sheet (α1) having a laminated structure formed by laminating a first support sheet (Y1) and a layer (X1) of the first curable resin (x1) to the bump forming surface of the semiconductor chip manufacturing wafer using the layer (X1) as an attachment surface. [8] A method for manufacturing a semiconductor chip as described in the above-mentioned [7], wherein the step (S-BG) is included after the step (S2) and before the step (S3), and the step (S-BG) is implemented by grinding the back side of the semiconductor chip wafer with the first composite film (α1) attached thereto, and then peeling off the first supporting film (Y1) from the first composite film (α1), and the step (S4) is implemented by cutting the portion formed in the groove of the first hardened resin film (r1) of the semiconductor chip wafer with the first hardened resin film (r1) attached thereto along the predetermined dividing line. [9] The method for manufacturing a semiconductor chip as described in the above-mentioned [7], wherein the step (S-BG) is included after the step (S3) and before the step (S4), and the step (S3) is implemented in a manner that the first supporting sheet (Y1) is not peeled off from the first composite sheet (α1), and the step (S-BG) is implemented by grinding the back side of the semiconductor chip manufacturing wafer in a state where the first composite sheet (α1) is attached, and then peeling the first supporting sheet (Y1) from the first composite sheet (α1), The aforementioned step (S4) is implemented by cutting the portion of the aforementioned first hardened resin film (r1) formed in the aforementioned groove along the aforementioned predetermined dividing line in the aforementioned semiconductor chip manufacturing wafer with the aforementioned first hardened resin film (r1). [10] The method for manufacturing a semiconductor chip as described in the aforementioned [7], wherein the aforementioned step (S-BG) is included after the aforementioned step (S3) and before the aforementioned step (S4), and after the aforementioned step (S2) and before the aforementioned step (S3), the aforementioned first supporting sheet (Y1) is peeled off from the aforementioned first composite sheet (α1), The aforementioned step (S-BG) is implemented by attaching a back grinding sheet (b-BG) to the surface of the aforementioned first hardened resin film (r1) of the aforementioned semiconductor chip manufacturing wafer with the first hardened resin film (r1), grinding the aforementioned back side of the aforementioned semiconductor chip manufacturing wafer with the aforementioned back grinding sheet (b-BG) attached, and then peeling off the aforementioned back grinding sheet (b-BG) from the aforementioned semiconductor chip manufacturing wafer with the first hardened resin film (r1). The aforementioned step (S4) is implemented by cutting the portion formed in the aforementioned groove in the aforementioned first hardened resin film (r1) of the aforementioned semiconductor chip manufacturing wafer with the first hardened resin film (r1) along the aforementioned predetermined dividing line. [11] The method for manufacturing a semiconductor chip as described in the above-mentioned [7], wherein the above-mentioned step (S4) includes the above-mentioned step (S-BG), and after the above-mentioned step (S2) and before the above-mentioned step (S3), the above-mentioned first supporting sheet (Y1) is peeled off from the above-mentioned first composite sheet (α1), The aforementioned step (S4) is implemented by cutting a notch along the aforementioned predetermined dividing line or forming a modified region along the aforementioned predetermined dividing line in the aforementioned first hardened resin film (r1) of the aforementioned semiconductor chip manufacturing wafer with the first hardened resin film (r1), and then as the aforementioned step (S-BG), a back grinding sheet (b-BG) is attached to the surface of the aforementioned first hardened resin film (r1) of the aforementioned semiconductor chip manufacturing wafer with the first hardened resin film (r1), and grinding the aforementioned back side of the aforementioned semiconductor chip manufacturing wafer in a state where the aforementioned back grinding sheet (b-BG) is attached. [12] The method for manufacturing a semiconductor chip as described in any one of the above [6] to [11] further includes the following step (T). ･Step (T): forming a second hardened resin film (r2) on the back side of the wafer for semiconductor chip manufacturing. [13] A method for manufacturing a semiconductor chip as described in any one of [6] to [12] above, wherein the width of the groove is 10 μm to 2000 μm. [14] A method for manufacturing a semiconductor chip as described in any one of [6] to [13] above, wherein the depth of the groove is 30 μm to 700 μm. [Effect of the Invention]

According to the present invention, it is possible to provide a curable resin film that can form a protective film with excellent coverage on both the bump forming surface and the side surface of a semiconductor chip, a composite sheet having the curable resin film, and a method for manufacturing a semiconductor chip using the curable resin film and the composite sheet.

In this specification, the so-called "active ingredient" refers to the ingredients contained in the composition of interest, excluding diluents such as water or organic solvents. In addition, in this specification, the weight average molecular weight and number average molecular weight are polystyrene conversion values measured by gel permeation chromatography (GPC) method. In addition, in this specification, regarding the preferred numerical range (for example, content range, etc.), the lower limit value and upper limit value described in stages can be combined independently. For example, from the description of "preferably 10~90, more preferably 30~60", it is also possible to combine "preferably lower limit value (10)" and "more preferably upper limit value (60)" to set it to "10~60".

[Curing resin film (first curing resin film (x1))] The curing resin film of the present invention is a curing resin film used to form a protective film on both the bump forming surface and the side surface of a semiconductor chip having a bump forming surface with bumps; and satisfies the following requirement (I). <Requirement (I)> Under the conditions of a temperature of 90°C and a frequency of 1 Hz, a test piece of the aforementioned curable resin film having a diameter of 25 mm and a thickness of 1 mm is strained, and the storage modulus of the aforementioned test piece is measured, and when the storage modulus of the aforementioned test piece when the strain of the aforementioned test piece is 1% is set as Gc1, and when the storage modulus of the aforementioned test piece when the strain of the aforementioned test piece is 300% is set as Gc300, the value of X calculated by the following formula (i) is 19 or more and less than 10,000.

The test piece for measuring the storage elastic modulus is in the form of a film, and its plane shape is circular. The test piece may be a single-layered curable resin film with a thickness of 1 mm, but in terms of ease of manufacture, it is preferably a laminated film composed of a plurality of single-layered curable resin films with a thickness of less than 1 mm. The thickness of the plurality of single-layered curable resin films constituting the laminated film may be the same, different, or only partially the same, but in terms of ease of manufacture, it is preferably the same for all.

In addition, in this manual, the so-called "storage elastic modulus of the test piece" is not limited to the aforementioned Gc1 and Gc300. It means "the storage elastic modulus of the test piece corresponding to the strain when the test piece of resin film with a diameter of 25mm and a thickness of 1mm is strained under the conditions of temperature 90°C and frequency 1Hz."

The curable resin film according to one aspect of the present invention may be formed as, for example, a composite sheet having a laminated structure including a support sheet and the curable resin film.

In this specification, a hardening resin film (hardening resin film of the present invention) used to form a hardening resin film as a protective film on both the bump forming surface and the side surface of a semiconductor chip is also referred to as a "first hardening resin film (x1)" or "first hardening resin (x1)". In addition, a hardening resin film formed by hardening the "first hardening resin film (x1)" or "first hardening resin (x1)" is also referred to as a "first hardening resin film (r1)". In addition, a hardening resin film used to form a hardening resin film as a protective film on the surface (back surface) opposite to the bump forming surface of a semiconductor chip is also referred to as a "second hardening resin film (x2)" or "second hardening resin (x2)". Furthermore, a hardened resin film formed by hardening the "second hardening resin film (x2)" or the "second hardening resin (x2)" is also referred to as a "second hardening resin film (r2)". In addition, in this specification, a composite sheet for forming a first hardening resin film (r1) as a protective film on both the bump forming surface and the side surface of a semiconductor chip is also referred to as a "first composite sheet (α1)". The "first composite sheet (α1)" has a laminated structure formed by laminating a "first supporting sheet (Y1)" and a "layer (X1) of the first hardening resin (x1)". Furthermore, a composite sheet for forming a second hardening resin film (r2) as a protective film on the back surface of a semiconductor chip is also referred to as a "second composite sheet (α2)". The "second composite sheet (α2)" has a laminated structure formed by laminating a "second supporting sheet (Y2)" and a "layer (X2) of a second curable resin (x2)".

A schematic cross-sectional view of the first curable resin film (x1) is shown in FIG1. In addition, the following illustrations are used to make the features of the present invention easier to understand. For convenience, the main parts are enlarged and displayed, and the dimensional ratios of the various components are not limited to the actual ones.

The first curable resin film (x1) shown in FIG. 1 has a first peeling film 151 on one side (also referred to as "first side" in this specification) x1a, and has a second peeling film 152 on the other side (also referred to as "second side" in this specification) x1b opposite to the first side x1a. The first curable resin film (x1) having this structure is suitable for storage in a roll shape, for example.

The first peeling film 151 and the second peeling film 152 may be known. The first peeling film 151 and the second peeling film 152 may be the same or different from each other. As an example of the first peeling film 151 and the second peeling film 152 being different, the peeling force required when peeling from the first curable resin film (x1) is different.

The first curable resin film (x1) shown in FIG1 is formed by removing one of the first release film 151 and the second release film 152, so that the exposed surface becomes the attachment surface to the attachment object. Then, the remaining other of the first release film 151 and the second release film 152 is removed, so that the exposed surface becomes the attachment surface of the first supporting sheet (Y1) used to form the first composite sheet (α1) described later.

In addition, although FIG. 1 shows an example in which the release film is provided on both sides (the first side x1a and the second side x1b) of the first curable resin film (x1), the release film may be provided only on any one side of the first curable resin film (x1), that is, only on the first side x1a or only on the second side x1b.

The first curable resin film (x1) may be either thermosetting or energy ray curable, or may have both thermosetting and energy ray curable properties.

In this specification, the so-called "energy ray" means an electromagnetic wave or charged particle beam that has energy quanta. Examples of energy rays include ultraviolet rays, radiation, electron beams, etc. Ultraviolet rays can be irradiated by using a high-pressure mercury lamp, fusion lamp, xenon lamp, fluorescent lamp, or LED lamp as an ultraviolet source. Electron beams can be irradiated by electron beam accelerators, etc. In addition, in this specification, the so-called "energy ray curability" means the property of curing by irradiation with energy rays, and "non-energy ray curability" means the property of not curing even if irradiated with energy rays.

The first curable resin film (x1) contains a resin component. In addition, the first curable resin film (x1) may contain or not contain components other than the resin component together with the resin component. As a preferred embodiment of the first curable resin film (x1), for example, various additives that are not equivalent to the resin component, filler, and any one of the resin components (resin component and filler) and have an effect of adjusting the storage elastic modulus of the first curable resin film (x1) can be cited.

Examples of the additive having the effect of adjusting the storage elastic modulus of the first curable resin film (x1) include rheology control agents (thixotropic agents), surfactants, silicone oil, and the like.

The first curable resin film (x1) is soft and suitable for attachment to an object having a concave-convex surface, such as a semiconductor chip wafer having a bump-forming surface with bumps and a groove as a predetermined dividing line. In the following description, "a semiconductor chip wafer having a bump-forming surface with bumps and a groove as a predetermined dividing line" may also be referred to as "a semiconductor chip wafer". The first curable resin film (x1) is pressed and attached to the bump-forming surface of the semiconductor chip wafer, so that the first curable resin film (x1) is filled into the groove with good embedding properties. Furthermore, the first curable resin film (x1) is pressed and adhered to the bump forming surface of the semiconductor chip manufacturing wafer, so that the bump passes through the first curable resin film (x1), and the top of the bump protrudes from the first curable resin film (x1). In addition, the first curable resin film (x1) covers the bump and spreads between the bumps, and while closely adhering to the bump forming surface, covers the surface of the bump, especially the surface near the bump forming surface, and buries the base of the bump. In this state, the residue of the first curable resin film (x1) can be suppressed on the upper part of the bump, mainly the top. Therefore, of course, the first curable resin film (r1) as the cured product of the first curable resin film (x1) is also suppressed from being attached to the upper part of the bump. Moreover, after being attached to the attachment object, the first curable resin film (x1) can easily maintain the initial (before attachment) area of the first curable resin film (x1), and can also suppress the phenomenon that the area after attachment is larger than the initial (before attachment) area of the first curable resin film (x1) (hereinafter also referred to as "protrusion"). Therefore, when the first curable resin film (x1) is attached to the bump forming surface of the semiconductor chip manufacturing wafer, poor embedding of the groove portion or the bump base portion can also be suppressed. Furthermore, when the first curable resin film (x1) is used, the first curable resin film (x1) and the first curable resin film (r1) as the cured product thereof are provided on the bump forming surface, so that the area other than the upper part of the bump or the area near the bump on the bump forming surface can be suppressed from being exposed unexpectedly (hereinafter also referred to as "shrinking"). These effects can be obtained by setting the X value specified in the above requirement (I) to be 19 or more and less than 10,000.

In addition, the presence or absence of the residue of the first curable resin film (x1) or the first curable resin film (r1) on the upper part of the bump can be confirmed by, for example, observing the upper part of the bump with an optical microscope or SEM (scanning electron microscope) or acquiring photographic data. In addition, the presence or absence of protrusion of the first curable resin film (x1) can be observed visually or the like. Furthermore, the presence or absence of shrinkage (cissing) of the first curable resin film (x1) or the first curable resin film (r1) can be confirmed by, for example, observing the bump formation surface with an optical microscope or SEM (scanning electron microscope) or acquiring photographic data.

In addition, when a resin film such as the first curable resin film (x1) is attached to an attached object and a protrusion occurs, the amount of the protrusion can be calculated by the following method. That is, the resin film in a protruding state is viewed from above, 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 obtained. Furthermore, the value of the width of the resin film before the initial (that is, before the protrusion occurs) is obtained at the position where the line segment before the maximum value is overlapped. Then, the amount of the protrusion of the resin film can be calculated by subtracting the value of the width of the resin film from the maximum value of the length of the line segment.

FIG2 is a plan view for schematically illustrating the protrusion amount of the aforementioned resin film when the plane shape of the resin film is circular. The resin film 101 shown in FIG2 is in a state of being attached to the attachment object 102 and being in a state of being protruded from the initial size. The symbol 101' shows the resin film of the initial size, which is simply displayed for easy understanding of the protrusion amount. The initial plane shape of the resin film 101' is circular here, but the plane shape of the resin film 101 in the protruding state is non-circular. However, this is an example, and the plane shape of the resin film 101 in the protruding state is not limited to that shown here.

In order to obtain the protrusion amount of the resin film 101, it is only necessary to find the maximum value of the length _D1 of the line segment connecting a point 1010a and another point 1010b on the outer periphery 1010 of the resin film 101, and then find the value _D0 of the initial width of the resin film 101' (i.e., before the protrusion) at the position overlapping with the previous line segment indicating the maximum value. The difference between _D1 and _D0 ( _D1 - _D0 ) is the aforementioned protrusion amount. The previous line segment indicating the maximum value in the resin film 101 may exist in a plan view passing through the center of a circle in the initial resin film 101'. In this case, the value of the initial width of the resin film 101' at the position overlapping with the previous line segment indicating the maximum value is the diameter of the resin film 101'.

In addition, here, although the protrusion amount of the resin film is described with reference to the drawings when the plane shape of the resin film is a circle, the protrusion amount of the resin film can be calculated by the same method when the plane shape is other than a circle.

When the first curable resin film (x1) is attached to the bump-forming surface of a semiconductor chip manufacturing wafer, the strain of the curable resin film is greatly different in the middle stage when the first curable resin film (x1) protrudes through the upper part of the bump and begins to intrude into the groove, and in the final stage when the first curable resin film (x1) is buried in the base of the bump and buried in the groove. More specifically, the strain of the first curable resin film (x1) in the aforementioned middle stage is small, and the strain of the first curable resin film (x1) in the aforementioned final stage is large. The first curable resin film (x1) adopts Gc1 as its storage elastic modulus when the strain is small, and adopts Gc300 as its storage elastic modulus when the strain is large. By setting Gc1 to be high, Gc300 to be low, and setting the X value (=Gc1/Gc300) specified in the above requirement (I) to be greater than 19 and less than 10,000, the excellent effect described above can be obtained.

From the viewpoint of making it easier to exert the effect of the present invention, the first curable resin film (x1) preferably has an upper limit of the X value specified in the above requirement (I) of 5000 or less, more preferably 2000 or less, further preferably 1000 or less, further preferably 500 or less, further preferably 300 or less, further preferably 100 or less, further preferably 70 or less. In addition, from the viewpoint of making the embedding property of the trench of the semiconductor wafer manufacturing wafer better, the X value specified in the above requirement (I) is preferably 25 or more, more preferably 30 or more, further preferably 40 or more, further preferably 50 or more, further preferably 60 or more.

In the first curable resin film (x1), Gc1 is not particularly limited as long as the X value specified in the above requirement (I) is 19 or more and less than 10000. However, from the viewpoint of more easily exerting the effect of the present invention, Gc1 is preferably 1×10 ⁴ to 1×10 ⁶ Pa, more preferably 3×10 ⁴ to 7×10 ⁵ Pa, and even more preferably 5×10 ⁴ to 5×10 ⁵ Pa.

In the first curable resin film (x1), Gc300 is not particularly limited as long as the X value is 19 or more and less than 10000. However, in the effect of the present invention, from the viewpoint of making the embedding property of the groove of the semiconductor chip manufacturing wafer better, Gc300 is preferably less than 15,000Pa, more preferably 10,000Pa or less, more preferably 5,000Pa or less, more preferably 4,000Pa or less, and further preferably 3,500Pa or less. In addition, from the viewpoint of suppressing the shrinkage (cissing) of the first curable resin film (x1), Gc300 is preferably 100Pa or more, more preferably 500Pa or more, and more preferably 1,000Pa or more.

In the first curable resin film (x1), it is preferred that, while the value of X is specified in the requirement (I), either or both of Gc1 and Gc300 satisfy the above range.

The storage elastic modulus of the first curable resin film (x1) is not limited to Gc1 and Gc300, and can be easily adjusted by adjusting one or both of the type and content of the components contained in the first curable resin film (x1). To this end, one or both of the type and content of the components contained in the composition used to form the first curable resin film (x1) can be adjusted. For example, when the first thermosetting resin film-forming composition (x1-1-1) described later is used, the storage elastic modulus of the first curable resin film (x1) can be easily adjusted by adjusting one or both of the types and contents of the main components such as the polymer component (A) and the filler (D) in the composition, and adjusting one or both of the types and contents of one or more additives (I) selected from rheology control agents, surfactants, and silicone oils. For example, if the content of one or both of the filler (D) and the additive (I) described above in the first curable resin film (x1) and the first curable resin film-forming composition is increased, Gc1 can be easily adjusted to a larger value, and as a result, the X value can be easily adjusted to a larger value.

The first curable resin film (x1) may be composed of one layer (single layer) or may be composed of two or more layers. When the first curable resin film (x1) is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.

In this specification, regardless of the case of the first curable resin film (x1), the phrase “multiple layers may be the same or different from each other” means “all layers may be the same, all layers may be different, or only some layers may be the same”. Furthermore, the phrase “multiple layers may be different from each other” means “at least one of the constituent material and thickness of each layer may be different from each other”.

From the perspective of improving the coverage of the bump-forming surface of the semiconductor wafer and improving the embedding property of the groove of the semiconductor wafer, the thickness of the first curable resin film (x1) is preferably 10 μm or more, more preferably 20 μm or more, more preferably 30 μm or more, and more preferably more than 30 μm. Furthermore, it is preferably 200 μm or less, more preferably 150 μm or less, more preferably 130 μm or less, more preferably 100 μm or less, and even more preferably 80 μm or less. Here, "the thickness of the first curable resin layer (X1)" means the thickness of the entire layer (X1), for example, the thickness of the layer (X1) composed of a plurality of layers means the total thickness of all layers constituting the layer (X1). Here, "the thickness of the first curable resin film (x1)" means the thickness of the entire first curable resin film (x1), for example, the thickness of the first curable resin film (x1) composed of a plurality of layers means the total thickness of all layers constituting the first curable resin film (x1).

<First curable resin film forming composition> The first curable resin film (x1) can be formed using the first curable resin film forming composition containing its constituent materials. For example, the first curable resin film (x1) can be formed by applying the first curable resin film forming composition to the surface of the object to be formed and drying it as needed. The content ratio of the components that do not vaporize at room temperature in the first curable resin film forming composition is usually the same as the content ratio of the aforementioned components in the first curable resin film (x1). In this specification, the so-called "normal temperature" means a temperature that is not particularly cold or hot, that is, a normal temperature, for example, a temperature of 15 to 25°C.

The first thermosetting resin film (x1-1) can be formed using a first thermosetting resin film forming composition (x1-1-1), and the first energy ray-curing resin film (x1-2) can be formed using a first energy ray-curing resin film forming composition (x1-2-1). In addition, in the present specification, when the first curable resin film (x1) has both thermosetting and energy ray-curing properties, and when the contribution of the thermosetting of the first curable resin film (x1) to the first curable resin film (r1) formed by curing the first curable resin film (x1) is greater than the contribution of the energy ray curing, the first curable resin film (x1) is treated as a thermosetting film. On the contrary, when the contribution of energy ray curing to the curing of the first curable resin film (x1) is greater than the contribution of heat curing, the first curable resin film (x1) is treated as energy ray curable.

The first curable resin film-forming composition can be applied by a known method, for example, a method using various coating machines such as a rotary coater, a spray coater, 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 wire mesh coater, a Meyer bar coater, and a kiss coater.

Regardless of whether the first curable resin film (x1) is heat-curable or energy-ray-curable, the drying conditions of the curable resin film-forming composition are not particularly limited. However, when the first curable resin film-forming composition contains the solvent described later, it is preferably heat-dried. Moreover, the curable resin film-forming composition containing the solvent is preferably heat-dried under conditions of, for example, 70 to 130°C for 10 seconds to 5 minutes. However, the first thermosetting resin film-forming composition (x1-1-1) is preferably heat-dried in a non-thermally curing manner for the composition itself and the first thermosetting resin film (x1-1) formed by the composition.

The first thermosetting resin film (x1-1) and the first energy ray-curable resin film (x1-2) are described in further detail below.

<First thermosetting resin film (x1-1)> When the first thermosetting resin film (x1-1) is cured to form the first cured resin film (r1) as the cured product, the curing conditions are not particularly limited as long as the degree of curing of the cured product is such that the cured product can fully exert its function, and can be appropriately selected according to the type of the first thermosetting resin film (x1-1), the purpose of the cured product, etc. The heating temperature during the curing of the first thermosetting resin film (x1-1) is preferably 100 to 200°C, more preferably 110 to 170°C, and particularly preferably 120 to 150°C. Furthermore, the heating time during the thermal curing is preferably 0.5 to 5 hours, more preferably 0.5 to 4 hours, and particularly preferably 1 to 3 hours.

<First curable resin film forming composition (x1-1-1)> As the first thermosetting resin film forming composition (x1-1-1), for example, there can be cited a first thermosetting resin film forming composition (x1-1-1) containing a polymer component (A), a thermosetting component (B), a filler (D) and an additive (I) (in this specification, sometimes simply referred to as "composition (x1-1-1)").

(Polymer component (A)) The polymer component (A) is a polymer compound used to impart film-forming properties or flexibility to the first thermosetting resin film (x1-1). The polymer component (A) has thermoplasticity but does not have thermosetting properties. In addition, in this specification, the polymer compound also includes products of polymerization reactions. The polymer component (A) contained in the composition (x1-1-1) and the first thermosetting resin film (x1-1) may be only one kind or two or more kinds. In the case of two or more kinds, the combination and ratio of the polymer components may be arbitrarily selected.

Examples of the polymer component (A) include polyvinyl acetal, acrylic resin, urethane resin, phenoxy resin, silicone resin, and saturated polyester resin. Among them, the polymer component (A) is preferably polyvinyl acetal from the viewpoint of adjusting Gc300 to an appropriate value and making it easier to adjust the X value to an appropriate value.

As the polyvinyl alcohol acetal mentioned above in the polymer component (A), known ones can be cited. Among them, as preferred polyvinyl alcohol acetal, for example, polyvinyl alcohol formal, polyvinyl alcohol butyral, etc. can be cited, and polyvinyl alcohol butyral is more preferred. As polyvinyl alcohol butyral, those having the constituent units shown by the following formulas (i)-1, (i)-2 and (i)-3 can be cited.

(In the formula, l, m, and n are independently integers greater than 1.)

The weight average molecular weight (Mw) of polyvinyl alcohol acetal is preferably 5,000 to 200,000, and more preferably 8,000 to 100,000. By having the weight average molecular weight of polyvinyl alcohol acetal in such a range, when the first thermosetting resin film (x1-1) is attached to the bump forming surface of a wafer for semiconductor chip manufacturing, the following effects can be further improved: the effect of suppressing the residue of the first thermosetting resin film (x1-1) on the upper part of the bump, the effect of suppressing the protrusion of the first thermosetting resin film (x1-1), the effect of suppressing the shrinkage (cissing) of the first thermosetting resin film (x1-1) and its cured product on the bump forming surface, and the effect of improving the embedding property of the first thermosetting resin film (x1-1) in the groove.

The glass transition temperature (Tg) of polyvinyl alcohol acetal is preferably 40-80°C, more preferably 50-70°C. By having the Tg of polyvinyl alcohol acetal in such a range, when the first thermosetting resin film (x1-1) is attached to the bump forming surface of the wafer for semiconductor chip manufacturing, the following effects can be further improved: the effect of suppressing the residue of the first thermosetting resin film (x1-1) on the upper part of the bump, the effect of suppressing the protrusion of the first thermosetting resin film (x1-1), the effect of suppressing the shrinkage (cissing) of the first thermosetting resin film (x1-1) and its cured product on the bump forming surface, and the effect of improving the embedding property of the first thermosetting resin film (x1-1) in the groove.

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

As the acrylic resin mentioned above in the polymer component (A), known acrylic polymers can be cited. The weight average molecular weight (Mw) of the acrylic resin is preferably 5,000 to 1,000,000, and more preferably 8,000 to 800,000. By setting the weight average molecular weight of the acrylic resin to such a range, when the first thermosetting resin film (x1-1) is attached to the bump forming surface of a wafer for semiconductor chip manufacturing, the following effects can be further improved: the effect of suppressing the residue of the first thermosetting resin film (x1-1) on the upper part of the bump, the effect of suppressing the protrusion of the first thermosetting resin film (x1-1), the effect of suppressing the shrinkage (cissing) of the first thermosetting resin film (x1-1) and its cured product on the bump forming surface, and the effect of enhancing the embedding property of the first thermosetting resin film (x1-1) in the groove.

The glass transition temperature (Tg) of the acrylic resin is preferably -50 to 70°C, more preferably -30 to 60°C. By having the Tg of the acrylic resin in such a range, when the first thermosetting resin film (x1-1) is attached to the bump forming surface of the wafer for semiconductor chip manufacturing, the following effects can be further improved: the effect of suppressing the residue of the first thermosetting resin film (x1-1) on the upper part of the bump, the effect of suppressing the protrusion of the first thermosetting resin film (x1-1), the effect of suppressing the shrinkage (cissing) of the first thermosetting resin film (x1-1) and its cured product on the bump forming surface, and the effect of improving the embedding property of the first thermosetting resin film (x1-1) in the groove.

When an acrylic resin has two or more constituent units, the glass transition temperature (Tg) of the acrylic resin can be calculated using the Fox equation. The Tg of the monomer from which the above constituent units are derived can be the value listed in the polymer data manual or the adhesive manual.

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

Examples of acrylic resins include polymers of one or more (meth)acrylates; copolymers of two or more monomers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene and N-hydroxymethylacrylamide; and 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-hydroxymethylacrylamide.

In this specification, the term "(meth)acrylic acid" is a concept that includes both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid, for example, "(meth)acrylate" is a concept that includes both "acrylate" and "methacrylate", and "(meth)acryl" is a concept that includes both "acryl" and "methacryl".

Examples of the (meth)acrylates constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, and octyl (meth)acrylate. n-octyl acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, 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), heptadecanyl (meth)acrylate, octadecyl (meth)acrylate (octadecyl (meth)acrylate), =(meth)acrylic acid alkyl esters whose alkyl groups are chain-like structures with carbon numbers of 1 to 18, such as stearyl (meth)acrylate, etc.; (meth)acrylic acid cycloalkyl esters such as isoborneol (meth)acrylate and dicyclopentyl (meth)acrylate; (meth)acrylic acid arylalkyl esters such as benzyl (meth)acrylate; (meth)acrylic acid cycloalkenyl esters such as dicyclopentenyl (meth)acrylate; (meth)acrylic acid cycloalkenyloxyalkyl esters such as dicyclopentenyloxyethyl (meth)acrylate; (meth)acrylic acid imidate; (meth)acrylic acid cycloalkenyl esters; (Meth)acrylates containing glycidyl groups, such as glycidyl (meth)acrylate; (Meth)acrylates containing hydroxyl 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, 4-hydroxybutyl (meth)acrylate; (Meth)acrylates containing substituted amino groups, such as N-methylaminoethyl (meth)acrylate. Here, the so-called "substituted amino group" means a group in which one or two hydrogen atoms of an amino group are replaced by a group other than hydrogen atoms.

The acrylic resin may have functional groups such as vinyl, (meth)acryl, amino, hydroxyl, carboxyl, isocyanate, etc. that can bond with other compounds. The aforementioned functional groups of the acrylic resin may bond with other compounds via the crosslinking agent (F) described below, or may bond directly with other compounds without the crosslinking agent (F). By bonding the acrylic resin with other compounds via the aforementioned functional groups, for example, the reliability of the package obtained using the first thermosetting resin film (x1-1) tends to be improved.

In the composition (x1-1-1), the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (that is, in the first thermosetting resin film (x1-1), the ratio of the content of the polymer component (A) to the total mass of the first thermosetting resin film (x1-1)) is preferably 5~25 mass%, and more preferably 5~15 mass%, regardless of the type of the polymer component (A).

(Thermosetting component (B)) Thermosetting component (B) is a component that has thermosetting properties and is used to thermoset the first thermosetting resin film (x1-1) to form a hard cured product. Thermosetting component (B) contained in the composition (x1-1-1) and the first thermosetting resin film (x1-1) may be only one kind or two or more kinds. In the case of two or more kinds, the combination and ratio of the components may be arbitrarily selected.

Examples of the thermosetting component (B) include epoxy-based thermosetting resins, polyimide resins, and unsaturated polyester resins. Among these, the thermosetting component (B) is preferably an epoxy-based thermosetting resin.

･Epoxy-based thermosetting resin Epoxy-based thermosetting resin is composed of epoxy resin (B1) and thermosetting agent (B2). The epoxy-based thermosetting resin contained in the composition (x1-1-1) and the first thermosetting resin film may be only one type or two or more types. When there are two or more types, the combination and ratio of the epoxy-based thermosetting resins may be arbitrarily selected.

･Epoxy resin (B1) The epoxy resin (B1) may be a known one, for example, a polyfunctional epoxy resin, a biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated product, o-cresol novolac epoxy resin, a dicyclopentadiene type epoxy resin, a biphenyl type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenylene skeleton type epoxy resin, and an epoxy compound having two or more functional groups.

The epoxy resin (B1) may be an epoxy resin having an unsaturated hydrocarbon group. The epoxy resin having an unsaturated hydrocarbon group has a higher compatibility with the acrylic resin than the epoxy resin not having an unsaturated hydrocarbon group. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, for example, the reliability of the package obtained by using the first thermosetting resin film (x1-1) tends to be improved.

Examples of epoxy resins having unsaturated hydrocarbon groups include compounds in which a part of the epoxy groups of a polyfunctional epoxy resin is converted into a group having an unsaturated hydrocarbon group. Such compounds are obtained, for example, by subjecting (meth)acrylic acid or a derivative thereof to an addition reaction of an epoxy group. In addition, examples of epoxy resins having unsaturated hydrocarbon groups include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring constituting the epoxy resin. The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (vinyl group), a 2-propenyl group (allyl group), a (meth)acrylyl group, a (meth)acrylamide group, and the like, preferably an acryl group.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but from the viewpoint of the curability of the first thermosetting resin film (x1-1) and the strength and heat resistance of the cured product of the first thermosetting resin film (x1-1), it is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000. The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1,000 g/eq, and more preferably 200 to 800 g/eq.

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

･Thermosetting agent (B2) Thermosetting agent (B2) functions as a curing agent for epoxy resin (B1). As thermosetting agent (B2), for example, there can be listed compounds having two or more functional groups that can react with epoxy groups in one molecule. As the aforementioned functional group, for example, there can be listed phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, and acid groups anhydrided, etc., preferably phenolic hydroxyl groups, amino groups, or acid groups anhydrided, and more preferably phenolic hydroxyl groups or amino groups.

Among the thermosetting agents (B2), examples of phenolic curing agents having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenol, novolac-type phenolic resins, dicyclopentadiene-based phenolic resins, and aralkylphenolic resins. Among the thermosetting agents (B2), examples of amine-based curing agents having an amine group include dicyandiamide (hereinafter, also referred to as "DICY") and the like.

Thermosetting agent (B2) may have an unsaturated hydrocarbon group. Examples of thermosetting agent (B2) having an unsaturated hydrocarbon group include compounds in which a portion of the hydroxyl groups of a phenolic resin is replaced by a group having an unsaturated hydrocarbon group, compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring of a phenolic resin, and the like. The unsaturated hydrocarbon group in thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.

The number average molecular weight of the resin component in the thermosetting agent (B2), such as a multifunctional phenol resin, a novolac type phenol resin, a dicyclopentadiene type phenol resin, an aralkyl type phenol resin, is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000. The molecular weight of the non-resin component in the thermosetting agent (B2), such as diphenol, dicyandiamide, etc., is not particularly limited, but is preferably, for example, 60 to 500.

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

In the composition (x1-1-1) and the first thermosetting resin film (x1-1), the content of the thermosetting agent (B2) is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass, for example, any one of 5 to 150 parts by mass, 10 to 100 parts by mass, and 15 to 75 parts by mass, relative to 100 parts by mass of the content of the epoxy resin (B1). When the content of the thermosetting agent (B2) is greater than the lower limit, the first thermosetting resin film (x1-1) is more easily cured. By making the content of the thermosetting agent (B2) below the upper limit, the moisture absorption rate of the first thermosetting resin film (x1-1) is reduced, for example, the reliability of the package obtained using the first thermosetting resin film (x1-1) is further improved.

In the composition (x1-1-1) and the first thermosetting resin film (x1-1), the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is preferably 600~1000 parts by mass relative to 100 parts by mass of the polymer component (A). By setting the aforementioned content of the thermosetting component (B) to such a range, when the first thermosetting resin film (x1-1) is attached to the bump forming surface of the semiconductor chip manufacturing wafer, the following effects can be further improved: the effect of suppressing the residue of the first thermosetting resin film (x1-1) on the upper part of the bump, the effect of suppressing the protrusion of the first thermosetting resin film (x1-1), the effect of suppressing the shrinkage (cissing) of the first thermosetting resin film (x1-1) and its cured product on the bump forming surface, and the effect of improving the embedding property of the first thermosetting resin film (x1-1) in the groove; and a hard cured product can be formed. In addition, in order to obtain such effects more significantly, the content of the thermosetting component (B) can be appropriately adjusted according to the type of the polymer component (A).

For example, when the polymer component (A) is the aforementioned polyvinyl alcohol acetal, in the composition (x1-1-1) and the first thermosetting resin film (x1-1), the content of the thermosetting component (B) is preferably 600~1,000 parts by mass, more preferably 650~1,000 parts by mass, and particularly preferably 650~950 parts by mass, relative to 100 parts by mass of the polymer component (A).

(Filling material (D)) By adjusting the amount of the filling material (D) in the composition (x1-1-1) and the first thermosetting resin film (x1-1), the aforementioned X value can be more easily adjusted. In addition, by adjusting the amount of the filling material (D) in the composition (x1-1-1) and the first thermosetting resin film (x1-1), the thermal expansion coefficient of the cured product of the first thermosetting resin film (x1-1) can be more easily adjusted. For example, by optimizing the thermal expansion coefficient of the cured product of the first thermosetting resin film (x1-1) for the object of formation of the cured product, the reliability of the package (Package) obtained using the first thermosetting resin film (x1-1) is further improved. Furthermore, by using the first thermosetting resin film (x1-1) containing the filler (D), the moisture absorption rate of the cured product of the first thermosetting resin film (x1-1) can be reduced, thereby improving the heat dissipation property.

The filler (D) may be either an organic filler or an inorganic filler, but preferably an inorganic filler. As preferred inorganic fillers, for example, powders such as silica, alumina, talc, calcium carbonate, titanium dioxide, red iron, silicon carbide, and boron nitride; beads obtained by sphericalizing these inorganic fillers; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. Among these, the inorganic filler is preferably silica or alumina.

The filler (D) contained in the composition (x1-1-1) and the first thermosetting resin film (x1-1) may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of the fillers may be selected arbitrarily.

In the composition (x1-1-1), the ratio of the content of the filler (D) to the total content of all components other than the solvent (that is, in the first thermosetting resin film (x1-1), the ratio of the content of the filler (D) to the total mass of the first thermosetting resin film (x1-1)) is preferably 5~45 mass%, more preferably 5~40 mass%, and even more preferably 5~30 mass%. By setting the above-mentioned ratio to such a range, when the first thermosetting resin film (x1-1) is attached to the bump forming surface of a semiconductor chip manufacturing wafer, the following effects can be further improved: the effect of suppressing the residue of the first thermosetting resin film (x1-1) on the upper part of the bump, the effect of suppressing the protrusion of the first thermosetting resin film (x1-1), the effect of suppressing the shrinkage (cissing) of the first thermosetting resin film (x1-1) and its cured product on the bump forming surface, and the effect of improving the embedding property of the first thermosetting resin film (x1-1) in the groove; and the above-mentioned thermal expansion coefficient can be more easily adjusted.

(Additive (I)) By adjusting the type or amount of the additive (I) in the composition (x1-1-1) and the first thermosetting resin film (x1-1), Gc1 can be appropriately adjusted, and the aforementioned X value can be more easily adjusted. Among them, the point at which the aforementioned X value can be more easily adjusted, as a preferred additive (I), for example, rheology control agents, surfactants, silicone oils, etc. can be listed.

More specifically, the aforementioned rheology control agent may include, for example, polyhydroxycarboxylic acid esters, polyvalent carboxylic acids, polyamide resins, etc. As the aforementioned surfactant, for example, modified silicone, acrylic polymers, etc. may be listed. As the aforementioned silicone oil, for example, aralkyl modified silicone oil, modified polydimethylsiloxane, etc. may be listed, and as the modifying group, aralkyl; polar groups such as hydroxyl; groups having unsaturated bonds such as vinyl and phenyl may be listed.

In addition to the above, the additives (I) may include various other general additives such as plasticizers, antistatic agents, antioxidants, gettering agents, ultraviolet absorbers, and thickeners.

The additive (I) contained in the composition (x1-1-1) and the first thermosetting resin film (x1-1) may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of the additives may be selected arbitrarily.

The content of the additive (I) in the composition (x1-1-1) and the first thermosetting resin film (x1-1) is not particularly limited and can be appropriately adjusted according to the type or purpose. For example, in the case of adjusting the aforementioned X value, the ratio of the content of the additive (I) to the total content of all components other than the solvent in the composition (x1-1-1) (that is, the ratio of the content of the additive (I) to the total mass of the first thermosetting resin film (x1-1)) is preferably 0.5 to 10% by mass, more preferably 0.5 to 7% by mass, and even more preferably 0.5 to 5% by mass.

(Hardening accelerator (C)) The composition (x1-1-1) and the first thermosetting resin film (x1-1) may contain a hardening accelerator (C). The hardening accelerator (C) is a component for adjusting the hardening speed of the composition (x1-1-1). Preferred hardening 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; and tetraphenylborates such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate.

The curing accelerator (C) contained in the composition (x1-1-1) and the first thermosetting resin film (x1-1) may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of the accelerators may be arbitrarily selected.

When the curing accelerator (C) is used, the content of the curing accelerator (C) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the content of the thermosetting component (B) in the composition (x1-1-1) and the first thermosetting resin film (x1-1). When the content of the curing accelerator (C) is equal to or greater than the lower limit, the effect of using the curing accelerator (C) can be more significantly obtained. By setting the content of the curing accelerator (C) to be below the upper limit, for example, the effect of suppressing the highly polar curing accelerator (C) from migrating to the interface side with the adherend under high temperature and high humidity conditions in the first thermosetting resin film (x1-1) and segregating is enhanced, and for example, the reliability of the package obtained using the first thermosetting resin film (x1-1) is further improved.

(Coupling agent (E)) The composition (x1-1-1) and the first thermosetting resin film (x1-1) may contain a coupling agent (E). By using a coupling agent (E) having a functional group that can react with an inorganic compound or an organic compound, the adhesion and tightness of the first thermosetting resin film (x1-1) to the object to be adhered can be improved. In addition, by using a coupling agent (E), the cured product of the first thermosetting resin film (x1-1) will not lose heat resistance and water resistance will be improved.

The coupling agent (E) is preferably a compound having a functional group that can react with the functional group of the polymer component (A), the thermosetting component (B), etc., and is more preferably a silane coupling agent. As preferred silane coupling agents mentioned above, for example, 3-glyceryloxypropyl trimethoxysilane, 3-glyceryloxypropyl methyl diethoxysilane, 3-glyceryloxypropyl triethoxysilane, 3-glyceryloxymethyl diethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-(2-aminoethylamino) ... Oxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-butylpropyltrimethoxysilane, 3-butylpropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazole silane, etc.

The coupling agent (E) contained in the composition (x1-1-1) and the first thermosetting resin film (x1-1) may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of the coupling agents may be arbitrarily selected.

When a coupling agent (E) is used, the content of the coupling agent (E) in the composition (x1-1-1) and the first thermosetting resin film (x1-1) is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total content of the polymer component (A) and the thermosetting component (B). When the content of the coupling agent (E) is greater than the lower limit, the effect of using the coupling agent (E), such as improvement in the dispersibility of the filler (D) in the resin or improvement in the adhesion between the first thermosetting resin film (x1-1) and the object to be attached, can be more significantly obtained. When the content of the coupling agent (E) is less than the upper limit, the generation of outgassing can be further suppressed.

(Crosslinking agent (F)) When a polymer component (A) having a functional group such as a vinyl group, a (meth)acryl group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, etc. that can bond with other compounds is used, the composition (X1-1-1) and the first thermosetting resin film (x1-1) may contain a crosslinking agent (F). The crosslinking agent (F) is a component used to crosslink the aforementioned functional groups in the polymer component (A) with other compounds. By crosslinking in this way, the initial adhesion and cohesion of the first thermosetting resin film (x1-1) can be adjusted.

Examples of the crosslinking agent (F) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelating crosslinking agents (crosslinking agents having a metal chelating structure), and aziridine crosslinking agents (crosslinking agents having an aziridine group).

Examples of the organic polyvalent isocyanate compounds include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds are collectively referred to as "aromatic polyvalent isocyanate compounds, etc."); trimers, isocyanurates, and adducts of the aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the aromatic polyvalent isocyanate compounds, etc. with polyol compounds, etc. The "adducts" are reaction products of the aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, or alicyclic polyvalent isocyanate compounds with a compound containing low molecular weight active hydrogen, such as ethylene glycol, propylene glycol, neopentyl glycol, trihydroxymethylpropane, or castor oil. Examples of the adducts include the xylylene diisocyanate adduct of trihydroxymethylpropane described below. The term "terminated isocyanate urethane prepolymer" refers to a prepolymer having a urethane bond and an isocyanate group at the terminal of the molecule.

More specifically, the organic polyvalent isocyanate compound includes, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; Diisocyanates; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; a compound obtained by adding any one or two or more of toluene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate to all or part of the hydroxyl groups of a polyol such as trihydroxymethylpropane; lysine diisocyanate, etc.

Examples of the organic polyvalent imine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxyamide), trihydroxymethylpropane-tri-β-aziridine propionate, tetrahydroxymethylmethane-tri-β-aziridine propionate, and N,N'-toluene-2,4-bis(1-aziridinecarboxyamide)triethylmelamine.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (F), a polymer containing a hydroxyl group 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 first thermosetting resin film (x1-1) through the reaction between the crosslinking agent (F) and the polymer component (A).

The crosslinking agent (F) contained in the composition (x1-1-1) and the first thermosetting resin film (x1-1) may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of the crosslinking agents can be selected arbitrarily.

When a crosslinking agent (F) is used, the content of the crosslinking agent (F) in the composition (x1-1-1) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the content of the polymer component (A). When the content of the crosslinking agent (F) is greater than the lower limit, the effect of using the crosslinking agent (F) can be more significantly obtained. When the content of the crosslinking agent (F) is less than the upper limit, excessive use of the crosslinking agent (F) can be suppressed.

(Energy ray curable resin (G)) The composition (x1-1-1) and the first thermosetting resin film (x1-1) may contain an energy ray curable resin (G). The first thermosetting resin film (x1-1) may change its properties by irradiation with energy rays by containing the energy ray curable resin (G).

The energy ray curable resin (G) is obtained by polymerizing (curing) an energy ray curable compound. Examples of the energy ray curable compound include compounds having at least one polymerizable double bond in the molecule, preferably acrylate compounds having a (meth)acryloyl group.

Examples of the acrylate compounds include trihydroxymethylpropane tri(meth)acrylate, tetrahydroxymethylmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and the like. (meth)acrylates containing a cyclic aliphatic skeleton such as dicyclopentyl di(meth)acrylate; polyalkylene glycol (meth)acrylates such as polyethylene glycol di(meth)acrylate; oligoester (meth)acrylates; urethane (meth)acrylate oligomers; epoxy-modified (meth)acrylates; polyether (meth)acrylates other than the aforementioned polyalkylene glycol (meth)acrylates; itaconic acid oligomers, etc.

The weight average molecular weight of the energy ray-curable compound is preferably 100 to 30,000, more preferably 300 to 10,000.

The energy ray-curable compound used for polymerization may be used alone or in combination of two or more. When two or more energy ray-curable compounds are used for polymerization, the combination and ratio thereof may be arbitrarily selected.

When the energy ray curable resin (G) is used, the content of the energy ray curable resin (G) is preferably 1 to 95 mass %, more preferably 5 to 90 mass %, and even more preferably 10 to 85 mass %, based on the total amount of the active ingredients in the composition (x1-1-1).

(Photopolymerization initiator (H)) When the composition (x1-1-1) and the first thermosetting resin film (x1-1) contain the energy ray curing resin (G), the composition (x1-1-1) and the first thermosetting resin film (x1-1) may contain a photopolymerization initiator (H) in order to efficiently carry out the polymerization reaction of the energy ray curing resin (G).

Examples of the photopolymerization initiator (H) include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoic acid methyl ester, benzoin dimethyl ketal, 2,4-diethylthioxanone, 1-hydroxycyclohexyl phenyl ketone, benzyl diphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, diphenylethanedione, bibenzyl, diacetyl, 1,2-diphenylmethane, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2-chloroanthraquinone.

The photopolymerization initiator (H) may be used alone or in combination of two or more. When two or more photopolymerization initiators (H) are used, the combination and ratio thereof may be arbitrarily selected.

In the composition (x1-1-1), the content of the photopolymerization initiator (H) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 5 parts by mass, relative to 100 parts by mass of the energy ray-curable resin (G).

(Other components) Within the scope of not impairing the effect of the present invention, the composition (x1-1-1) and the first thermosetting resin film (x1-1) may contain other components that are not equivalent to any of the above-mentioned polymer component (A), thermosetting component (B), curing accelerator (C), filler (D), coupling agent (E), crosslinking agent (F), energy ray curing resin (G), photopolymerization initiator (H) and additive (I).

The composition (x1-1-1) and the first thermosetting resin film (x1-1) may contain only one or more of the aforementioned other components. In the case of two or more, the combination and ratio of the aforementioned other components may be arbitrarily selected. The content of the aforementioned other components in the composition (x1-1-1) and the first thermosetting resin film (x1-1) is not particularly limited, and may be appropriately selected according to the purpose.

(Solvent) The composition (x1-1-1) preferably further contains a solvent. The composition (x1-1-1) containing a solvent has good handling properties. The aforementioned solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having amide bonds) such as dimethylformamide and N-methylpyrrolidone, etc. The solvent contained in the composition (x1-1-1) may be only one kind or two or more kinds. In the case of two or more kinds, the combination and ratio of the solvents may be arbitrarily selected.

As for the solvent contained in the composition (x1-1-1), for example, methyl ethyl ketone can be cited as a more preferable one in terms of being able to more uniformly mix the components contained in the composition (x1-1-1).

The content of the solvent in the composition (x1-1-1) is not particularly limited and may be appropriately selected according to the types of components other than the solvent, for example.

<Method for producing the first thermosetting resin film-forming composition (x1-1-1)> The first thermosetting resin film-forming composition (x1-1-1) is obtained by blending the components used to constitute it. The order of addition of the components when blending is not particularly limited, and two or more components may be added at the same time. The method of mixing the components when blending is not particularly limited, and it can be appropriately selected from the following known methods: a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a stirrer, a method of mixing by applying ultrasonic waves, etc. The temperature and time when adding and mixing the components are not particularly limited as long as the components are not degraded, and can be appropriately adjusted, but the temperature is preferably 15~30℃.

<First energy ray curable resin film (x1-2)> When the first energy ray curable resin film (x1-2) is cured to form the first curable resin film (r1) as the cured product, the curing conditions are not particularly limited as long as the degree of curing of the cured product is such that the cured product can fully exert its function, and can be appropriately selected according to the type of the first energy ray curable resin film (x1-2), the use of the cured product, etc. For example, the energy ray irradiance during the curing of the first energy ray curable resin film (x1-2) is preferably 180~280mW/ ^cm2 . In addition, the light amount of the energy ray during the curing is preferably 450~1000mJ/ ^cm2 .

<First energy ray-curable resin film-forming composition (x1-2-1)> As the first energy ray-curable resin film-forming composition (x1-2-1), for example, there can be listed a first energy ray-curable resin film-forming composition (x1-2-1) containing an energy ray-curable component (a), a filler and an additive (in this specification, sometimes simply referred to as "composition (x1-2-1)").

(Energy ray curable component (a)) The energy ray curable component (a) is a component that can be cured by irradiation with energy rays, and is also a component used to impart film-forming properties or flexibility to the first energy ray curable resin film (x1-2). The energy ray curable component (a) is preferably uncured, preferably has adhesiveness, and more preferably is uncured and has adhesiveness.

Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000, and a compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80,000. The polymer (a1) may be at least partially crosslinked with a crosslinking agent or may be uncrosslinked.

･Polymer (a1) having an energy ray curable group with a weight average molecular weight of 80,000 to 2,000,000 As examples of the polymer (a1) having an energy ray curable group with a weight average molecular weight of 80,000 to 2,000,000, there can be cited: an acrylic polymer (a11) having a functional group that can react with a group possessed by another compound; and an acrylic resin (a1-1) obtained by polymerizing an energy ray curable compound (a12) having an energy ray curable group having a group that reacts with the aforementioned functional group and an energy ray curable double bond.

Examples of the functional group that can react with a group possessed by other compounds include hydroxyl, carboxyl, amino, substituted amino (a group in which one or two hydrogen atoms of an amino are replaced by a group other than hydrogen atoms), and epoxy. However, in terms of preventing corrosion of circuits such as semiconductor wafers or semiconductor chips, the functional group is preferably a group other than a carboxyl group. Among these, the functional group is preferably a hydroxyl group.

･Acrylic polymer (a11) having functional groups As the acrylic polymer (a11) having functional groups, for example, there can be listed: a copolymerization of an acrylic monomer having the functional groups and an acrylic monomer not having the functional groups, or a copolymerization of a monomer other than the acrylic monomer (non-acrylic monomer) in addition to the above monomers. In addition, the acrylic polymer (a11) can be a random copolymer or a block copolymer.

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

Examples of the monomer containing a hydroxyl group include hydroxyalkyl (meth)acrylates such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; and non-(meth)acrylic unsaturated alcohols (unsaturated alcohols having no (meth)acryloyl skeleton) such as vinyl alcohol and allyl alcohol.

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

The acrylic monomer having the above-mentioned functional group is preferably a monomer containing a hydroxyl group or a monomer containing a carboxyl group, and more preferably a monomer containing a hydroxyl group.

The acrylic monomer having the functional group constituting the acrylic polymer (a11) 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.

Examples of acrylic monomers not having the aforementioned functional groups 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, propyl (meth)acrylate, 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, butyl ... Alkyl esters such as isononyl (meth)acrylate, 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), heptadecanyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate) and the like are (meth)acrylate alkyl esters in which the alkyl group constituting the alkyl ester is a chain structure having 1 to 18 carbon atoms.

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

The acrylic monomer not having the functional group constituting the acrylic polymer (a11) 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.

Examples of the non-acrylic monomers include olefins such as ethylene and norbornene; vinyl acetate; styrene, etc. The non-acrylic monomers constituting the acrylic polymer (a11) may be only one type or two or more types. When there are two or more types, the combination and ratio of the non-acrylic monomers may be arbitrarily selected.

In the acrylic polymer (a11), the ratio (content) of the amount of the constituent units derived from the acrylic monomer having the functional group relative to the total amount of the constituent units constituting the acrylic polymer (a11) is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass. By making the ratio within such a range, in the acrylic resin (a1-1) obtained by copolymerizing the acrylic polymer (a11) and the energy ray-curable compound (a12), the content of the energy ray-curable group can easily adjust the degree of hardening of the hardened product of the first energy ray-curable resin film (x1-2) to a preferred range.

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be one kind or two or more kinds. When two or more kinds are used, the combination and ratio of the acrylic polymers may be arbitrarily selected.

In the composition (x1-2-1), the ratio of the content of the acrylic resin (a1-1) to the total content of the components other than the solvent (that is, in the first energy ray-curable resin film (x1-2), the ratio of the content of the acrylic resin (a1-1) to the total mass of the aforementioned film) is preferably 1~40 mass %, more preferably 2~30 mass %, and particularly preferably 3~20 mass %.

･Energy ray curing compound (a12) The energy ray curing compound (a12) preferably has one or more selected from the group consisting of isocyanate group, epoxy group and carboxyl group as a group that can react with the functional group possessed by the acrylic polymer (a11), and more preferably has an isocyanate group as the aforementioned group. For example, when the energy ray curing compound (a12) has an isocyanate group as the aforementioned group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the aforementioned functional group.

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

Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1-(diacryloyloxymethyl)ethyl isocyanate; Acryloyl monoisocyanate compounds obtained by the reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth)acrylate; Acryloyl monoisocyanate compounds obtained by the reaction of a diisocyanate compound or a polyisocyanate compound, a polyol compound, and hydroxyethyl (meth)acrylate, etc. Among them, the energy ray-curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.

The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) 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.

In the aforementioned acrylic resin (a1-1), the ratio of the content of the energy ray curable group derived from the aforementioned energy ray curable compound (a12) relative to the content of the aforementioned functional group derived from the aforementioned acrylic polymer (a11) is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. By having the aforementioned content ratio in such a range, the adhesion of the cured product of the energy ray curable resin film (x1-2) is further increased. In addition, when the aforementioned energy ray curable compound (a12) is a monofunctional compound (having one aforementioned group in one molecule), the upper limit of the aforementioned content ratio is 100 mol%, but when the aforementioned energy ray curable compound (a12) is a polyfunctional compound (having two or more aforementioned groups in one molecule), the upper limit of the aforementioned content ratio may exceed 100 mol%.

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

When at least a part of the polymer (a1) is crosslinked with a crosslinking agent, the polymer (a1) may be a monomer which is not equivalent to any of the monomers described above as constituting the acrylic polymer (a11) and has a group reactive with the crosslinking agent, and crosslinked at the group reactive with the crosslinking agent, or may be a polymer which is crosslinked at a group reactive with the functional group derived from the energy ray-curable compound (a12).

The composition (x1-2-1) and the first energy ray-curable resin film (x1-2) may contain only one kind of the aforementioned polymer (a1) or two or more kinds. When there are two or more kinds, the combination and ratio of the polymers may be arbitrarily selected.

Compound (a2) having a molecular weight of 100 to 80,000 and having an energy ray-curable group The energy ray-curable group in the compound (a2) having a molecular weight of 100 to 80,000 and having an energy ray-curable group may include a group containing an energy ray-curable double bond, and preferably, a (meth)acryl group, a vinyl group, and the like.

The compound (a2) is not particularly limited as long as it satisfies the above conditions, and examples thereof include low molecular weight compounds having an energy ray curable group, epoxy resins having an energy ray curable group, phenol resins having an energy ray curable group, and the like.

Among the aforementioned compounds (a2), examples of low molecular weight compounds having an energy ray-curable group include multifunctional monomers or oligomers, and preferably acrylate compounds having a (meth)acryloyl group. Examples of the aforementioned acrylate compounds include 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]propane, )phenyl]fluorene, 2,2-bis[4-((meth)acryloyloxypolypropoxy)phenyl]propane, tricyclodecanedimethanol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloyloxypropane and other bifunctional (meth)acrylates; Tris(2-(meth)acryloyloxyethyl)isocyanurate, ε-caprolactone-modified tris(2-(meth)acryloyloxyethyl)isocyanurate esters, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, ditrihydroxymethylpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like multifunctional (meth)acrylates; Urethane (meth)acrylate oligomers and the like multifunctional (meth)acrylate oligomers, etc.

Among the aforementioned compounds (a2), epoxy resins having energy ray curable groups and phenol resins having energy ray curable groups may be, for example, those described in paragraph 0043 of "Japanese Patent Publication No. 2013-194102". Such resins are also applicable to resins constituting the thermosetting component described later, but are regarded as the aforementioned compounds (a2) in the present invention.

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

The composition (x1-2-1) and the first energy ray-curable resin film (x1-2) may contain only one compound (a2) or two or more compounds. When there are two or more compounds, the combination and ratio thereof may be arbitrarily selected.

(Polymer (b) without energy ray curing group) When the composition (x1-2-1) and the first energy ray curing resin film (x1-2) contain the aforementioned compound (a2) as the aforementioned energy ray curing component (a), it is preferred that they further contain a polymer (b) without energy ray curing group. The aforementioned polymer (b) may be at least partially crosslinked by a crosslinking agent or may be uncrosslinked.

Examples of polymers (b) that do not have an energy-ray-hardening group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, acrylic urethane resins, and the like. Among these, the aforementioned polymer (b) is preferably an acrylic polymer (hereinafter, also referred to as "acrylic polymer (b-1)").

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

Examples of the acrylic monomers constituting the acrylic polymer (b-1) include alkyl (meth)acrylates, (meth)acrylates having a cyclic skeleton, (meth)acrylates containing a glycidyl group, (meth)acrylates containing a hydroxyl group, (meth)acrylates containing a substituted amino group, etc. Here, "substituted amino group" is as described above.

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

Examples of the aforementioned (meth)acrylates having a cyclic skeleton include (meth)acrylate cycloalkyl esters such as isoborneol (meth)acrylate and dicyclopentanyl (meth)acrylate; (meth)acrylate arylalkyl esters such as benzyl (meth)acrylate; (meth)acrylate cycloalkenyl esters such as dicyclopentenyl (meth)acrylate; and (meth)acrylate cycloalkenyloxyalkyl esters such as dicyclopentenyloxyethyl (meth)acrylate.

Examples of the aforementioned (meth)acrylate containing a glycidyl group include glycidyl (meth)acrylate, etc. Examples of the aforementioned (meth)acrylate containing a hydroxyl group include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Examples of the aforementioned (meth)acrylate containing a substituted amino group include N-methylaminoethyl (meth)acrylate, etc.

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

As the aforementioned polymer (b) not having an energy ray-curable group that is at least partially cross-linked by a cross-linking agent, for example, a reactive functional group in the aforementioned polymer (b) reacts with a cross-linking agent. The aforementioned reactive functional group can be appropriately selected according to the type of the cross-linking agent, etc., and is not particularly limited. For example, when the cross-linking agent is a polyisocyanate compound, as the aforementioned reactive functional group, a hydroxyl group, a carboxyl group, an amine group, etc. can be listed, and among these, a hydroxyl group with high reactivity with an isocyanate group is preferred. In addition, when the cross-linking agent is an epoxy compound, as the aforementioned reactive functional group, a carboxyl group, an amine group, etc. can be listed, and among these, a carboxyl group with high reactivity with an epoxy group is preferred. However, from the viewpoint of preventing corrosion of the circuit of the semiconductor wafer or semiconductor chip, the reactive functional group is preferably a group other than a carboxyl group.

As the aforementioned polymer (b) having a reactive functional group and not having an energy ray-hardening group, for example, there can be cited those obtained by polymerizing at least a monomer having the aforementioned reactive functional group. In the case of an acrylic polymer (b-1), as the monomer constituting the acrylic monomer or non-acrylic monomer, any one or both of which have the aforementioned reactive functional group can be used. As the aforementioned polymer (b) having a hydroxyl group as a reactive functional group, for example, there can be cited those obtained by polymerizing a (meth)acrylate containing a hydroxyl group. In addition, there can also be cited those obtained by polymerizing a monomer in which one or two or more hydrogen atoms in the aforementioned acrylic monomer or non-acrylic monomer are substituted with the aforementioned reactive functional group.

In the aforementioned polymer (b) having a reactive functional group, the ratio (content) of the amount of the constituent units derived from the monomer having a reactive functional group relative to the total amount of the constituent units constituting the polymer (b) is preferably 1 to 20% by mass, more preferably 2 to 10% by mass. When the aforementioned ratio is within such a range, the degree of crosslinking in the aforementioned polymer (b) becomes a more preferred range.

The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000, in order to improve the film-forming property of the composition (IV).

The polymer (b) not having an energy ray-curable group contained in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2) may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio thereof may be selected arbitrarily.

As the composition (x1-2-1), there can be cited a composition containing either or both of the aforementioned polymer (a1) and the aforementioned compound (a2). Furthermore, when the composition (x1-2-1) contains the aforementioned compound (a2), it is preferred that it further contains a polymer (b) having no energy ray-curable group, and in this case, it is preferred that it further contains the aforementioned (a1). Furthermore, the composition (x1-2-1) may not contain the aforementioned compound (a2), but may contain both the aforementioned polymer (a1) and the polymer (b) having no energy ray-curable group.

In the case where the composition (x1-2-1) contains the aforementioned polymer (a1), the aforementioned compound (a2) and a polymer (b) not having an energy ray-curable group, in the composition (x1-2-1), the content of the aforementioned compound (a2) is preferably 10 to 400 parts by mass, and more preferably 30 to 350 parts by mass, relative to 100 parts by mass of the total content of the aforementioned polymer (a1) and the polymer (b) not having an energy ray-curable group.

In the composition (x1-2-1), the ratio of the total content of the energy ray curable component (a) and the polymer (b) having no energy ray curable group to the total content of the components other than the solvent (that is, in the first energy ray curable resin film (x1-2), the ratio of the total content of the energy ray curable component (a) and the polymer (b) having no energy ray curable group to the total mass of the film) is preferably 5 to 90 mass%, more preferably 10 to 80 mass%, and particularly preferably 20 to 70 mass%. When the ratio is within such a range, the energy ray curability of the first energy ray curable resin film (x1-2) becomes better.

(Filling material) By adjusting the amount of the filling material in the composition (x1-2-1) and the first energy line curing resin film (x1-2), the aforementioned X value can be more easily adjusted. In addition, by adjusting the amount of the filling material in the composition (x1-2-1) and the first energy line curing resin film (x1-2), the thermal expansion coefficient of the cured product of the first energy line curing resin film (x1-2) can be more easily adjusted. For example, by optimizing the thermal expansion coefficient of the cured product of the first energy line curing resin film (x1-2) for the object of forming the protective film, the reliability of the package obtained using the first energy line curing resin film (x1-2) is further improved. Furthermore, by using the first energy ray-curable resin film (x1-2) containing a filler, the moisture absorption rate of the cured product of the first energy ray-curable resin film (x1-2) can be reduced, thereby improving the heat dissipation property.

The aforementioned filler contained in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2) may be the same as the filler (D) contained in the aforementioned composition (x1-1-1) and the first thermosetting resin film (x1-1).

The content of the filler in the composition (x1-2-1) and the first energy ray curable resin film (x1-2) may be the same as the content of the filler (D) in the composition (x1-1-1) and the first thermosetting resin film (x1-1).

The filler contained in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2) may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of the fillers may be arbitrarily selected.

In the composition (x1-2-1), the ratio of the filler content to the total content of all components other than the solvent (i.e., in the first energy ray-curable resin film (x1-2), the ratio of the filler content to the total mass of the first energy ray-curable resin film (x1-2)) can be, for example, 5~45 mass%. By setting the above-mentioned ratio to such a range, when the first energy-curable resin film (x1-2) is attached to the bump-forming surface of a semiconductor chip manufacturing wafer, the following effects can be further improved: the effect of suppressing the residue of the first energy-curable resin film (x1-2) on the upper part of the bump, the effect of suppressing the protrusion of the first energy-curable resin film (x1-2), the effect of suppressing the shrinkage (cissing) of the first energy-curable resin film (x1-2) and its cured product on the bump-forming surface, and the effect of enhancing the embedding property of the first energy-curable resin film (x1-2) in the groove; and the above-mentioned thermal expansion coefficient can be more easily adjusted.

(Additives) The aforementioned X value can be more easily adjusted by adjusting the type or amount of additives in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2).

The aforementioned additives contained in the composition (x1-2-1) and the first energy ray curable resin film (x1-2) may be the same as the additive (I) contained in the composition (x1-1-1) and the first thermosetting resin film (x1-2) described above. For example, from the point of view of being able to more easily adjust the aforementioned X value, the preferred additives include rheology control agents, surfactants, silicone oils, etc.

The content of the additive in the composition (x1-2-1) and the first energy ray curable resin film (x1-2) may be the same as the content of the additive (I) in the composition (X1-1-1) and the first heat curable resin film (x1-1).

The additives contained in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2) may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of the additives may be arbitrarily selected.

The content of the additive in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2) is not particularly limited and can be appropriately adjusted according to the type or purpose. For example, in the case of adjusting the aforementioned X value, the ratio of the content of the additive to the total content of all components other than the solvent in the composition (x1-2-1) (that is, the ratio of the content of the additive to the total mass of the first energy ray-curable resin film (x1-2) in the first energy ray-curable resin film (x1-2)) can be, for example, 0.5 to 10 mass%.

(Other components) Within the scope of not impairing the effect of the present invention, the composition (x1-2-1) and the first energy ray curable resin film (x1-2) may contain other components that are not equivalent to the energy ray curable component (a), the aforementioned filler and the aforementioned additive. As the aforementioned other components, for example, thermosetting components, photopolymerization initiators, coupling agents, crosslinking agents, etc. can be listed. For example, by using the composition (x1-2-1) containing the aforementioned energy ray curable component (a) and thermosetting components, the adhesion of the first energy ray curable resin film (x1-2) to the adherend is improved by heating, and the strength of the cured product of the first energy ray curable resin film (x1-2) is also improved.

The aforementioned thermosetting component, photopolymerization initiator, coupling agent and crosslinking agent in the composition (x1-2-1) may be the same as the thermosetting component (B), photopolymerization initiator, coupling agent (E) and crosslinking agent (F) in the composition (x1-1-1), respectively.

The composition (x1-2-1) and the first energy ray-curable resin film (x1-2) may contain only one of the above-mentioned other components, or two or more of them. In the case of two or more of them, the combination and ratio of them can be arbitrarily selected. The content of the above-mentioned other components in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2) is not particularly limited, and can be appropriately selected according to the purpose.

(Solvent) It is preferable that the composition (x1-2-1) further contains a solvent. The composition (x1-2-1) containing a solvent has good handling properties. As the solvent contained in the composition (x1-2-1), for example, the same solvent as the solvent contained in the composition (x1-1-1) described above can be listed. The solvent contained in the composition (x1-2-1) may be only one kind or two or more kinds. In the case of two or more kinds, the combination and ratio of the solvents can be arbitrarily selected. The content of the solvent in the composition (x1-2-1) is not particularly limited. For example, it can be appropriately selected according to the type of components other than the solvent.

<Method for producing the first energy ray-curable protective film-forming composition> The first energy ray-curable resin film-forming composition (x1-2-1) is obtained by blending the components constituting the first energy ray-curable resin film-forming composition (x1-2-1), for example, can be produced by the same method as the first heat-curable resin film-forming composition (x1-1-1) described above, except that the types of the blended components are different.

[First composite sheet (α1)] As described above, the first curable resin film (x1) can be laminated with the first supporting sheet (Y1) to form the first composite sheet (α1). An example of the structure of the first composite sheet (α1) is shown in FIG3. The first composite sheet (α1) is a composite sheet (α1) having a first curable resin (x1) layer (X1) provided on one surface of the first supporting sheet (Y1), as in the first composite sheet (α1) shown in FIG3. By providing a layer (X1) of the first curable resin (x1) on one surface of the first supporting sheet (Y1), the layer (X1) of the first curable resin (x1) is stably supported and protected when the layer (X1) of the first curable resin (x1) is transported as a product package or when the layer (X1) of the first curable resin (x1) is transported within a step.

In addition, the specific structure of the first composite sheet (α1) is shown in FIG. 4 to FIG. 6. The first composite sheet (α1) is the first composite sheet (α1a) shown in FIG. 4, the first support sheet (Y1) is the substrate 51, and the first curable resin (x1) layer (X1) is provided on one side of the substrate 51. In addition, the first composite sheet (α1) can also be the first composite sheet (α1b) shown in FIG. 5, the first support sheet (Y1) is an adhesive sheet formed by laminating the substrate 51 and the adhesive layer 61, and the adhesive layer 61 of the adhesive sheet and the first curable resin (x1) layer (X1) are attached. Furthermore, the first composite sheet (α1) may also be a first composite sheet (α1c) as shown in FIG6, wherein the first support sheet (Y1) is an adhesive sheet formed by sequentially laminating a substrate 51, an intermediate layer 71, and an adhesive layer 61, and the adhesive layer 61 of the adhesive sheet is attached to a layer (X1) of a first curable resin (x1). The adhesive sheet formed by sequentially laminating a substrate 51, an intermediate layer 71, and an adhesive layer 61 can be used as a back grinding tape. That is, since the first composite sheet (α1c) shown in FIG6 has a back-grinding tape as the first supporting sheet (Y1), it can be suitably used when the back side of the semiconductor chip wafer is ground and thinned after the first curing resin (x1) layer (X1) of the first composite sheet (α1c) is bonded to the bump forming surface of the semiconductor chip wafer.

The first curable resin (x1) and the first supporting sheet (Y1) used in the first composite sheet (α1) are described below. ＜First supporting sheet (Y1)＞ The first supporting sheet (Y1) functions as a support for supporting the first curable resin (x1). The first supporting sheet (Y1) may be composed of only a substrate 51 as shown in FIG4, or may be a laminate of a substrate 51 and an adhesive layer 61 as shown in FIG5, or may be a laminate of a substrate 51, an intermediate layer 71, and an adhesive layer 61 in sequence as shown in FIG6. The laminate of a substrate 51, an intermediate layer 71, and an adhesive layer 61 in sequence may be suitable for use as a back grinding sheet (b-BG).

The following describes the substrate of the first supporting sheet (Y1), the adhesive layer and the intermediate layer that the first supporting sheet (Y1) may have.

(Substrate) The substrate is in the form of a sheet or film, and its constituent materials include, for example, the following various resins. As resins constituting the substrate, for example, polyethylene 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 resin; ethylene-vinyl acetate copolymers, ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylate copolymers, and ethylene-norbornene copolymers (copolymers obtained using ethylene as a monomer); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers; Resins (resins obtained using vinyl chloride as a monomer); polystyrene; polycycloolefins; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene 2,6-naphthalene dicarboxylate, and fully aromatic polyesters in which all constituent units have aromatic cyclic groups; copolymers of two or more of the aforementioned polyesters; poly(meth)acrylates; polyurethanes; polyurethane acrylates; polyimides; polyamides; polycarbonates; fluororesins; polyacetals; modified polyphenylene ethers; polyphenylene sulfides; polysulfones; polyether ketones, etc. In addition, as the resin constituting the substrate, for example, polymer alloys such as mixtures of the aforementioned polyesters and other resins can also be listed. The polymer alloy of the polyester and other resins is preferably a resin other than polyester in a smaller amount. In addition, as the resin constituting the substrate, for example, there can be listed crosslinked resins formed by crosslinking one or more of the above-mentioned resins exemplified above; and modified resins such as ionic polymers formed by using one or more of the above-mentioned resins exemplified above.

The resin constituting the base material may be used alone or in combination of two or more. When there are two or more resins constituting the base material, the combination and ratio thereof may be arbitrarily selected.

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

The thickness of the substrate is preferably 5 μm to 1,000 μm, more preferably 10 μm to 500 μm, further preferably 15 μm to 300 μm, and further preferably 20 μm to 150 μm. Here, "the thickness of the substrate" means the thickness of the entire substrate. For example, the thickness of a substrate composed of multiple layers means the total thickness of all layers constituting the substrate.

The substrate preferably has high thickness accuracy, that is, the thickness unevenness is suppressed regardless of any part. Among the above-mentioned constituent materials, materials with high thickness accuracy that can be used to constitute such a substrate include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, etc.

In addition to the aforementioned main constituent materials such as the resin, the substrate may also contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, softeners (plasticizers), etc.

The substrate may be transparent or opaque, may be colored according to the purpose, or may be deposited with other layers. Furthermore, when the first curable resin film (x1) is the first energy ray curable resin film (x1-2), and when the adhesive layer is an energy curable adhesive layer, the substrate is preferably one that allows energy rays to pass through.

The substrate can be manufactured by a known method. For example, a substrate containing a resin can be manufactured by molding a resin composition containing the above-mentioned resin.

(Adhesive layer) The adhesive layer is in the form of a sheet or a film and contains an adhesive. Examples of adhesives include acrylic resins (adhesives made of resins having (meth)acrylic groups), urethane resins (adhesives made of resins having urethane bonds), rubber resins (adhesives made of resins having rubber structures), silicone resins (adhesives made of resins having siloxane bonds), epoxy resins (adhesives made of resins having epoxy groups), polyvinyl ethers, polycarbonates, and other adhesive resins. Among these, acrylic resins are preferred.

In the present invention, the term "adhesive resin" includes both adhesive resins and adhesive resins. For example, it includes not only resins that have adhesive properties themselves, but also resins that exhibit adhesive properties by using other components such as additives, or resins that exhibit adhesive properties by the presence of a trigger such as heat or water.

The adhesive layer may be a single layer or a plurality of layers of two or more. When the adhesive layer is a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.

The thickness of the adhesive layer is preferably 1 μm to 1000 μm, more preferably 5 μm to 500 μm, and even more preferably 10 μm to 100 μm. Here, "the thickness of the adhesive layer" means the thickness of the entire adhesive layer. For example, the thickness of an adhesive layer composed of multiple layers means the total thickness of all layers constituting the adhesive layer.

The adhesive layer may be formed using an energy ray-curable adhesive or a non-energy ray-curable adhesive. The adhesive layer formed using an energy ray-curable adhesive can easily adjust the physical properties before and after curing.

(Intermediate layer) The intermediate layer is in the form of a thin sheet or a film, and its constituent material can be appropriately selected according to the purpose and is not particularly limited. For example, when the purpose is to suppress the deformation of the first hardened resin film (r1) due to the reflection of the bump shape existing on the semiconductor surface on the protective film covering the semiconductor surface, as a better constituent material of the intermediate layer, urethane (meth) acrylate and the like can be listed in terms of high unevenness tracking and improved adhesion of the intermediate layer.

The intermediate layer may be only one layer (single layer) or may be two or more layers. When the intermediate layer is a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.

The thickness of the intermediate layer can be appropriately adjusted according to the height of the bumps on the semiconductor surface to be protected, but in order to easily absorb the impact of the higher bumps, it is preferably 50μm to 600μm, more preferably 70μm to 500μm, and even more preferably 80μm to 400μm. Here, "the thickness of the intermediate layer" means the thickness of the entire intermediate layer. For example, the thickness of the intermediate layer composed of multiple layers means the total thickness of all layers constituting the intermediate layer.

Next, the manufacturing method of the first composite sheet (α1) is described.

[Manufacturing method of the first composite sheet (α1)] The first composite sheet (α1) can be manufactured by laminating the above-mentioned layers in order in a corresponding positional relationship. For example, when manufacturing the first supporting sheet (Y1), when laminating an adhesive layer or an intermediate layer on a substrate, the adhesive layer or the intermediate layer can be laminated by applying an adhesive composition or an intermediate layer forming composition on the substrate and drying or irradiating energy rays as needed. Examples of coating methods include rotary coating, spray coating, rod coating, knife coating, roller coating, roller-knife coating, blade coating, die coating, and gravure coating.

In addition, for example, when the first curable resin (x1) is further laminated on the adhesive layer laminated on the substrate, the thermosetting resin composition (x1-1-1) or the energy ray curable resin composition (x1-2-1) can be applied on the adhesive layer to directly form the first curable resin (x1) layer (X1). Similarly, when the adhesive layer is further laminated on the intermediate layer laminated on the substrate, the adhesive composition can be applied on the intermediate layer to directly form the adhesive layer.

In this way, when a continuous two-layer laminate structure is formed using any composition, a composition can be further applied on the layer formed by the aforementioned composition to form a new layer. However, among the two layers, the layer to be laminated later is preferably formed in advance on another release film using the aforementioned composition, and the exposed surface of the formed layer opposite to the side in contact with the aforementioned release film is bonded to the exposed surface of the remaining layers that have been formed to form a continuous two-layer laminate structure. At this time, the aforementioned composition is preferably applied to the release-treated surface of the release film. The release film can be removed as needed after the laminate structure is formed.

[Second composite sheet (α2)] The second composite sheet (α2) is not particularly limited as long as it can form a protective film on the back side of the semiconductor wafer. For example, the same structure as the first composite sheet (α1) can be adopted. Therefore, the second curable resin film (x2) of the second composite sheet (α2) can be made of the same material and structure as the first curable resin film (x1). However, in general, the back side of the semiconductor wafer does not have bumps or grooves and is smooth. Therefore, the second curable resin film (x2) is not required to satisfy the requirement (I) of the first curable resin film (x1). Therefore, in the second curable resin film (x2), the X value can be less than 18 and can also be greater than 10,000.

(Coloring agent (J)) Here, from the viewpoint of improving the visibility of the printed characters formed by the laser marking and improving the design of the semiconductor chip by making the grinding marks on the back of the semiconductor chip difficult to see, the second curable resin film (x2) and the second curable resin film forming composition for forming the second curable resin film (x2) preferably contain a coloring agent (J). As the coloring agent (J), for example, well-known ones such as inorganic pigments, organic pigments, and organic dyes can be listed. Examples of the organic pigments and organic dyes include ammonium pigments, cyanine pigments, merocyanidin pigments, croconium pigments, squalium pigments, azulenium pigments, polymethine pigments, naphthoquinone pigments, pyrylium pigments, phthalocyanine pigments, naphthocyanin pigments, naphtholactam pigments, azo pigments, condensed azo pigments, indigo pigments, peroxylane pigments, and perylene pigments. Pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinoline yellow pigments, pyrrole pigments, thioindigo pigments, metal complex pigments (metal complex dyes), dithiol metal complex pigments, indoxyl pigments, triallylmethane pigments, anthraquinone pigments, naphthol pigments, azomethine pigments, benzimidazolone pigments, pyranthrone pigments, and threne pigments. Examples of the aforementioned inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments, ITO (indium tin oxide) pigments, and ATO (antimony tin oxide) pigments.

The colorant (J) contained in the second curable resin film (x2) and the composition for forming the second curable resin film may be only one kind or two or more kinds. When there are two or more kinds of colorants (J), the combination and ratio thereof can be arbitrarily selected. When a colorant (J) is used, the content of the colorant (J) in the second curable resin film (x2) can be appropriately adjusted according to the purpose. For example, as described above, the second curable resin film (r2) formed by curing the second curable resin film (x2) has a printing applied by laser irradiation. By adjusting the content of the colorant (J) in the second curable resin (x2) and adjusting the light transmittance of the protective film, the visibility of the printing can be adjusted. Furthermore, by adjusting the content of the coloring agent (J), the design of the protective film can be improved, making it difficult to see the grinding marks on the back of the semiconductor wafer. If these points are taken into consideration, the ratio of the content of the coloring agent (J) relative to the total content of all components other than the solvent (also referred to as the total mass of the solid components of the second curable resin film forming composition) in the second curable resin film forming composition used to form the second curable resin film (x2) (that is, the content of the coloring agent (J) in the second curable resin film (x2)) is preferably 0.1 to 10 mass%, more preferably 0.1 to 7.5 mass%, and particularly preferably 0.1 to 5 mass%. By making the above content of the coloring agent (J) above the above lower limit, the effect of using the coloring agent (J) can be more significantly obtained. Furthermore, when the content of the coloring agent (J) is equal to or less than the upper limit value, an excessive decrease in the light transmittance of the second curable resin film (x2) can be suppressed.

In addition, the first curable resin film (x1) and the first curable resin film forming composition may also contain a coloring agent (J). However, from the viewpoint of ensuring the visibility of the predetermined dividing line of the wafer for semiconductor chip manufacturing, the content of the coloring agent (J) is preferably within a range of transparency that can ensure the visibility of the predetermined dividing line.

Furthermore, the second supporting sheet (Y2) of the second composite sheet (α2) may have the same structure as the first supporting sheet (Y1). Specifically, the second supporting sheet (Y2) is the same as the first supporting sheet (Y1), and may be composed only of the substrate 51 as shown in FIG4, or may be an adhesive sheet composed of a laminated substrate 51 and an adhesive layer 61 as shown in FIG5, or may be an adhesive sheet composed of a laminated substrate 51, an intermediate layer 71, and an adhesive layer 61 as shown in FIG6. The substrate, intermediate layer, and adhesive layer of the second supporting sheet (Y2) may have the same structure and material as the substrate, intermediate layer, and adhesive layer of the first supporting sheet (Y1).

[Usage method of the first curable resin film (x1)] The first curable resin film (x1) can be used to form a curable resin film (first curable resin film (r1)) as a protective film on both the aforementioned bump forming surface and the side surface of a semiconductor chip having a bump forming surface with bumps. More specifically, the first curable resin film (x1) can be used to form a curable resin film (first curable resin film (r1)) as a protective film on both the aforementioned bump forming surface and the side surface of a semiconductor chip having a bump forming surface with bumps in the method for manufacturing a semiconductor chip described later in which a semiconductor chip having a bump forming surface with bumps and a groove serving as a predetermined dividing line is used to manufacture a wafer.

[Usage of the second curable resin film (x2)] The second curable resin film (x2) can be used to form a curable resin film (second curable resin film (r2)) as a protective film on the back side of a semiconductor chip having a bump forming surface with bumps. More specifically, the first curable resin film (x1) can be used to form a curable resin film (second curable resin film (r2)) as a protective film on the back side of a semiconductor chip having a bump forming surface with bumps in step (T) of the semiconductor chip manufacturing method described later for manufacturing a wafer using a semiconductor chip having a bump forming surface with bumps and a groove serving as a predetermined dividing line.

[Usage of the first composite sheet (α1)] The first composite sheet (α1) can be used to form a hardened resin film (first hardened resin film (r1)) as a protective film on both the aforementioned bump forming surface and the side surface of a semiconductor chip having a bump forming surface with bumps. More specifically, the first composite sheet (α1) can be used to form a hardened resin film (first hardened resin film (r1)) as a protective film on both the aforementioned bump forming surface and the side surface of a semiconductor chip having a bump forming surface with bumps in the method for manufacturing a semiconductor chip described later by using a semiconductor chip having a bump forming surface with bumps and a groove serving as a predetermined dividing line to manufacture a wafer.

[Usage of the second composite sheet (α2)] The second composite sheet (α2) can be used to form a hardened resin film (second hardened resin film (r2)) as a protective film on the back side of a semiconductor chip having a bump forming surface with bumps. More specifically, the second composite sheet (α2) can be used to form a hardened resin film (second hardened resin film (r2)) as a protective film on the back side of a semiconductor chip having a bump forming surface with bumps in step (T) of a method for manufacturing a semiconductor chip described later in which a semiconductor chip having a bump forming surface with bumps and a groove serving as a predetermined dividing line is used to manufacture a wafer.

[Method for manufacturing semiconductor chips of the present invention] The schematic diagram of the steps of the method for manufacturing semiconductor chips of the present invention is shown in FIG7. The method for manufacturing semiconductor chips of the present invention generally includes: a step of preparing a wafer for semiconductor chip manufacturing (S1), a step of attaching a first composite sheet (α1) (S2), a step of curing a first curable resin (x1) (S3), and a step of singulation (S4), and further includes a step of grinding the back side of the wafer for semiconductor chip manufacturing (S-BG). In the method for manufacturing semiconductor chips of one aspect of the present invention, the first curable resin film (x1) can be used, but from the viewpoint of improving the handling property, etc., it is preferable to use the first composite sheet (α1).

In detail, the method for manufacturing a semiconductor chip according to one aspect of the present invention uses the above-mentioned first composite sheet (α1) and sequentially includes the following steps (S1) to (S4). ･Step (S1): a step of preparing a semiconductor wafer for use, wherein a groove serving as a predetermined dividing line is formed on the bump forming surface of a semiconductor wafer having a bump forming surface with bumps so as not to reach the back surface ･Step (S2): a step of pressing and attaching a first curable resin (x1) to the bump forming surface of the semiconductor wafer for use, and burying the first curable resin (x1) in the groove formed on the semiconductor wafer for use while covering the bump forming surface of the semiconductor wafer for use with the first curable resin (x1) ･ Step (S3): hardening the first curable resin (x1) to obtain a semiconductor wafer with a first curable resin film (r1) Step (S4): singulating the semiconductor wafer with a first curable resin film (r1) along the predetermined dividing line to obtain a semiconductor wafer with at least the bump forming surface and the side surface covered by the first curable resin film (r1) Furthermore, after the step (S2) and before the step (S3), after the step (S3) and before the step (S4), or in the step (S4), the following step (S-BG) is included. ･Step (S-BG): A step of grinding the back side of the semiconductor wafer.

By using the manufacturing method including the above steps, a semiconductor chip can be obtained in which not only the bump forming surface but also the side surface is covered with the first hardened resin film (r1) with excellent strength and the first hardened resin film (r1) as a protective film is difficult to peel off. In addition, the so-called "covering" here means that the first hardened resin film (r1) is formed along the shape of the semiconductor chip on at least the bump forming surface and the side surface of a semiconductor chip. That is, the present invention is clearly different from the sealing technology of sealing a plurality of semiconductor chips in resin.

The following describes each step of the method for manufacturing the semiconductor chip of the present invention in detail. In addition, in the following description, "semiconductor chip" may be simply referred to as "chip", and "semiconductor wafer" may be simply referred to as "wafer".

[Step (S1)] An example of a semiconductor wafer prepared in step (S1) is shown in a top view in FIG8 and in a schematic cross-sectional view in FIG9. In step (S1), a semiconductor wafer manufacturing wafer 10 is prepared in which a groove 13 serving as a predetermined dividing line is formed on a bump forming surface 11a of a semiconductor wafer 11 having bump forming surface 11a with bumps 12 so as not to reach a back surface 11b. In addition, in FIG8, bumps are omitted in the illustration.

The shape of the bump 12 is not particularly limited, and can be any shape as long as it can contact and fix with the electrode on the substrate for chip mounting. For example, in FIG. 9 , the bump 12 is set to be spherical, but the bump 12 can also be a spheroid. The spheroid can be, for example, a spheroid extending in the vertical direction relative to the bump forming surface 11a of the wafer 11, or a spheroid extending in the horizontal direction relative to the bump forming surface 11a of the wafer 11. In addition, the bump 12 can also be a columnar (pillar) shape.

The height of the bump 12 is not particularly limited and can be changed appropriately according to design requirements. For example, it is 30μm~300μm, preferably 60μm~250μm, and more preferably 80μm~200μm. In addition, the so-called "height of the bump 12" means the height of the part at the highest position of the bump forming surface 11a when focusing on one bump.

The number of the bumps 12 is not particularly limited and can be changed appropriately according to design requirements.

The wafer 11 is, for example, a semiconductor wafer having circuits such as wiring, capacitors, diodes, and transistors formed on the surface. The material of the wafer is not particularly limited, and examples thereof include silicon wafers, silicon carbide wafers, compound semiconductor wafers, glass wafers, and sapphire wafers.

The size of the wafer 11 is not particularly limited, but from the perspective of improving batch processing efficiency, it is usually 8 inches (200 mm in diameter) or larger, preferably 12 inches (300 mm in diameter) or larger. In addition, the shape of the wafer is not limited to a circle, and may be a square shape such as a square or a rectangle. In the case of a square wafer, from the perspective of improving batch processing efficiency, the size of the wafer 11 is preferably such that the length of the longest side is greater than the above-mentioned size (diameter).

The thickness of the wafer 11 is not particularly limited, but from the viewpoint of easily suppressing the warp caused by the shrinkage during the curing of the first curing resin (x1) and suppressing the grinding amount of the back side 11b of the wafer 11 in the subsequent step and shortening the time required for back side grinding, the thickness is preferably 100μm~1,000μm, more preferably 200μm~900μm, and even more preferably 300μm~800μm.

In the bump forming surface 11a of the semiconductor chip manufacturing wafer 10 prepared in step (S1), a plurality of grooves 13 are formed in a grid shape as predetermined dividing lines when the semiconductor chip manufacturing wafer 10 is singulated. The plurality of grooves 13 are cut grooves formed when the blade first dicing method (Dicing Before Grinding) is applied, and are formed with a depth shallower than the thickness of the wafer 11, so that the deepest part of the groove 13 does not reach the back side 11b of the wafer 11. The plurality of grooves 13 can be formed by cutting using a conventionally known wafer cutting device equipped with a cutting blade. In addition, the plurality of grooves 13 can also be formed by cutting using a laser or the like instead of a blade. In addition, the plurality of grooves 13 can be formed so that the manufactured semiconductor wafer has a desired size and shape, and the grooves 13 do not necessarily have to be formed in a grid pattern as shown in Fig. 8. The size of a semiconductor wafer is generally about 0.5 mm×0.5 mm to 1.0 mm×1.0 mm, but is not limited to this size.

The width of the groove 13 is preferably 10 μm to 2,000 μm, more preferably 30 μm to 1,000 μm, further preferably 40 μm to 500 μm, and further preferably 50 μm to 300 μm from the viewpoint of improving embedding properties of the first curable resin (x1).

The depth of the groove 13 can be adjusted according to the thickness of the wafer used and the required chip thickness, and is preferably 30 μm to 700 μm, more preferably 60 μm to 600 μm, and even more preferably 100 μm to 500 μm.

The aspect ratio of the groove 13 may be 2-6, 2.5-5, or 3-5.

The semiconductor wafer manufacturing wafer 10 prepared in step (S1) is supplied to step (S2).

[Step (S2)] The outline of step (S2) is shown in FIG10. In step (S2), the first curable resin (x1) is pressed and attached to the bump forming surface 11a of the semiconductor chip manufacturing wafer 10. Here, from the viewpoint of the handling property of the first curable resin (x1), the first curable resin (x1) is preferably used by laminating on a supporting sheet. Therefore, in step (S2), it is preferred that the first composite sheet (α1) having a laminated structure formed by laminating a first support sheet (Y1) and a layer (X1) of a first curable resin (x1) is pressed and attached to the bump forming surface 11a of the semiconductor chip wafer 10 with the aforementioned layer (X1) as an attachment surface. By step (S2), as shown in FIG. 4, while the bump forming surface 11a of the semiconductor chip wafer 10 is covered with the first curable resin (x1), the first curable resin (x1) is buried in the groove 13 formed in the semiconductor chip wafer 10.

By embedding the first curable resin (x1) in the groove 13 formed in the semiconductor chip manufacturing wafer 10, when the semiconductor chip manufacturing wafer 10 is singulated in step (S4), the side surface of the semiconductor chip can be covered with the first curable resin (x1). That is, by step (S2), a coating that is a precursor of the first curable resin film (r1) covering the side surface of the semiconductor chip can be formed, which is necessary to improve the strength of the semiconductor chip and suppress the peeling of the first curable resin film (r1) as a protective film.

In addition, from the perspective of making the first curable resin (x1) embeddable in the groove 13, the pressing force when attaching the first composite sheet (α1) to the semiconductor chip wafer 10 is preferably 1kPa~200kPa, more preferably 5kPa~150kPa, and even more preferably 10kPa~100kPa. In addition, the pressing force when attaching the first composite sheet (α1) to the semiconductor chip wafer 10 can be appropriately changed from the initial attachment to the final attachment. For example, from the perspective of making the embeddability of the first curable resin (x1) in the groove 13 better, it is better to reduce the pressing force at the initial attachment and gradually increase the pressing force.

Furthermore, when the first composite sheet (α1) is attached to the semiconductor chip manufacturing wafer 10, when the first curable resin (x1) is a thermosetting resin, it is preferably heated from the viewpoint of making the embedding property of the first curable resin (x1) in the groove 13 better. When the first curable resin (x1) is a thermosetting resin, the fluidity of the first curable resin (x1) is temporarily improved by heating, and it is hardened by continuing to heat. Therefore, by heating within the range of the improved fluidity of the first curable resin (x1), the first curable resin (x1) is easily spread throughout the entire groove 13, and the embedding property of the first curable resin (x1) in the groove 13 can be further improved. As a specific heating temperature (attachment temperature), it is preferably 50°C to 150°C, more preferably 60°C to 130°C, and even more preferably 70°C to 110°C. In addition, the heating treatment performed on the first curable resin (x1) is not included in the curing treatment of the first curable resin (x1).

Furthermore, when attaching the first composite sheet (α1) to the semiconductor chip manufacturing wafer 10, it is preferably carried out in a reduced pressure environment. Thereby, the groove 13 becomes negative pressure, and the first curable resin (x1) becomes easy to spread throughout the groove 13. As a result, the embedding property of the first curable resin (x1) in the groove 13 becomes better. As a specific pressure of the reduced pressure environment, it is preferably 0.001kPa~50kPa, more preferably 0.01kPa~5kPa, and more preferably 0.05kPa~1kPa.

Furthermore, from the perspective of making the first curable resin (x1) more embeddable in the groove 13, the thickness of the layer (X1) of the first curable resin (x1) in the first composite sheet (α1) is preferably greater than 30 μm and less than 200 μm, more preferably 60 μm to 150 μm, and even more preferably 80 μm to 130 μm.

Furthermore, since the first curable resin (x1) layer (X1) is composed of the first curable resin (x1), the above-mentioned requirement (I) is satisfied. Therefore, since the X value is greater than 19 and less than 10,000, when the first composite sheet (α1) is attached to the bump forming surface 11a of the semiconductor chip manufacturing wafer 10, the effect of suppressing the residue of the first curable resin (x1) on the upper part of the bump 12, the effect of suppressing the protrusion of the layer (X1) of the first curable resin (x1), and the effect of suppressing the shrinkage (cissing) of the first curable resin (x1) on the bump forming surface 11a and the first curable resin film (r1) as its cured product are excellent, and the embedding property of the first curable resin (x1) in the groove 13 is also good.

Here, the first supporting sheet (Y1) of the first composite sheet (α1) preferably has the functions of supporting the first curable resin (x1) and serving as a back grinding sheet. At this time, when the back side 11b of the wafer 11 is ground with the first composite sheet (α1) attached, the first supporting sheet (Y1) functions as a back grinding sheet, and the back grinding step can be easily performed.

[Step (S3), Step (S4) and Step (S-BG)] Through the steps up to the above-mentioned step (S2), a laminated body is formed by attaching the first composite sheet (α1) to the semiconductor chip manufacturing wafer 10. The laminated body is preferably supplied to any one of the first to fourth embodiments described below in accordance with the timing of implementing the step (S-BG). Hereinafter, with respect to the first to fourth embodiments, the description of the timing of implementing the step (S-BG) is mixed, while explaining the step (S3) and the step (S4).

<First Implementation Form> In the first implementation form, as shown in FIG7 , step (S-BG) is performed after step (S2) and before step (S3). A schematic diagram of the first implementation form is shown in FIG11 .

(First embodiment: step (S-BG)) In the first embodiment, first, step (S-BG) is performed. Specifically, as shown in (1-a) of FIG. 11 , the back side 11b of the semiconductor chip manufacturing wafer 10 is ground while the first composite sheet (α1) is attached. "BG" in FIG. 11 means back side grinding, which is also the same in the subsequent drawings. Then, as shown in (1-b) of FIG. 11 , the first supporting sheet (Y1) is peeled off from the first composite sheet (α1). The grinding amount when grinding the back side 11b of the semiconductor chip wafer 10 is sufficient as long as at least the bottom of the groove 13 of the semiconductor chip wafer 10 is exposed, but the grinding may be further performed so that the first curable resin (x1) embedded in the groove 13 is also ground together with the semiconductor chip wafer 10. In the first embodiment, since the first support sheet (Y1) is peeled off before the step (S3) is implemented, even if the first curable resin (x1) is a thermosetting resin and a heat treatment is applied for curing in the step (S3), the first support sheet (Y1) is not required to have heat resistance. Therefore, the design freedom of the first support sheet (Y1) is improved.

(First embodiment: step (S3)) After performing step (S-BG), perform step (S3). Specifically, as shown in (1-c) of FIG. 11, the first curable resin (x1) is cured to obtain a semiconductor chip manufacturing wafer 10 with a first curable resin film (r1). The first curable resin film (r1) formed by curing the first curable resin (x1) is stronger than the first curable resin (x1) at room temperature. Therefore, by forming the first curable resin film (r1), the bump neck can be well protected. Furthermore, in step (S4) shown in (1-d) of FIG. 11, by singulating the semiconductor wafer with the first hardened resin film (r1) into wafers 10, a semiconductor wafer whose side surface is also covered by the first hardened resin film (r1) can be obtained, and a semiconductor wafer with excellent strength can be obtained. In addition, the first hardened resin film (r1) as a protective film is also prevented from peeling off.

(First embodiment: curing method) The curing of the first curable resin (x1) can be performed by either heat curing or energy ray irradiation curing, depending on the type of curable component contained in the first curable resin (x1). As a condition for heat curing, the curing temperature 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 heat curing is preferably 0.5 to 5 hours, more preferably 0.5 to 4 hours, and particularly preferably 1 to 3 hours. The conditions for curing by energy ray irradiation can be appropriately set according to the type of energy ray used. For example, when ultraviolet rays are used, the illumination is preferably 180-280 mW/cm ² and the light quantity is preferably 450-1000 mJ/cm ² . In the process of curing the first curable resin (x1) to form the first curable resin film (r1), from the viewpoint of removing bubbles that may enter when the first curable resin (x1) is embedded in the groove 13 in step (S2), the first curable resin (x1) is preferably a thermosetting resin. That is, when the first curable resin (x1) is a thermosetting resin, the fluidity of the first curable resin (x1) is temporarily improved by heating, and the first curable resin (x1) is cured by continuing to heat. By utilizing this phenomenon, when the fluidity of the first curable resin (x1) becomes higher, bubbles that enter when the first curable resin (x1) is embedded in the groove 13 can be removed, and the first curable resin (x1) can be cured in a state where the embedding property of the first curable resin (x1) in the groove 13 becomes better. In addition, from the viewpoint of shortening the curing time, the first curable resin (x1) is preferably an energy ray curable resin. In addition, the details of the first curable resin (x1) used for forming the first curable resin film (r1) will be described later.

(First embodiment: step (S4)) After performing step (S3), perform step (S4). Specifically, as shown in (1-d) of FIG. 11, the semiconductor chip with the first hardened resin film (r1) is made by cutting the portion formed in the groove of the first hardened resin film (r1) of the wafer 10 along the predetermined dividing line. The cutting can be appropriately performed by a conventionally known method such as blade cutting or laser cutting. Thereby, a semiconductor chip 40 can be obtained in which at least the bump forming surface 11a and the side surface are covered with the first hardened resin film (r1). Since the bump forming surface 11a and the side surface are covered with the first hardened resin film (r1), the semiconductor chip 40 has excellent strength. Furthermore, the bump forming surface 11a and the side surface are continuously covered by the first hardened resin film (r1) without gaps, so the bonding surface (interface) between the bump forming surface 11a and the first hardened resin film (r1) is not exposed on the side surface of the semiconductor chip 40. The exposed portion exposed on the side surface of the semiconductor chip 40 in the bonding surface (interface) between the bump forming surface 11a and the first hardened resin film (r1) is likely to become a starting point for film peeling. The semiconductor chip 40 of the present invention does not have such an exposed portion, so film peeling from the exposed portion is not likely to occur during the process of manufacturing the semiconductor chip 40 by cutting the semiconductor chip manufacturing wafer 10 or after manufacturing. Therefore, a semiconductor chip 40 in which peeling of the first hardened resin film (r1) serving as a protective film is suppressed can be obtained.

In addition, in step (S4), when the first hardened resin film (r1) of the semiconductor wafer 10 with the first hardened resin film (r1) is cut along the predetermined dividing line, the first hardened resin film (r1) is preferably transparent. Since the first hardened resin film (r1) is transparent, the semiconductor wafer 11 can be seen through it, so that the visibility of the predetermined dividing line can be ensured. Therefore, it is easy to cut along the predetermined dividing line.

<Second Implementation Form> In the second implementation form, as shown in FIG4 , step (S-BG) is performed after step (S3) and before step (S4). A schematic diagram of the second implementation form is shown in FIG6 .

(Second embodiment: step (S3)) In the second embodiment, first, step (S3) is performed. Specifically, as shown in (2-a) of FIG. 12, the first curable resin (x1) is cured in a state where the first composite sheet (α1) is attached, and a semiconductor chip manufacturing wafer 10 with a first curable resin film (r1) is obtained. The first curable resin film (r1) formed by curing the first curable resin (x1) is stronger than the first curable resin (x1) at room temperature. Therefore, by forming the first curable resin film (r1), the bump neck can be well protected. Furthermore, in step (S4), by singulating the semiconductor chip with the first curing resin film (r1) into the wafer 10, a semiconductor chip whose side is also covered by the first curing resin film (r1) can be obtained, and a semiconductor chip with excellent strength can be obtained. In addition, the first curing resin film (r1) as a protective film is also suppressed from peeling off. The curing method can be the same method as the curing method described in the first embodiment. By performing the heat curing treatment without peeling off the first supporting sheet (Y1), the first supporting sheet (Y1) can suppress the flow of the surface of the first curing resin (x1) temporarily generated when curing the first curing resin (x1) during the heat curing, and the flatness of the first curing resin film (r1) in the bump forming surface can be improved. Furthermore, by curing the first curable resin (x1) before grinding the back surface 11b of the semiconductor wafer manufacturing wafer 10, warping of the semiconductor wafer manufacturing wafer 10 can be suppressed.

(Second embodiment: step (S-BG)) After step (S3), step (S-BG) is performed. As shown in (2-b) of FIG. 12, the back side 11b of the semiconductor chip working wafer 10 is ground while the first composite sheet (α1) is attached. In addition, the grinding amount when grinding the back side 11b of the semiconductor chip working wafer 10 is sufficient as long as at least the bottom of the groove 13 of the semiconductor chip working wafer 10 is exposed, but the grinding may be further performed so that the first hardened resin film (r1) embedded in the groove 13 is also ground together with the semiconductor chip working wafer 10. Next, as shown in (2-c) of FIG. 12, the first supporting sheet (Y1) is peeled off from the first composite sheet (α1).

(Second embodiment: step (S4)) After performing step (S-BG), perform step (S4) in the same manner as in the first embodiment. Specifically, as shown in (2-d) of FIG. 12, the semiconductor chip with the first hardened resin film (r1) is made by cutting the portion of the first hardened resin film (r1) formed in the groove of the wafer 10 along the predetermined dividing line. The cutting can be appropriately performed by a conventionally known method such as blade cutting or laser cutting. Thereby, a semiconductor chip 40 can be obtained in which at least the bump forming surface 11a and the side surface are covered with the first hardened resin film (r1). The semiconductor chip 40 has excellent strength because the bump forming surface 11a and the side surface are covered with the first hardened resin film (r1). In addition, for the reasons already described, the semiconductor chip 40 can be obtained in which the peeling of the first hardened resin film (r1) as a protective film is suppressed.

<Third embodiment> In the third embodiment, as shown in FIG. 4 , the step (S-BG) is performed after the step (S3) and before the step (S4), which is the same as the second embodiment. However, the back grinding sheet (b-BG) is used separately, which is different from the second embodiment. A schematic diagram of the third embodiment is shown in FIG. 13 .

(Third embodiment: step (S3)) In the third embodiment, first, step (S3) is performed, but before that, as shown in (3-a) of FIG. 13, the first supporting sheet (Y1) is peeled off from the first composite sheet (α1). Thereafter, step (S3) is performed. Specifically, as shown in (3-b) of FIG. 13, the first curable resin (x1) is cured to obtain a semiconductor chip manufacturing wafer 10 with a first curable resin film (r1). The curing method can be the same method as the curing method described in the first embodiment. Since the first support sheet (Y1) is peeled off before the step (S3) is performed, even if the first curable resin (x1) is a thermosetting resin and a heat treatment is performed for curing in the step (S3), the first support sheet (Y1) is not required to be heat resistant. Therefore, the design freedom of the first support sheet (Y1) is improved. In addition, by curing the first curable resin (x1) before grinding the back side 11b of the semiconductor chip manufacturing wafer 10, the warping of the semiconductor chip manufacturing wafer 10 can be suppressed.

(Third embodiment: step (S-BG)) After performing step (S3), perform step (S-BG). Specifically, as shown in (3-c) of FIG. 13, a back grinding sheet (b-BG) is attached to the surface of the first hardened resin film (r1) of the semiconductor wafer 10 with the first hardened resin film (r1). Then, as shown in (3-d) of FIG. 13, after grinding the back side 11b of the semiconductor wafer 10 with the back grinding sheet (b-BG) attached, as shown in (3-e) of FIG. 13, the back grinding sheet (b-BG) is peeled off from the semiconductor wafer 10 with the first hardened resin film (r1). Since the back grinding sheet (b-BG) is not used in step (S3), even if the first curable resin (x1) is a thermosetting resin and a heat treatment is applied for curing in step (S3), the back grinding sheet (b-BG) is not required to have heat resistance. Therefore, the design freedom of the back grinding sheet (b-BG) is improved. In addition, the grinding amount when grinding the back side 11b of the semiconductor chip working wafer 10 is sufficient as long as at least the bottom of the groove 13 of the semiconductor chip working wafer 10 is exposed, but it is also possible to further grind so that the first curing resin film (r1) buried in the groove 13 is also ground together with the semiconductor chip working wafer 10.

(Third embodiment: step (S4)) After the step (S-BG) is performed, the step (S4) is performed in the same manner as in the first and second embodiments. Specifically, as shown in (3-f) of FIG. 13, the semiconductor chip with the first hardened resin film (r1) is made by cutting the portion formed in the groove of the first hardened resin film (r1) of the wafer 10 along the predetermined dividing line. The cutting can be appropriately performed by a conventionally known method such as blade cutting or laser cutting. Thereby, a semiconductor chip 40 can be obtained in which at least the bump forming surface 11a and the side surface are covered with the first hardened resin film (r1). The semiconductor chip 40 has excellent strength because the bump forming surface 11a and the side surface are covered with the first hardened resin film (r1). In addition, for the reasons already described, the semiconductor chip 40 can be obtained in which the peeling of the first hardened resin film (r1) as a protective film is suppressed.

<Fourth Implementation Form> In the fourth implementation form, as shown in FIG. 4 , step (S-BG) is performed in step (S4). A schematic diagram of the fourth implementation form is shown in FIG. 14 .

(Fourth embodiment: step (S3)) In the fourth embodiment, first, step (S3) is performed, but before that, as shown in (4-a) of FIG. 14, the first supporting sheet (Y1) is peeled off from the first composite sheet (α1). Thereafter, step (S3) is performed. Specifically, as shown in (4-b) of FIG. 14, the first curable resin (x1) is cured to obtain a semiconductor chip manufacturing wafer 10 with a first curable resin film (r1). The curing method can be the same method as the curing method described in the first embodiment. Since the first support sheet (Y1) is peeled off before the step (S3) is performed, even if the first curable resin (x1) is a thermosetting resin and a heat treatment is performed for curing in the step (S3), the first support sheet (Y1) is not required to be heat resistant. Therefore, the design freedom of the first support sheet (Y1) is improved. In addition, by curing the first curable resin (x1) before grinding the back side 11b of the semiconductor chip manufacturing wafer 10, the warping of the semiconductor chip manufacturing wafer 10 can be suppressed.

(Fourth embodiment: step (S4) including step (S-BG)) After step (S3) is implemented, as shown in (4-c) of FIG. 14, a cut is made along the predetermined dividing line in the first hardened resin film (r1) of the semiconductor chip manufacturing wafer 10 with the first hardened resin film (r1) formed in the portion of the groove 13. From the perspective of facilitating singulation, the depth of the cut is preferably set to a depth that reaches the deepest part of the groove 13. Thus, in the step (S-BG) described later, the semiconductor chip manufacturing wafer 10 with the first hardened resin film (r1) is singulated along the cut. Alternatively, although omitted in the figure, a modified region may be formed along the predetermined dividing line in the portion of the groove 13 formed in the first hardened resin film (r1) of the semiconductor chip working wafer 10 with the first hardened resin film (r1). The modified region may be formed by laser or plasma processing, etc. Thus, in the step (S-BG) described later, cracks are generated starting from the modified region, and the semiconductor chip working wafer 10 with the first hardened resin film (r1) is singulated along the modified region. Then, step (S-BG) is performed. Specifically, as shown in (4-d) of FIG. 14, a back grinding sheet (b-BG) is attached to the surface of the first hardened resin film (r1) of the semiconductor wafer 10 with the first hardened resin film (r1). Then, as shown in (4-e) of FIG. 14, the back side 11b of the semiconductor wafer 10 is ground while the back grinding sheet (b-BG) is attached. Finally, as shown in (4-f) of FIG. 14, the back grinding sheet (b-BG) is peeled off from the semiconductor wafer 10 with the first hardened resin film (r1). Thereby, a semiconductor wafer 40 in which at least the bump forming surface 11a and the side surface are covered with the first hardened resin film (r1) can be obtained. In addition, the grinding amount when grinding the back side 11b of the semiconductor chip wafer 10 is at least the amount of the bottom of the groove 13 of the semiconductor chip wafer 10 exposed, but it is also possible to grind further so that the first hardened resin film (r1) embedded in the groove 13 is also ground together with the semiconductor chip wafer 10. The semiconductor chip 40 has excellent strength because the bump forming surface 11a and the side surface are covered with the first hardened resin film (r1). In addition, since the back grinding sheet (b-BG) is not used in step (S3), even if the first hardening resin (x1) is a thermosetting resin and a heat treatment is applied for hardening in step (S3), the back grinding sheet (b-BG) is not required to have heat resistance. Therefore, the design freedom of the back grinding sheet (b-BG) is improved.

Here, in the first to fourth embodiments, in step (S-BG), the first support sheet (Y1) or the back grinding sheet (b-BG) is used for explanation, but in one embodiment of the present invention, the first support sheet (Y1) or the back grinding sheet (b-BG) can be replaced to form a resin layer (Z1) for back grinding. Specifically, a resin (z1) having fluidity can be used to coat the surface of the first hardened resin film (r1) and the bumps exposed from the first hardened resin film (r1), and then the resin (z1) can be hardened to form a resin layer (Z1) for back grinding, and the grinding step can be performed as a substitute for the back grinding sheet. In addition, when the surface of the first hardened resin film (r1) and the bumps exposed from the first hardened resin film (r1) are coated with the resin (z1), the coating is performed via a flexible resin film (z2) that can follow the unevenness of the bumps. After the step (S-BG), the unnecessary resin layer (Z1) for back grinding can be easily peeled off.

[Step (T)] In one aspect of the semiconductor chip manufacturing method of the present invention, it is preferred to further include the following step (T). ･Step (T): A step of forming a second hardened resin film (r2) on the aforementioned back side of the aforementioned semiconductor chip manufacturing wafer

By the manufacturing method of the above-mentioned embodiment, a semiconductor chip 40 can be obtained in which at least the bump forming surface 11a and the side surface are covered with the first hardened resin film (r1). However, the back surface of the semiconductor chip 40 is exposed. Therefore, from the perspective of protecting the back surface of the semiconductor chip 40 and further improving the strength of the semiconductor chip 40, it is preferable to implement the above-mentioned step (T).

In more detail, the above step (T) preferably includes the following steps (T1) to (T2) in sequence. ･Step (T1): a step of attaching the second curable resin (x2) to the back side of the semiconductor chip manufacturing wafer ･Step (T2): a step of curing the second curable resin (x2) to form a second curable resin film (r2) In addition, in step (T1), it is preferred to use a second laminate (α2) having a laminated structure formed by laminating a second support sheet (Y2) and a layer (X2) of the second curable resin (x2). In detail, step (T1) is preferably a step of attaching the second laminate (α2) having a laminate structure formed by laminating a second support sheet (Y2) and a second curable resin (x2) to the back side of a semiconductor chip manufacturing wafer with the aforementioned layer (X2) as an attachment surface. At this time, the timing of peeling off the second support sheet (Y2) from the second laminate (α2) may be between step (T1) and step (T2) or after step (T2).

Here, when the second composite body (α2) is used in step (T1), the second supporting sheet (Y2) of the second composite sheet (α2) preferably has the functions of supporting the second curable resin (x2) and serving as a cutting sheet. In the case of the manufacturing method of the first to third embodiments, in step (S4), by attaching the second composite sheet (α2) to the back side 11b of the semiconductor wafer 10 with the first curing resin film (r1), when singulation by cutting is performed, the second supporting sheet (Y2) functions as a cutting sheet, and cutting can be easily performed.

Here, as in the manufacturing method of the first embodiment, when step (S3) is performed after step (S-BG), step (T1) is performed before step (S3), and then step (S3) and step (T2) can be performed simultaneously. That is, the first curable resin (x1) and the second curable resin (x2) can be cured simultaneously. In this way, the number of curing treatments can be reduced.

Specifically, in the manufacturing method of the first embodiment to the third embodiment, step (T) includes the following step (T1-1) and the following step (T1-2) in sequence, ･Step (T1-1): After step (S-BG) and before step (S4), a step of attaching the second curable resin (x2) to the back side of the semiconductor chip manufacturing wafer ･Step (T1-2): After step (S4 ) before or after the second hardening resin (x2) is hardened to form a second hardening resin film (r2) In step (S4), it is preferred that when the portion of the first hardening resin film (r1) formed in the groove of the semiconductor chip manufacturing wafer with the first hardening resin film (r1) is cut along the predetermined dividing line, the second hardening resin (x2) or the second hardening resin film (r2) is also cut together. Furthermore, in the manufacturing method of the fourth embodiment, step (T) includes the following step (T2-1) and the following step (T2-2) in sequence, •Step (T2-1): After step (S-BG) and after step (S4), directly attaching the second curable resin (x2) to the back side of the semiconductor chip manufacturing wafer in a state where the back grinding sheet (b-BG) is attached •Step (T2-2): Curing the second curable resin (x2) to form a second curable resin film (r2) Furthermore, step (T) preferably includes the following step (T2-3) before or after step (T2-2). ･Step (T2-3): A step of dividing the second hardening resin layer (x2) or the second hardening resin film (r2) along the cut

[Other Steps] An aspect of the semiconductor chip manufacturing method of the present invention may include other steps without departing from the scope of the present invention. As such treatment, for example, wet etching treatment or dry etching treatment of the bump formation surface after the protective film (first hardened resin film (r1) is formed can be listed. [Example]

The present invention is specifically described by the following embodiments, but the present invention is not limited to the following embodiments.

1. Raw materials for producing the first thermosetting resin film-forming composition (x1-1-1) The raw materials used for producing the first thermosetting resin film-forming composition (x1-1-1) are shown below.

(1) Polymer component (A) (A)-1: Polyvinyl butyral ("S-LEC BL-10" manufactured by Sekisui Chemical Industries, Ltd., weight average molecular weight 25,000, glass transition temperature 59°C) having structural units represented by the following formulae (i)-1, (i)-2 and (i)-3. (A)-2: Acrylic resin (weight average molecular weight 800,000, glass transition temperature -28°C) obtained by copolymerizing butyl acrylate (55 parts by mass), methyl acrylate (10 parts by mass), glycidyl methacrylate (20 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass). (In the formula, l ₁ is approximately 28, m ₁ is 1 to 3, and n ₁ is an integer between 68 and 74.)

(2) Epoxy resin (B1) (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) (B1)-2: Liquid bisphenol F type epoxy resin ("YL983U" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 165~175 g/eq) (B1)-3: Polyfunctional aromatic type epoxy resin ("EPPN-502H" manufactured by Nippon Kayaku Co., Ltd.), epoxy equivalent 158~178 g/eq) (B1)-4: Dicyclopentadiene type epoxy resin ("EPICLON HP-7200HH", epoxy equivalent 254~264g/eq)

(3) Thermosetting agent (B2) (B2)-1: Novolac type phenolic resin ("BRG-556" manufactured by Showa Denko Co., Ltd.) (B2)-2: O-cresol type novolac resin ("Phenolite KA-1160" manufactured by DIC Corporation)

(4) Curing accelerator (C) (C)-1: 2-phenyl-4,5-dihydroxymethylimidazole ("Curezol 2PHZ-PW" manufactured by Shikoku Chemical Industries, Ltd.)

(5) Filler (D) (D)-1: Epoxy-modified spherical silica (Admanano YA050C-MKK manufactured by Admatechs, average particle size 50 nm)

(6) Additives (I) (I)-1: Surfactant (acrylic polymer, BYK "BYK-361N") (I)-2: Silicone oil (aralkyl modified silicone oil, Momentive Performance Materials Japan Inc. "XF42-334") (I)-3: Rheology control agent (polyhydroxycarboxylate, BYK "BYK-R606")

2. Examples 1-2, Comparative Examples 1-3 2-1. Example 1 (1) Preparation of the first thermosetting resin film-forming composition (x1-1-1) By dissolving or dispersing the polymer component (A)-1 (100 parts by mass), epoxy resin (B1)-1 (350 parts by mass), epoxy resin (B1)-4 (270 parts by mass), (B2)-1 (190 parts by mass), curing accelerator (C)-1 (2 parts by mass), filler (D)-1 (90 parts by mass) and additive (I)-3 (9 parts by mass) in methyl ethyl ketone and stirring at 23°C, a thermosetting resin film-forming composition (x1-1-1) having a total concentration of all components other than the solvent of 45% by mass was obtained. In addition, the blending amounts of components other than the solvent shown here are all blending amounts of the target substance excluding the solvent.

(2) Preparation of the first thermosetting resin film (x1-1) A release film (SP-PET381031 manufactured by Lintec Corporation, 38 μm thick) was used in which one side of a polyethylene terephthalate film was subjected to a release treatment by polysilicon treatment. The composition (x1-1-1) obtained above was applied on the release-treated surface and dried by heating at 120°C for 2 minutes to form a first thermosetting resin film (x1-1) having a thickness of 45 μm.

2-2. Example 2, Comparative Examples 1 to 3 The types and contents of the components contained in the first thermosetting resin film-forming composition (x1-1-1) are as shown in Table 1 described later. Except for changing one or both of the types and contents of the blending components during the production of the first thermosetting resin film-forming composition (x1-1-1), a first thermosetting resin film (x1-1) having a thickness of 45 μm was formed in the same manner as in Example 1. In addition, the entry "-" in the column of the components contained in Table 1 means that the first thermosetting resin film-forming composition (x1-1-1) does not contain the component.

3. Evaluation 3-1. Production of the first composite sheet (α1) A back grinding tape ("E-8510HR" manufactured by Lintec Co., Ltd.) was used as the first support sheet (Y1), and the back grinding tape was laminated to the first thermosetting resin film (x1-1) on the release film of Examples 1~2 and Comparative Examples 1~3 obtained above. Thus, a first composite sheet (α1) formed by laminating the first support sheet (Y1) and the first thermosetting resin film (x1-1) was obtained.

3-2. Determination of Gc1 and Gc300 of the first thermosetting resin film (x1-1), calculation of the X value Except for changing the coating amount of the composition (x1-1-1), 20 sheets of the first thermosetting resin film (x1-1) with a thickness of 50μm were prepared in the same manner as above. Then, the first thermosetting resin films (x1-1) were laminated, and the obtained laminated films were cut into a circular plate with a diameter of 25mm to prepare a test piece of the first thermosetting resin film (x1-1) with a thickness of 1mm. The setting position of the test piece in the viscoelasticity measuring device ("MCR301" manufactured by Anton Paar) was preheated at 90°C, and the test piece of the first thermosetting resin film (x1-1) obtained above was placed on the setting position. The test piece was fixed to the aforementioned setting position by pressing the measuring jig against the upper surface of the test piece. Then, under the conditions of temperature of 90°C and measuring frequency of 1Hz, the strain generated in the test piece was gradually increased in the range of 0.01%~1000%, and the storage elastic modulus Gc of the 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.

3-3. Determination of the protrusion amount of the first thermosetting resin film (x1-1) A release film ("SP-PET381031" manufactured by Lintec Corporation, 38 μm thick) made by subjecting one side of a polyethylene terephthalate film to a release treatment by polysilicone treatment was used, and the composition (x1-1-1) obtained above was applied on the release-treated surface, and heat-dried at 120°C for 2 minutes to form a first thermosetting resin film (x1-1) with a thickness of 30 μm. Then, the first thermosetting resin film (x1-1) was processed together with the release film into a circular shape with a diameter of 170 mm to prepare a test piece with a release film attached. The exposed surface of the obtained test piece (in other words, the surface opposite to the side with the release film) is fully bonded to the surface of a transparent tape-shaped back grinding tape ("E-8180" manufactured by Lintec Corporation), thereby obtaining a laminate as shown in FIG15. FIG15 is a plan view schematically showing the state of the obtained laminate when viewed from the top of the back grinding tape side. As shown here, the obtained laminate 101 is composed of the back grinding tape 107, the test piece 120 (the first thermosetting resin film (x1-1)) and the release film laminated in order in the thickness direction.

Next, the peeling film is removed from the obtained laminate, and the exposed surface of the newly generated test piece (in other words, the surface of the test piece opposite to the side with the back grinding tape) is pressed against a surface of a silicon wafer with a diameter of 12 inches, and the test piece is attached to the surface of the silicon wafer. At this time, the test piece is attached using an attachment device (roller laminator, "RAD-3510 F/12" manufactured by Lintec) under the conditions of stage temperature: 90°C, attachment speed: 2mm/sec, attachment pressure: 0.5MPa, and roller attachment height: -200μm, while heating the first thermosetting resin film (x1-1). Next, for the aforementioned 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 periphery is measured, and the measured value (maximum value of the length of the aforementioned line segment) is used to refer to Figure 2 and calculate the protrusion amount (mm) of the aforementioned test piece (in other words, the first thermosetting resin film (x1-1)) by the method already described. The results are shown in Table 1. In addition, when the protrusion amount is 170mm, it is judged that there is no shape change from the original test piece and no protrusion occurs. On the other hand, when the protrusion amount exceeds 170mm, it is judged that there is a shape change from the original test piece and protrusion occurs.

3-4. Confirmation of the presence or absence of residue of the first thermosetting resin film (x1-1) on the top of the bump The peeling film is removed from the first composite sheet (α1) obtained in "3-1. Production of the first composite sheet (α1)", and the surface (exposed surface) of the first thermosetting resin film (x1-1) thus exposed is pressed onto the bump forming surface of a semiconductor wafer having a diameter of 8 inches and having bumps, thereby attaching the first composite sheet (α1) from which the peeling film is removed to the bump forming surface of the semiconductor wafer. At this time, as a semiconductor wafer, a bump height of 210μm, a bump width of 250μm, and a distance between bumps of 400μm are used. Furthermore, the first composite sheet (α1) was attached using an attachment device (roller laminating machine, "RAD-3510 F/12" manufactured by Lintec) under the conditions of stage temperature: 90°C, attachment speed: 2mm/sec, attachment pressure: 0.5MPa, and roller attachment height: -200μm, while heating the first composite sheet (α1). Then, a multi-wafer bonding machine ("RAD-2700 F/12" manufactured by Lintec) was used to remove the first support sheet (Y1) from the first thermosetting resin film (x1-1) to expose the first thermosetting resin film (x1-1). Next, a scanning electron microscope (SEM, "VE-9700" manufactured by Keyence) was used to observe the surface of the bump of the semiconductor wafer from a direction perpendicular to the bump formation surface of the semiconductor wafer and a direction at an angle of 60° to confirm the presence or absence of residue of the first thermosetting resin film (x1-1) on the top of the bump. If residue was present on the top of the bump, it was determined as "residue was present", and if residue was not present on the top of the bump, it was determined as "residue was not present". The results are shown in Table 1.

3-5. Confirmation of the presence or absence of shrinkage (cissing) of the first thermosetting resin film (x1-1) on the bump forming surface The presence or absence of shrinkage (cissing) of the cured product of the first thermosetting resin film (x1-1) on the surface of the semiconductor chip on the bump forming surface was investigated using a 12-inch semiconductor wafer without a bump formed. Specifically, a 12-inch silicon wafer without a bump was used, and the first composite sheet (α1) was attached in the same manner as in the above-mentioned "3-4. Confirmation of the presence or absence of residue of the thermosetting resin film (x1-1) on the upper part of the bump", and the first supporting sheet (Y1) was removed from the first thermosetting resin film (x1-1). Next, the first thermosetting resin film attached to the semiconductor wafer was heat-treated in a pressurized oven ("RAD-9100" manufactured by Lintec) at a temperature of 130°C, a time of 2 hours, and an internal pressure of 0.5 MPa, thereby thermally curing the first thermosetting resin film (x1-1). Next, an optical microscope ("VHX-1000" manufactured by Keyence) was used to observe the entire laminate of the first thermosetting resin film (x1-1) (the first cured resin film (r1)) and the semiconductor wafer from the side of the cured product. Next, if there is a region where the exposure of the semiconductor wafer can be directly confirmed, it is determined as "there is cissing", and if there is no region where the exposure of the semiconductor wafer can be directly confirmed, it is determined as "there is no cissing".

3-5. Evaluation of the embedding property of the groove (1) Preparation of wafer for semiconductor chip manufacturing A 12-inch silicon wafer (wafer thickness 750μm) cut in half along the predetermined dividing line was used as the wafer for semiconductor chip manufacturing. The width of the half-cut portion of the silicon wafer (the width of the groove) was 60μm, and the depth of the groove was 230μm.

(2) Evaluation method The release film is removed from the first composite sheet (α1) obtained in "3-1. Production of the first composite sheet (α1)", and the surface (exposed surface) of the first thermosetting resin film (x1-1) exposed thereby is adhered to the surface side (half-cut formation surface) of a semiconductor chip manufacturing wafer while being pressed under the following conditions. ･Attachment device: Fully automatic bonding machine (manufactured by Lintec Co., Ltd., product name "RAD-3510") ･Roller pressure: 0.5MPa ･Roller height: -400μm ･Attachment speed: 5mm/sec ･Attachment temperature: 90℃ After peeling off the first support sheet (Y1) from the first thermosetting resin film (x1-1), the semiconductor chip wafer with the first thermosetting resin film (x1-1) attached thereto is heated at 130℃ for 4 hours to be cured to form a first cured resin film (r1). Next, the semiconductor chip manufacturing wafer was cut from the half-cut formation surface to the back side, and the embedding property of the first hardened resin film (r1) in the groove portion of the half-cut portion was observed using an optical microscope ("VHX-1000" manufactured by Keyence). The embedding property evaluation criteria are as follows. S: The shape of the first hardened resin film (r1) is not deformed, and the embedding property is the best. A: Although the shape of the first hardened resin film (r1) is slightly deformed near the entrance of the groove, the embedding property is good. B: The embedding property is poor.

4. Results The components and evaluation results of the first thermosetting resin film-forming composition (x1-1-1) are shown in Table 1. In addition, the results of "3-5. Evaluation of embedding properties in grooves" (picture instead of photograph) are shown in FIG16.

The results shown in Table 1 show the following. It can be seen that in Examples 1 and 2 where the X value is 19 or more and less than 10,000, no protrusion is observed, no residue on the top of the bump, no shrinkage (cissing) is observed during attachment, and the groove embedding property is also good. In contrast, it can be seen that if the X value is less than 19 as in Comparative Examples 1 and 3, one or more of the following will occur: the occurrence of protrusion, the occurrence of residue on the top of the bump, and poor embedding property. In addition, it can be seen from the figure-substituted photograph of Figure 16 that if protrusion occurs as in Comparative Example 1, the groove embedding property becomes poor. In addition, in Comparative Example 3, the first thermosetting resin film (x1-1) does not penetrate into the groove. Furthermore, it can be seen that when the X value is 10,000 or more as in Comparative Example 2, cissing occurs in the bump forming surface.

From the above results, it can be seen that by using the first thermosetting resin film (x1-1) of Examples 1 and 2 to form a semiconductor chip with a first curing resin film (r1) as a wafer, and subjecting it to the above-mentioned step (S4) and the above-mentioned step (S-BG) for singulation, a semiconductor chip can be obtained in which the bump forming surface and the side surface are well covered by the first curing resin film (r1).

10: Wafer for semiconductor chip manufacturing 11: Wafer 11a: Bump forming surface 11b: Back surface 12: Bump 13: Groove 40: Semiconductor chip x1: First curable resin r1: First curable resin film X1: Layer Y1: First supporting sheet α1: First composite sheet x2: Second curable resin r2: Second curable resin film X2: Layer Y2: Second supporting sheet α2: Second composite sheet 51: Substrate 61: Adhesive layer 71: Intermediate layer

[Fig. 1] is a schematic cross-sectional view of the first curable resin film (x1). [Fig. 2] is a plan view for schematically illustrating the protrusion amount of the resin film when the plane shape of the resin film is a circle. [Fig. 3] is a schematic cross-sectional view showing the structure of the first composite sheet (α1) used in the manufacturing method of the present invention. [Fig. 4] is a schematic cross-sectional view showing an example of the specific structure of the first composite sheet (α1). [Fig. 5] is a schematic cross-sectional view showing another example of the specific structure of the first composite sheet (α1). [Fig. 6] is a schematic cross-sectional view showing another example of the specific structure of the first composite sheet (α1). [Fig. 7] is a schematic diagram of the steps of the manufacturing method of the semiconductor chip of the present invention. [FIG. 8] is a top view showing an example of a wafer for semiconductor chip manufacturing prepared in step (S1). [FIG. 9] is a schematic cross-sectional view showing an example of a wafer for semiconductor chip manufacturing prepared in step (S1). [FIG. 10] is a schematic diagram showing step (S2). [FIG. 11] is a schematic diagram showing the manufacturing method of the first embodiment. [FIG. 12] is a schematic diagram showing the manufacturing method of the second embodiment. [FIG. 13] is a schematic diagram showing the manufacturing method of the third embodiment. [FIG. 14] is a schematic diagram showing the manufacturing method of the fourth embodiment. [Fig. 15] is a schematic plan view of a laminate including a first thermosetting resin film (x1-1) produced when measuring the protrusion amount of the first thermosetting resin film (x1-1). [Fig. 16] is a diagram-substituting photograph showing the cross-sectional observation results of the embedding properties of the grooves in Examples 1 and 2 and Comparative Example 1.

151: The first peeling film

152: Second peeling film

x1: First hardening resin

x1a: Page 1

x1b: Side 2

Claims (14)

A curable resin film is used to form a protective film on both the bump forming surface and the side surface of a semiconductor chip having a bump forming surface with bumps; and the curable resin film satisfies the following requirement (I): <Requirement (I)> Under the conditions of temperature 90°C and frequency 1 Hz, a test piece of the curable resin film having a diameter of 25 mm and a thickness of 1 mm is subjected to stress. The storage elastic modulus of the test piece is measured. When the strain of the test piece is 1%, the storage elastic modulus of the test piece is set to Gc1, and when the strain of the test piece is 300%, the storage elastic modulus of the test piece is set to Gc300. The value of X calculated by the following formula (i) is greater than 19 and less than 10,000, X=Gc1/Gc300. . . . (i). The curable resin film of claim 1, wherein in the aforementioned requirement (I), Gc300 is less than 15,000. A composite sheet is used to form a hardened resin film as a protective film on both the bump forming surface and the side surface of a semiconductor chip having a bump forming surface with bumps, and has a laminated structure formed by laminating a support sheet and a hardening resin layer, wherein the hardening resin is a hardening resin film as claimed in claim 1 or 2. A use of a curable resin film, which is to use the curable resin film as claimed in claim 1 or 2 to form a curable resin film as a protective film on both the bump forming surface and the side surface of a semiconductor chip having a bump forming surface with bumps. A use of a composite sheet, which is to use the composite sheet as claimed in claim 3 to form a hardened resin film as a protective film on both the bump forming surface and the side surface of a semiconductor chip having a bump forming surface with bumps. A method for manufacturing a semiconductor chip comprises the following steps (S1) to (S4) in sequence: step (S1): preparing a semiconductor chip manufacturing wafer, wherein the semiconductor chip manufacturing wafer is a semiconductor wafer having a bump forming surface with bumps, and a groove portion serving as a predetermined dividing line is formed on the bump forming surface of the semiconductor wafer in a manner that does not reach the back surface; step (S2): applying a first curable resin to the semiconductor wafer; (x1) is pressed and attached to the bump-forming surface of the semiconductor chip manufacturing wafer, and the first curable resin (x1) is used to cover the bump-forming surface of the semiconductor chip manufacturing wafer, and the first curable resin (x1) is buried in the groove formed on the semiconductor chip manufacturing wafer; step (S3): the first curable resin (x1) is made to ) to obtain a semiconductor wafer with a first hardened resin film (r1); step (S4): singulating the semiconductor wafer with the first hardened resin film (r1) along the predetermined dividing line to obtain a semiconductor wafer with at least the bump forming surface and the side surface covered by the first hardened resin film (r1); further, in the step (S2) After and before the aforementioned step (S3), After the aforementioned step (S3) and before the aforementioned step (S4), or in the aforementioned step (S4), the following step (S-BG) is included, step (S-BG): the step of grinding the aforementioned back side of the wafer used for the aforementioned semiconductor chip manufacturing; and using the curable resin film as claimed in claim 1 or 2 as the aforementioned first curable resin (x1). The method for manufacturing a semiconductor chip as claimed in claim 6, wherein the aforementioned step (S2) is implemented by pressing and attaching the first composite sheet (α1) having a laminated structure formed by laminating a first supporting sheet (Y1) and a layer (X1) of the aforementioned first curable resin (x1) to the aforementioned bump forming surface of the aforementioned semiconductor chip manufacturing wafer using the aforementioned layer (X1) as an attachment surface. The method for manufacturing a semiconductor chip as claimed in claim 7, wherein the step (S-BG) is included after the step (S2) and before the step (S3), and the step (S-BG) is implemented by grinding the back surface of the semiconductor chip manufacturing wafer with the first composite sheet (α1) attached thereto, and then peeling off the first supporting sheet (Y1) from the first composite sheet (α1), and the step (S4) is implemented by cutting the portion formed in the groove of the first hardened resin film (r1) of the semiconductor chip manufacturing wafer with the first hardened resin film (r1) along the predetermined dividing line. A method for manufacturing a semiconductor chip as claimed in claim 7, wherein the step (S-BG) is included after the step (S3) and before the step (S4), and the step (S3) is performed without peeling the first supporting sheet (Y1) from the first composite sheet (α1), and the step (S-BG) is performed by In the state, after grinding the back side of the semiconductor chip manufacturing wafer, the first supporting sheet (Y1) is peeled off from the first composite sheet (α1), and the step (S4) is implemented by cutting the portion formed in the groove of the first hardened resin film (r1) of the semiconductor chip manufacturing wafer with the first hardened resin film (r1) along the predetermined dividing line. A method for manufacturing a semiconductor chip as claimed in claim 7, wherein the step (S-BG) is included after the step (S3) and before the step (S4), and the first supporting sheet (Y1) is peeled off from the first composite sheet (α1) after the step (S2) and before the step (S3), and the step (S-BG) is performed by attaching a back grinding sheet (b-BG) to the first hardening resin film (r1) of the semiconductor chip manufacturing wafer with the first hardening resin film (r2). 1), after grinding the back side of the semiconductor wafer with the back side grinding sheet (b-BG) attached thereto, the back side grinding sheet (b-BG) is peeled off from the semiconductor wafer with the first hardened resin film (r1), and the step (S4) is performed by cutting the portion of the first hardened resin film (r1) of the semiconductor wafer with the first hardened resin film (r1) formed in the groove along the predetermined dividing line. The method for manufacturing a semiconductor chip as claimed in claim 7, wherein the step (S4) includes the step (S-BG), and after the step (S2) and before the step (S3), the first supporting sheet (Y1) is peeled off from the first composite sheet (α1), and the step (S4) is performed by forming the first hardened resin film (r1) of the semiconductor chip with the first hardened resin film (r1) in the first hardened resin film (r1) of the wafer. After the groove portion is cut along the aforementioned predetermined dividing line or the modified area is formed along the aforementioned predetermined dividing line, as the aforementioned step (S-BG), a back grinding sheet (b-BG) is attached to the surface of the aforementioned first hardened resin film (r1) of the aforementioned semiconductor wafer manufacturing wafer with the aforementioned first hardened resin film (r1), and the aforementioned back side of the aforementioned semiconductor wafer manufacturing wafer is ground while the aforementioned back grinding sheet (b-BG) is attached. A method for manufacturing a semiconductor chip as claimed in any one of claims 6 to 11, further comprising the following step (T): step (T): forming a second hardened resin film (r2) on the aforementioned back side of the wafer used for manufacturing the semiconductor chip. A method for manufacturing a semiconductor chip as claimed in any one of claims 6 to 11, wherein the width of the groove is 10 μm to 2000 μm. A method for manufacturing a semiconductor chip as claimed in any one of claims 6 to 11, wherein the depth of the groove is 30 μm to 700 μm.