CN111656491A

CN111656491A - Method for manufacturing semiconductor chip

Info

Publication number: CN111656491A
Application number: CN201980010027.XA
Authority: CN
Inventors: 田久真也; 山田忠知
Original assignee: Lintec Corp
Current assignee: Lintec Corp
Priority date: 2018-03-30
Filing date: 2019-03-26
Publication date: 2020-09-11
Also published as: TWI825080B; WO2019189173A1; TW202004874A; JP7267259B2; KR20200138154A; JPWO2019189173A1

Abstract

The present invention provides a method for manufacturing a semiconductor chip with a first protective film, the method comprising: attaching a thermosetting resin film to a first surface of a semiconductor wafer having a bump on the bump side; forming a first protective film on the first surface of the semiconductor wafer by thermally curing the thermosetting resin film; performing half-cut dicing on the semiconductor wafer from the side of the first surface on which the first protective film is formed; and removing residues of the first protection film on the tops of the heads of the bumps by performing plasma irradiation on one side of the half-cut first surface of the semiconductor wafer, and simultaneously singulating the semiconductor wafer.

Description

Method for manufacturing semiconductor chip

Technical Field

The present invention relates to a method for manufacturing a semiconductor chip. More specifically, the present invention relates to a method for manufacturing a semiconductor chip with a first protective film for protecting a bump formation surface.

The present application claims priority based on japanese patent application No. 2018-069682, filed in japanese application No. 2018-3-30, and the contents of which are incorporated herein by reference.

Background

Conventionally, when a multi-pin LSI package used for an MPU, a gate array, or the like is mounted on a printed wiring board, a flip-chip mounting method has been employed in which a semiconductor chip having protruding electrodes (hereinafter, referred to as "bumps" in this specification) made of eutectic solder, high-temperature solder, gold, or the like formed on connection pad portions thereof is used as a semiconductor chip, and these bumps are brought into contact with corresponding terminal portions on a chip mounting board by a so-called flip-chip method so as to be fusion/diffusion bonded.

The semiconductor chip used in the mounting method can be obtained, for example, by: a surface of a semiconductor wafer having bumps formed on a circuit surface, which is opposite to the circuit surface (in other words, a bump formation surface), is ground and cut to be singulated (singulated). In the process of obtaining the semiconductor chip, a curable resin film is generally attached to the bump formation surface for the purpose of protecting the bump formation surface and the bump of the semiconductor wafer, and the film is cured to form a protective film (hereinafter, this may be referred to as "first protective film" in this specification) on the bump formation surface.

The curable resin film is generally attached to the bump formation surface of the semiconductor wafer in a state softened by heating. The curable resin film spreads between the bumps so as to cover the bumps of the semiconductor wafer, adheres to the bump formation surface, and covers the surfaces of the bumps, particularly the surfaces of the portions near the bump formation surface, thereby embedding the bumps. Then, the curable resin film is further cured to cover the bump formation surface of the semiconductor wafer and the surface of the bump in the vicinity of the bump formation surface, thereby serving as a protective film for protecting these regions. Further, the semiconductor wafer is singulated into semiconductor chips, and finally, semiconductor chips provided with a protective film on the bump formation surface (in this specification, these semiconductor chips may be referred to as "semiconductor chips with a protective film").

The semiconductor chip with the protective film is mounted on a substrate to form a semiconductor package, and the semiconductor package is used to form a target semiconductor device. In order for the semiconductor package and the semiconductor device to function properly, it is necessary to prevent the bumps of the semiconductor chip with the protective film from being electrically connected to the circuits on the substrate. However, the curable resin film sometimes remains on the top of the head of the bump. The curable resin film remaining on the top of the head of the bump is cured in the same manner as the curable resin film in the other region, and becomes a cured product having the same composition as the protective film (in this specification, it is sometimes referred to as "protective film residue"). In this way, since the top of the head of the bump is the area where the bump is electrically connected to the circuit on the substrate, when the amount of the residue of the protective film is large, the electrical connection between the bump of the semiconductor chip with the protective film and the circuit on the substrate is obstructed, resulting in a decrease in the electrical characteristics in the reliability test.

That is, at a stage before the semiconductor chip with the protective film is mounted on the substrate, it is required that there is almost no protective film residue on the tops of the bumps of the semiconductor chip with the protective film.

As a method for removing the protective film on the top of the head of the bump, a method for manufacturing a semiconductor device by performing plasma processing has been proposed (see patent document 1). A semiconductor device having excellent connection reliability can be efficiently manufactured by performing plasma treatment on a protective film on a bump formation surface, removing a resin film covering the top of a bump, dicing and singulating the semiconductor chip with a dicing blade, and electrically connecting the bump exposed from the top of the head and an electrode of a substrate.

Further, there is also known a method of etching and dividing a semiconductor wafer by covering a region of the semiconductor wafer other than a scribe line with a resist in advance and irradiating a portion corresponding to the scribe line not covered with the resist with plasma (patent document 2 and the like).

Documents of the prior art

Patent document

Patent document 1: international publication No. 2016/194431

Patent document 2: japanese laid-open patent publication No. 2004-193305

Disclosure of Invention

Technical problem to be solved by the invention

However, the dicing method disclosed in patent document 1 requires a plasma treatment process to remove the resin film on the top of the bump head before the dicing process, and thus has a difficulty in terms of productivity. In addition, the dicing method disclosed in patent document 2 requires a resist film coating, exposure, and development process before the dicing step, and thus has a difficulty in productivity.

Accordingly, an object of the present invention is to provide a method for manufacturing a semiconductor chip, which can simultaneously remove the residue of the first protection film on the top of the head of the bump and singulate the semiconductor wafer, and which has excellent productivity.

Means for solving the problems

The present invention includes the following aspects.

[1] A method of manufacturing a semiconductor chip with a first protective film, the method comprising:

attaching a thermosetting resin film on a first surface of a semiconductor wafer having bumps on the bump side;

forming a first protective film on the first surface of the semiconductor wafer by thermally curing the thermosetting resin film;

performing half-cut dicing (half-cut dicing) on the semiconductor wafer on which the first protective film is formed from one side of the first surface; and

removing residues of the first protection film at the top of the head of the bump by plasma irradiation to one side of the first surface of the semiconductor wafer half-cut, and simultaneously singulating the semiconductor wafer.

[2] A method of manufacturing a semiconductor chip with a first protective film, the method comprising:

attaching a thermosetting resin film of a first protective film forming sheet including a first support sheet and the thermosetting resin film provided on the first support sheet to a first surface of a semiconductor wafer having bumps on the bump side;

peeling the first support sheet from the thermosetting resin film;

performing half-cut dicing on the semiconductor wafer from one side of the first surface; and

removing residues of the first protection film on the top of the head of the bump by performing plasma irradiation on one side of the half-cut first surface of the semiconductor wafer, and simultaneously singulating the semiconductor wafer.

[3] The method for manufacturing a semiconductor chip with a first protective film according to [1] or [2], wherein, with respect to the semiconductor wafer half-cut, a remaining thickness a (μm) of a half-cut portion of the semiconductor wafer, a thickness B (μm) of the first protective film on the first surface of the semiconductor wafer, a thickness C (μm) of the first protective film on a top of a head of the bump, an etching rate a (μm/min) of the semiconductor wafer based on plasma irradiation, an etching rate B (μm/min) of the first protective film based on plasma irradiation, and a time t (min) of plasma irradiation satisfy relationships of the following expression (1), expression (2), and expression (3).

A<at···(1)

B>bt···(2)

C<bt···(3)

[4] A method of manufacturing a semiconductor chip with a first protective film, the method comprising:

performing half-cut dicing of the semiconductor wafer to which the thermosetting resin film is attached from one side of the first surface;

removing the thermosetting resin film on the top of the head of the bump by performing plasma irradiation on one side of the half-cut first surface of the semiconductor wafer, and simultaneously singulating the semiconductor wafer; and

and thermally curing the thermosetting resin film attached to the singulated semiconductor wafer to form a first protective film on the first surface of the semiconductor wafer.

[5] A method of manufacturing a semiconductor chip with a first protective film, the method comprising:

peeling the first support sheet from the thermosetting resin film;

[6] The method for manufacturing a semiconductor chip with a first protective film according to [4] or [5], wherein, with respect to the semiconductor wafer half-cut, a remaining thickness a (μm) of a half-cut portion of the semiconductor wafer, a thickness D (μm) of the thermosetting resin film on the first surface of the semiconductor wafer, a thickness E (μm) of the thermosetting resin film on a top of a head of the bump, an etching rate a (μm/min) of the semiconductor wafer by plasma irradiation, an etching rate D (μm/min) of the thermosetting resin film by plasma irradiation, and a time t (min) of plasma irradiation satisfy the relationship of the following expression (1), expression (4), and expression (5).

A<at···(1)

D>dt···(4)

E<dt···(5)

Effects of the invention

According to the present invention, by performing plasma irradiation after half-dicing a semiconductor wafer, it is possible to perform dicing by plasma irradiation without covering a resist film, and it is possible to simultaneously achieve removal of the residue of the first protective film on the top of the head of the bump and singulation of the semiconductor wafer, and the productivity is excellent. In addition, since dicing is performed by plasma irradiation after half-dicing, occurrence of chipping (chipping) can be reduced, and chip strength can be improved.

Drawings

Fig. 1 is a schematic view schematically showing a first embodiment of a method for manufacturing a semiconductor chip with a first protective film according to the present invention.

Fig. 2 is a schematic view schematically showing a first embodiment of the method for manufacturing a semiconductor chip with a first protective film according to the present invention.

Fig. 3 is a schematic view schematically showing a second embodiment of the method for manufacturing a semiconductor chip with a first protective film according to the present invention.

Detailed Description

Method for manufacturing semiconductor chip with first protective film

< first embodiment >

Fig. 1 and 2 are schematic views schematically showing a first embodiment of a method for manufacturing a semiconductor chip with a first protective film according to the present invention.

For the sake of convenience, the drawings used in the following description may show the main parts enlarged, and the dimensional ratios of the respective components are not necessarily the same as those in the actual case.

The method for manufacturing a semiconductor chip with a first protective film according to the first embodiment includes:

attaching the thermosetting resin film 12 of a first protective film forming sheet 1 ((a) in fig. 1) including a first supporting sheet 101 and the thermosetting resin film 12 provided on the first supporting sheet 101, to a first surface 9a on the bump 91 side of a semiconductor wafer 9 ((b) in fig. 1) having a bump 91 ((c) in fig. 1);

grinding a second surface 9b of the semiconductor wafer 9 on the opposite side of the first surface 9a (fig. 1 (d));

attaching a dicing tape 14 on the ground second surface 9b of the semiconductor wafer 9 ((e) in fig. 1);

peeling the first support sheet 101 from the thermosetting resin film 12 ((f) in fig. 2);

forming a first protective film 12' (fig. 2(g)) on the first surface of the semiconductor wafer 9 by thermally curing the thermosetting resin film 12;

half-cut dicing the semiconductor wafer 9 from the side of the first face ((h) in fig. 2);

the plasma irradiation is performed on the side of the first surface of the semiconductor wafer 9 that is half-cut, the residue of the first protection film 12' of the top portion 910 of the bump 91 is removed, and at the same time, the semiconductor wafer 9 is singulated ((i) in fig. 2).

First, as shown in fig. 1a and 1 b, the first protective film forming sheet 1 is disposed so that the thermosetting resin film 12 faces the first bump-side surface 9a (which may be referred to as a "bump forming surface") of the semiconductor wafer 9.

The first protective film forming sheet 1 includes a thermosetting resin film 12 on a first support sheet 101. The first support sheet 101 preferably includes a cushion layer 13 on the first base material 11. The first protective film forming sheet of the present invention includes, as one side surface, a first support sheet and a thermosetting resin film provided on the first support sheet. As another aspect, the first protective film forming sheet of the present invention includes a first base material, a buffer layer provided on the first base material, and a thermosetting resin film provided on the buffer layer.

The first protective film forming sheet 1 will be described in detail later.

The height of the bump 91 of the semiconductor wafer 9 is not particularly limited, but is preferably 40 to 200 μm, more preferably 50 to 180 μm, and particularly preferably 60 to 140 μm.

In the present specification, the "height of the bump" refers to the height of a portion of the bump that is located at the highest position from the bump formation surface (i.e., the distance in the vertical direction from the bump formation surface of the semiconductor wafer to the highest position of the bump).

The width of the bump 91 is not particularly limited, but is preferably 60 to 250 μm, more preferably 80 to 220 μm, and particularly preferably 120 to 180 μm.

In the present specification, the "width of the bump" refers to the maximum value of a line segment connecting 2 different points on the bump surface with a straight line when the bump is viewed from a downward direction perpendicular to the bump forming surface.

The distance between the adjacent bumps 91 is not particularly limited, but is preferably 100 to 350 μm, more preferably 130 to 300 μm, and particularly preferably 160 to 250 μm.

In the present specification, the term "distance between adjacent bumps" refers to the minimum value of the distance between surfaces of adjacent bumps.

Thickness A of semiconductor wafer₀The thickness is not particularly limited, but is preferably 50 to 200. mu.m, more preferably 65 to 180. mu.m, and particularly preferably 80 to 150. mu.m.

In addition, in the present specification, "thickness a of semiconductor wafer₀"refers to the thickness of the semiconductor wafer, and particularly to the thickness of the semiconductor wafer after grinding.

Unless otherwise specified, "thickness" in the present specification is an average value of values measured by a constant-pressure thickness gauge at 10 randomly selected positions.

Then, the bumps 91 on the semiconductor wafer 9 are brought into contact with the thermosetting resin film 12, and the first protective film forming sheet 1 is pressure-bonded to the semiconductor wafer 9. Thereby, the first surface 12a of the thermosetting resin film 12 is sequentially brought into pressure contact with the surface 91a of the bump 91 and the first surface 9a of the semiconductor wafer 9. At this time, the thermosetting resin film 12 is heated, so that the thermosetting resin film 12 is softened, spreads between the bumps 91 so as to cover the bumps 91, adheres to the first surface 9a, and covers the surface 91a of the bumps 91, particularly the surface 91a of the semiconductor wafer 9 in the vicinity of the first surface 9a, thereby embedding the bumps 91.

As a method of pressure-bonding the first protective film forming sheet 1 and the semiconductor wafer 9, a known method of bonding various sheets to an object by pressure bonding may be used, and for example, a method using a laminating roller may be mentioned.

The heating temperature when the first protective film forming sheet 1 and the semiconductor wafer 9 are pressure bonded may be a temperature at which the thermosetting resin film 12 is not cured at all or is not excessively cured, and is preferably 80 to 100 ℃, and more preferably 85 to 95 ℃.

The pressure at which the first protective film forming sheet 1 and the semiconductor wafer 9 are pressure bonded is not particularly limited, but is preferably 0.1 to 1.5Mpa, and more preferably 0.3 to 1 Mpa.

As described above, when the first protective film forming sheet 1 and the semiconductor wafer 9 are pressed against each other, the thermosetting resin film 12 in the first protective film forming sheet 1 receives pressure from the bump 91, and the first surface 12a of the thermosetting resin film 12 is initially deformed into a concave shape.

In summary, the first protective film forming sheet 1 is attached to the first surface 9a of the semiconductor wafer 9 through the thermosetting resin film 12 ((c) in fig. 1).

Then, the second surface 9b (i.e., the back surface) of the semiconductor wafer 9 on the opposite side to the bump formation surface is ground as necessary ((d) in fig. 1), and then a dicing sheet is attached to the back surface ((e) in fig. 1). The dicing sheet may be provided with, for example, a second protective film forming film which is cured to form a second protective film for protecting the back surfaces of the semiconductor wafer and the semiconductor chips.

Then, only the thermosetting resin film 12 in the first protective film forming sheet 1 bonded to the first surface 9a of the semiconductor wafer 9 is left on the first surface 9a, and the first support sheet 101 is peeled from the thermosetting resin film 12 ((f) in fig. 2). For example, in the case of the first protective film forming sheet 1 shown in fig. 1, the "first support sheet 101" includes the first base material 11 and the buffer layer 13.

In the method of manufacturing a semiconductor chip with a first protective film according to the first embodiment, although the first support sheet 101 is used as described above, the steps of fig. 1 (a) to 1 (d) are not essential and any method may be used as long as the method of fig. 2 (f) can be manufactured.

Then, the thermosetting resin film 12 is cured, thereby forming the first protection film 12' (2 (g) in the drawing) on the bump formation surface of the semiconductor wafer.

The semiconductor wafer 9 provided with the first protection film 12' is half-cut (fig. 2 (h)). The "half-cut dicing" is a dicing method of cutting into the semiconductor wafer 9 and the first protective film 12 'from one side of the first protective film 12' so as not to completely cut the semiconductor wafer 9. As a method of half-cut dicing, a method of half-cut dicing of the semiconductor wafer 9 together with the first protection film 12 'from the side of the first protection film 12' may be used, and the dicing may be blade dicing or laser grooving may be used.

In the method for manufacturing a semiconductor chip according to the present invention, the steps of the method for manufacturing a semiconductor chip with a first protective film according to the first embodiment may be performed in the order mentioned above, and for example, as a modification of the method for manufacturing a semiconductor chip with a first protective film according to the first embodiment, there may be mentioned a method including the steps of:

attaching the thermosetting resin film 12 of the first protective film forming sheet 1 (fig. 1a) having the thermosetting resin film 12 on the first support sheet 101 to the first surface 9a of the semiconductor wafer 9 having the bump 91 (fig. 1 b) on the bump 91 side (fig. 1 c);

attaching a dicing tape 14 ((e) in fig. 1) on the ground second surface 9b of the semiconductor wafer 9;

performing half-cut dicing on the semiconductor wafer 9 from one side of the first surface;

forming a first protective film 12' (fig. 1 (h)) on the first surface of the semiconductor wafer 9 by thermally curing the thermosetting resin film 12; and

As another modification of the method for manufacturing a semiconductor chip with a first protective film according to the first embodiment, there is a method including the following steps, and the steps may be performed in this order:

attaching a thermosetting resin film 12 on a first surface 9a of a semiconductor wafer 9 having a bump 91 on the bump 91 side ((f) in fig. 2);

forming a first protective film 12' (fig. 2 (h)) on the first surface of the semiconductor wafer 9 by thermally curing the thermosetting resin film 12; and

The remaining thickness A of the half-cut portion of the semiconductor wafer (i.e., from the semiconductor)Thickness of the wafer excluding the half-cut portion) is not particularly limited, but is preferably the thickness a of the semiconductor wafer₀1/5-4/5, more preferably the thickness A₀1/4-3/4, particularly preferably the thickness A₀1/3-2/3. The remaining thickness A of the half-cut portion of the semiconductor wafer is preferably 25 to 100 μm, more preferably 32 to 90 μm, and particularly preferably 40 to 75 μm.

The plasma irradiation is performed on the side of the first surface of the semiconductor wafer 9 that is half-cut, the residue of the first protection film 12' of the top portion 910 of the bump 91 is removed, and at the same time, the semiconductor wafer 9 is singulated ((i) in fig. 2). By performing plasma irradiation after half-dicing the semiconductor wafer 9, it is possible to perform dicing by plasma irradiation without covering a resist film, and it is possible to simultaneously achieve removal of the residue of the first protection film 12' on the top portion 910 of the bump 91 and singulation of the semiconductor wafer 9, and productivity is excellent. In addition, since the dicing is performed by performing the plasma irradiation after the half-cut dicing, occurrence of chipping can be reduced, and the strength of the chip can be improved. Further, the residue of the first protection film 12' at the top 910 of the bump 91 may enter and remain in the recess formed at the top 910 of the bump 91. The residues of the first protection film 12' remaining in the recess of the top 910 of the bump 91 can be removed by plasma irradiation, and therefore a semiconductor device having excellent connection reliability can be efficiently manufactured.

The plasma processing apparatus for performing plasma irradiation is not particularly limited, and a known plasma processing apparatus can be used. The conditions of the plasma treatment vary depending on the types of the first protective film 12' and the semiconductor wafer 9, and are not particularly limited, however, for the semiconductor wafer half-diced, the remaining thickness a (μm) of the half-diced portion of the semiconductor wafer, the thickness B (μm) of the first protection film on the bump-side first surface of the semiconductor wafer (i.e., the thickness of the first protection film of the portion without bumps on the semiconductor wafer), the thickness C (μm) of the first protection film on the tops of the heads of the bumps, the etching rate a (μm/min) of the semiconductor wafer by plasma irradiation, the etching rate B (μm/min) of the first protection film by plasma irradiation, and the time t (min) of plasma irradiation preferably satisfy the relationship of the following expression (1), expression (2), and expression (3).

A<at···(1)

B>bt···(2)

C<bt···(3)

In addition, the remaining thickness a of the half-cut portion, the thickness B of the first protection film on the bump-side first surface of the semiconductor wafer, and the thickness C of the first protection film on the crown portion of the bump may be obtained as the following values: the thickness was measured by a scanning electron microscope at arbitrary 5 positions in the range of the obtained semiconductor chip, and the obtained values were expressed as an average.

In the present specification, the "etching rate" refers to a rate at which each object is etched when each object is irradiated with plasma.

In the range of the obtained semiconductor chip, it is more preferable that the maximum value a 'of the remaining thickness of the half-cut portion satisfies the formula (1)' when there is unevenness in the remaining thickness of the half-cut portion, it is more preferable that the minimum value B 'of the thickness of the first protection film on the first surface on the bump side satisfies the formula (2)' when there is unevenness in the thickness of the first protection film on the first surface on the bump side, and it is more preferable that the maximum value C 'of the thickness of the first protection film on the crown of the bump satisfies the formula (3)' when there is unevenness in the thickness of the first protection film on the crown of the bump.

A’<at···(1)’

B’>bt···(2)’

C’<bt···(3)’

The relationship among the formula (1), the formula (2), and the formula (3) is preferably satisfied, and the relationship among the formula (1) ', the formula (2) ' and the formula (3) ' is more preferably satisfied, whereby the semiconductor wafer irradiated with plasma for a time t (minute) is singulated, the thickness of the first protective film on the bump-side first surface is B-bt >0, and the semiconductor chip with the first protective film protecting the bump formation surface can be obtained.

As an irradiation gas in plasma irradiation, a fluorine-based stable gas (SF) can be mentioned₆、CF₄、C₂F₆、C₂F₄、CHF₃、C₄F₈、NF₃、XeF₂Etc.), O₂Ar, etc. from the viewpoint of excellent etching properties of the semiconductor wafer, SF is preferred₆、CF₄Or CHF₃。

The plasma power condition is preferably 100 to 8000W.

The etching rate a of the semiconductor wafer by plasma irradiation is preferably 0.3 to 30 μm/min, preferably 0.4 to 25 μm/min, and preferably 0.5 to 20 μm/min. The etching rate b of the first protective film by plasma irradiation is preferably 0.1 to 2 μm/min, preferably 0.2 to 1.5 μm/min, and preferably 0.3 to 1.0 μm/min.

Since the first protection film on the crown of the bump is compressed by the bump, the thickness C (μm) of the first protection film on the crown of the bump becomes thinner than the thickness B (μm) of the first protection film on the bump-side first surface of the semiconductor wafer. In contrast, since the first protective film is formed of a thermosetting resin, the etching rate a (μm/min) of the semiconductor wafer by the plasma irradiation is sufficiently higher than the etching rate b (μm/min) of the first protective film by the plasma irradiation. Therefore, by adjusting the time t (minute) for plasma irradiation, the conditions for plasma irradiation satisfying the relationships of the above-described equations (1), (2), and (3) can be easily adjusted.

For example, for a semiconductor wafer having a thickness B of 30 μm of the first protective film on the bump-side first surface of the semiconductor wafer, a thickness C of 3 μm of the first protective film on the crown of the bump, and a thickness of 100 μm, half-dicing is performed until the remaining thickness A is 50 μm, and the plasma irradiation gas is SF₆The etching rate a of the semiconductor wafer is set to 15 μm/min and the etching rate b of the first protective film is set to 1.5 μm/min by performing plasma irradiation under the condition that the plasma power is 2000W, and the above-mentioned expressions (1) and (1) are satisfied(2) And the relation of the formula (3).

Thereafter, the operation can be performed by the same method as the conventional method until the semiconductor device is manufactured. That is, the semiconductor chip with the first protective film is picked up, and the picked-up semiconductor chip is flip-chip mounted on the wiring board, thereby finally manufacturing the semiconductor device.

< second embodiment >

The method for manufacturing a semiconductor chip with a first protective film according to the second embodiment includes:

attaching a thermosetting resin film 12 on the first surface on the bump side of the semiconductor wafer 9 having bumps ((f) in fig. 3);

half-cut dicing (fig. 3 (g')) is performed on the semiconductor wafer 9 from the side of the first face;

performing plasma irradiation from the side of the half-cut first surface of the semiconductor wafer 9, removing the thermosetting resin film 12 on the head top portions of the bumps, and simultaneously singulating the semiconductor wafer 9 ((h') in fig. 3); and

the thermosetting resin film 12 is thermally cured, and a first protective film 12 '(fig. 3 (i')) is formed on the first surface of the semiconductor wafer 9.

In the method of manufacturing a semiconductor chip with a first protective film according to the second embodiment, the method of the embodiment shown in fig. 3 (f) includes steps through fig. 1 (a), 1 (b), 1 (c), 1 (d) and 3 (f), but the steps of fig. 1 (a) to 1 (d) are not essential and any method may be employed.

The half-cut first surface side of the semiconductor wafer 9 is subjected to plasma irradiation, thereby removing the residue of the thermosetting resin film 12 at the head top 910 of the bump 91 and simultaneously singulating the semiconductor wafer 9 ((h') in fig. 3). By performing plasma irradiation after half-dicing the semiconductor wafer 9, not only dicing can be performed by plasma irradiation without covering a resist film, but also removal of the residue of the thermosetting resin film 12 at the top portions 910 of the bumps 91 and singulation of the semiconductor wafer 9 can be simultaneously achieved, and productivity is excellent. In addition, since the dicing is performed by performing the plasma irradiation after the half-cut dicing, occurrence of chipping can be reduced, and the strength of the chip can be improved. Further, the residue of the thermosetting resin film 12 on the top portion 910 of the bump 91 may enter the recess formed on the top portion 910 of the bump 91 and remain. The residue of the thermosetting resin film 12 remaining in the recessed portion of the top portion 910 of the bump 91 can be removed by plasma irradiation, and therefore a semiconductor device excellent in connection reliability can be efficiently manufactured.

The plasma processing apparatus for performing plasma irradiation is not particularly limited, and a known plasma processing apparatus can be used. The conditions of the plasma treatment vary depending on the type of the thermosetting resin film 12 and the semiconductor wafer 9, and are not particularly limited, but for the half-cut semiconductor wafer, it is preferable that the remaining thickness a (μm) of the half-cut portion of the semiconductor wafer, the thickness D (μm) of the thermosetting resin film 12 on the first surface on the bump side of the semiconductor wafer (that is, the thickness of the thermosetting resin film of the portion without bumps on the semiconductor wafer), the thickness E (μm) of the thermosetting resin film 12 on the head top portion of the bumps, the etching rate a (μm/min) of the semiconductor wafer by the plasma irradiation, the etching rate D (μm/min) of the thermosetting resin film 12 by the plasma irradiation, and the time t (min) of the plasma irradiation satisfy the following formula (1), The relation between the formula (4) and the formula (5).

A<at···(1)

D>dt···(4)

E<dt···(5)

The remaining thickness a of the half-cut portion, the thickness D of the thermosetting resin film 12 on the bump-side first surface of the semiconductor wafer, and the thickness E of the first protective film on the crown of the bump can be obtained as the following values: the average value of the thickness was measured by a scanning electron microscope at arbitrary 5 positions in the range of the obtained semiconductor chip.

In the range of the obtained semiconductor chip, it is more preferable that the maximum value a 'of the remaining thickness of the half-cut portion satisfies the formula (1)' when there is unevenness in the remaining thickness of the half-cut portion, it is more preferable that the minimum value D 'of the thickness of the thermosetting resin film 12 on the first surface on the bump side satisfies the formula (4)' when there is unevenness in the thickness of the thermosetting resin film 12 on the first surface on the bump side, and it is more preferable that the maximum value E 'of the thickness of the thermosetting resin film 12 on the top of the head of the bump satisfies the formula (5)' when there is unevenness in the thickness of the first protective film on the top of the head of the bump.

A’<at···(1)’

D’>bt···(4)’

E’<bt···(5)’

The relationship among the expressions (1), (4) and (5) is preferably satisfied, and the relationship among the expressions (1) ', (4) ' and (5) ' is more preferably satisfied, whereby the semiconductor wafer irradiated with plasma for a time t (minute) is singulated, the thickness of the first protective film on the bump-side first surface is D-dt >0, and a semiconductor chip with the first protective film protecting the bump-formed surface can be obtained.

The etching rate a of the semiconductor wafer by plasma irradiation is preferably 0.3 to 30 μm/min, preferably 0.4 to 25 μm/min, and preferably 0.5 to 20 μm/min. The etching rate d of the thermosetting resin film 12 by plasma irradiation is preferably 0.1 to 2 μm/min, preferably 0.2 to 1.5 μm/min, and preferably 0.3 to 1.0 μm/min.

Since the first protective film on the crown portion of the bump is compressed by the bump, the thickness E (μm) of the thermosetting resin film 12 on the crown portion of the bump becomes thinner than the thickness D (μm) of the thermosetting resin film 12 on the first surface on the bump side of the semiconductor wafer. Since the semiconductor wafer is easily etched by the plasma irradiation, the etching rate a (μm/min) of the semiconductor wafer by the plasma irradiation is sufficiently larger than the etching rate d (μm/min) of the thermosetting resin film 12 by the plasma irradiation. Therefore, by adjusting the time t (minute) for plasma irradiation, the conditions for plasma irradiation satisfying the relationships of the above-described equations (1), (4), and (5) can be easily adjusted.

For example, a semiconductor wafer having a thickness D of the thermosetting resin film 12 on the first surface on the bump side of the semiconductor wafer of 30 μm, a thickness E of the thermosetting resin film 12 on the top of the head of the bump of 3 μm, and a thickness of 100 μm is half-cut to a remaining thickness A of 50 μm, and the plasma irradiation gas is SF₆By performing plasma irradiation under the condition of a plasma power of 2000W, the etching rate a of the semiconductor wafer can be set to 15 μm/min, and the etching rate b of the first protective film can be set to 1.5 μm/min, so that the relationships among the above-mentioned expressions (1), (4) and (5) can be satisfied.

First protective film forming sheet

Fig. 1 (a) is a cross-sectional view schematically showing an embodiment of the first protective film forming sheet 1 including the thermosetting resin film 12 on the first support sheet 101.

The first protective film forming sheet 1 shown in fig. 1 (a) includes a first support sheet 101 and a thermosetting resin film 12 provided on one surface 101a of the first support sheet 101. More specifically, the first protective film forming sheet 1 includes a first base 11, a buffer layer 13 provided on the first base 11, and a thermosetting resin film 12 provided on the buffer layer 13, and the first base 11 and the buffer layer 13 constitute a first support sheet 101.

The first protective film forming sheet is not limited to the sheet shown in fig. 1 (a), and a part of the structure of the sheet shown in fig. 1 (a) may be modified, deleted, or added within a range not to impair the effect of the present invention.

Next, the respective layers constituting the first protective film forming sheet will be described.

Very good thermosetting resin film

The thermosetting resin film is used to protect the first surface on the bump side (i.e., the bump formation surface) of the semiconductor wafer and the bumps provided on the bump formation surface.

The thermosetting resin film of the present invention is softened by heating and heat-cured by further heating, as in the case of a general resin film, and has a property of being hardened when returning to normal temperature after heat curing, as compared with a thermosetting resin film at normal temperature (23 ℃) before heat curing. Thus, the first protective film formed on the surface having the bump functions as a protective film.

The thermosetting resin film is in the form of a sheet or a film, and the material of the thermosetting resin film is not particularly limited.

The thermosetting resin film may be 1 layer (single layer) or a plurality of 2 or more layers. In the case of a plurality of layers, these plurality of layers may be the same as or different from each other, and the combination of these plurality of layers is not particularly limited.

The thickness of the thermosetting resin film is preferably 1 to 100 μm, more preferably 5 to 75 μm, and particularly preferably 5 to 50 μm. By setting the thickness of the thermosetting resin film to the lower limit or more, the first protective film having higher protective performance can be formed.

Further, by setting the thickness of the thermosetting resin film to the upper limit or less, the thickness is suppressed from becoming excessively thick.

Here, the "thickness of the thermosetting resin film" means the thickness of the entire thermosetting resin film, and for example, the thickness of the thermosetting resin film composed of a plurality of layers means the total thickness of all the layers constituting the thermosetting resin film.

Very good first protective film

The first protective film is a film obtained by thermally curing a first surface (i.e., a bump formation surface) on the bump side of the semiconductor wafer and a bump provided on the bump formation surface.

The thickness B (μm) of the first protective film on the bump-side first surface of the semiconductor wafer (i.e., the thickness of the first protective film of the portion of the semiconductor wafer where there are no bumps) is the same as the thickness of the thermosetting resin film. Since the first protection film on the crown portion of the bump is compressed by the bump, the thickness C (μm) of the first protection film on the crown portion of the bump is thinner than the thickness B (μm) of the thermosetting resin film, that is, the thickness of the first protection film on the first surface on the bump side of the semiconductor wafer. The thickness B of the first protective film on the bump-side first surface of the semiconductor wafer is preferably 1.1 to 100 μm, more preferably 5 to 75 μm, and particularly preferably 10 to 50 μm.

The thickness C of the first protective film on the top of the head of the bump is preferably 0.11 to 10 μm, more preferably 0.5 to 7.5 μm, and particularly preferably 1 to 5 μm.

Composition for Forming thermosetting resin film

The thermosetting resin film is formed from a thermosetting resin film-forming composition containing a constituent material thereof. For example, a thermosetting resin film can be formed at a target site by applying a thermosetting resin film-forming composition to a surface to be formed of a thermosetting resin film and drying the composition as necessary. A more specific method for forming the thermosetting resin film will be described in detail later together with a method for forming other layers. The content ratio of the components that do not vaporize at normal temperature (23 ℃) in the composition for forming a thermosetting resin film is generally the same as the content ratio of the components of the thermosetting resin film.

The coating of the composition for forming a thermosetting resin film may be carried out by a known method, and examples thereof include methods using various coaters such as an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a curtain coater, a die coater, a knife coater, a screen coater, a meyer bar coater, and a kiss coater.

The drying conditions of the thermosetting resin film-forming composition are not particularly limited, and when the thermosetting resin film-forming composition contains a solvent described later, it is preferably dried by heating, and in this case, for example, it is preferably dried at 70 to 130 ℃ for 10 seconds to 5 minutes.

< composition for Forming resin layer >

Examples of the composition for forming a thermosetting resin film include a composition for forming a thermosetting resin film containing a polymer component (a) and a thermosetting component (B) (in the present specification, this may be abbreviated as "composition for forming a resin layer").

[ Polymer component (A) ]

The polymer component (a) is a polymer compound that imparts film formability, flexibility, and the like to the thermosetting resin film, and is considered to be a component formed by polymerization of a polymerizable compound. The polymerization reaction in the present specification also includes a polycondensation reaction.

The polymer component (a) contained in the resin layer forming composition and the thermosetting resin film may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

Examples of the polymer component (a) include polyvinyl acetal, acrylic resin, polyester, urethane resin, acrylic urethane resin, silicone resin, rubber resin, phenoxy resin, and thermoplastic polyimide.

The polyvinyl acetal in the polymer component (a) may be a known polyvinyl acetal.

Among these, preferable polyvinyl acetals include polyvinyl formal and polyvinyl butyral, and more preferable polyvinyl butyral.

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

[ chemical formula 1]

In the formula I₁、m₁And n₁Each is a content ratio (% by mole) of each structural unit relative to the total number of moles of all structural units constituting the polyvinyl butyral).

The polyvinyl acetal preferably has a weight average molecular weight (Mw) of 5000 to 200000, more preferably 8000 to 100000.

The proportion of structural units having a butyraldehyde group is l₁(degree of butyralation) relative to the constituent polyvinyl alcoholThe total mole number of all the structural units of the butyral is preferably 40 to 90 mole%, more preferably 50 to 85 mole%, and particularly preferably 60 to 76 mole%.

Content ratio m of structural units having acetyl group₁The amount of the polyvinyl butyral resin is preferably 0.1 to 9 mol%, more preferably 0.5 to 8 mol%, and particularly preferably 1 to 7 mol% based on the total number of moles of all the structural units constituting the polyvinyl butyral resin.

Content ratio n of structural units having hydroxyl group₁The amount of the polyvinyl butyral resin is preferably 10 to 60 mol%, more preferably 10 to 50 mol%, and particularly preferably 20 to 40 mol% based on the total number of moles of all the structural units constituting the polyvinyl butyral resin.

The polyvinyl acetal preferably has a glass transition temperature (Tg) of 40 to 80 ℃ and more preferably 50 to 70 ℃.

The glass transition temperature can be measured, for example, by a differential scanning calorimetry apparatus (product name "DSC A2000" manufactured by TA Instruments) at a temperature rising and falling rate of 20 ℃/min.

The ratio of 3 or more monomers constituting the polyvinyl acetal can be selected arbitrarily.

As the acrylic resin in the polymer component (a), a known acrylic polymer can be mentioned.

The weight average molecular weight (Mw) of the acrylic resin is preferably 10000 to 2000000, more preferably 100000 to 1500000. When the weight average molecular weight of the acrylic resin is not less than the lower limit, the shape stability (stability with time during storage) of the thermosetting resin layer is improved. Further, by setting the weight average molecular weight of the acrylic resin to be not more than the upper limit, the thermosetting resin layer can easily follow the uneven surface of the adherend, and generation of voids and the like between the adherend and the thermosetting resin layer can be further suppressed.

In the present specification, unless otherwise specified, "weight average molecular weight" refers to a polystyrene equivalent value measured by a Gel Permeation Chromatography (GPC) method.

The glass transition temperature (Tg) of the acrylic resin is preferably-50 to 70 ℃, more preferably-30 to 50 ℃. When Tg of the acrylic resin is not less than the lower limit, adhesion between the first protective film and the first support sheet is suppressed, and the peelability of the first support sheet is improved. When the Tg of the acrylic resin is not more than the upper limit, the adhesive strength between the thermosetting resin film and the first protective film and the adherend is improved.

The acrylic resin is, for example, a polymer of one or two or more kinds of (meth) acrylic acid esters; examples of the (meth) acrylate include copolymers obtained by copolymerizing one or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide.

Examples of the (meth) acrylic ester constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (also referred to as lauryl (meth) acrylate), tridecyl (meth) acrylate, dodecyl (meth) acrylate, and the like, Alkyl (meth) acrylates having a chain structure in which the alkyl group constituting the alkyl ester has 1 to 18 carbon atoms, such as tetradecyl (meth) acrylate (also referred to as myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (also referred to as palmityl (meth) acrylate), heptadecyl (meth) acrylate, and octadecyl (meth) acrylate (also referred to as stearyl (meth) acrylate);

cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate;

aralkyl (meth) acrylates such as benzyl (meth) acrylate;

cycloalkenyl (meth) acrylates such as dicyclopentenyl (meth) acrylate;

cycloalkenyloxyalkyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate;

(meth) acrylic acid imide;

glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate;

hydroxyl group-containing (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 substituted amino group-containing (meth) acrylates such as N-methylaminoethyl (meth) acrylate.

The "substituted amino group" refers to a group in which 1 or 2 hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom.

In the present specification, "(meth) acrylic acid" is a concept including "acrylic acid" and "methacrylic acid". The same applies to terms similar to those of (meth) acrylic acid, for example, "(meth) acrylate" is a concept including "acrylate" and "methyl acrylate", and "(meth) acryl" is a concept including "acryl" and "methacryl".

The acrylic resin may be composed of only one monomer, or two or more monomers, and when two or more monomers are used, the combination and ratio thereof may be arbitrarily selected.

The acrylic resin may have a functional group capable of bonding with other compounds, such as a vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group, and isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a crosslinking agent (F) described later, or may be directly bonded to another compound without via the crosslinking agent (F). The acrylic resin is bonded to another compound through the functional group, and thus the reliability of the package obtained using the first protective film forming sheet tends to be improved.

In the present invention, for example, as the polymer component (a), a thermoplastic resin other than polyvinyl acetal and an acrylic resin (hereinafter, it may be abbreviated as "thermoplastic resin") may be used alone without using polyvinyl acetal and an acrylic resin, or may be used together with polyvinyl acetal and an acrylic resin. By using the thermoplastic resin, the releasability of the first protective film from the first support sheet is improved, or the thermosetting resin film is made to easily follow the uneven surface of the adherend, and generation of voids and the like between the adherend and the thermosetting resin film is further suppressed.

The weight average molecular weight of the thermoplastic resin is preferably 1000 to 100000, and more preferably 3000 to 80000.

The glass transition temperature (Tg) of the thermoplastic resin is preferably-30 to 150 ℃, and more preferably-20 to 120 ℃.

Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutylene, polybutadiene, and polystyrene.

The thermoplastic resin contained in the resin layer forming composition and the thermosetting resin film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.

In the resin layer-forming composition, the proportion of the content of the polymer component (a) to the total content (total mass) of all components except the solvent (i.e., the content of the polymer component (a) of the thermosetting resin film) is preferably 5 to 85 mass%, more preferably 5 to 80 mass%, and may be, for example, any one of 5 to 70 mass%, 5 to 60 mass%, 5 to 50 mass%, 5 to 40 mass%, and 5 to 30 mass%, regardless of the type of the polymer component (a). However, the content of these components in the resin layer-forming composition is merely an example.

The polymer component (A) may be a thermosetting component (B). In the present invention, when the resin layer forming composition contains the above-mentioned components belonging to both the polymer component (a) and the thermosetting component (B), the resin layer forming composition is regarded as containing the polymer component (a) and the thermosetting component (B).

[ thermosetting component (B) ]

The thermosetting component (B) is a component for forming the hard first protective film by curing the thermosetting resin film.

The thermosetting component (B) contained in the resin layer forming composition and the thermosetting resin film may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

Examples of the thermosetting component (B) include epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, etc., and epoxy thermosetting resins are preferred.

(epoxy thermosetting resin)

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

The epoxy thermosetting resin contained in the resin layer forming composition and the thermosetting resin film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.

Epoxy resin (B1)

Examples of the epoxy resin (B1) include known epoxy resins, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol a diglycidyl ether and hydrogenated products thereof, o-cresol novolac epoxy resins, dicyclopentadiene epoxy resins, biphenyl epoxy resins, bisphenol a epoxy resins, bisphenol F epoxy resins, and epoxy resins having a phenylene skeleton.

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can be used. The compatibility of the epoxy resin having an unsaturated hydrocarbon group with the acrylic resin is higher than that of the epoxy resin having no unsaturated hydrocarbon group with the acrylic resin. Therefore, by using the epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the first protective film forming sheet is improved.

Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by converting a part of epoxy groups of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group.

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

The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethylene group (also referred to as a vinyl group), a 2-propenyl group (also referred to as an allyl group), a (meth) acryloyl group, and a (meth) acrylamide group, and an acryloyl group is preferable.

The weight average molecular weight of the epoxy resin (B1) is preferably 15000 or less, more preferably 10000 or less, and particularly preferably 5000 or less.

The lower limit of the weight average molecular weight of the epoxy resin (B1) is not particularly limited. Among them, the weight average molecular weight of the epoxy resin (B1) is preferably 300 or more, and more preferably 500 or more, from the viewpoint of curability of the thermosetting resin film and further improvement in strength and heat resistance of the first protective film.

The weight average molecular weight of the epoxy resin (B1) can be appropriately adjusted to fall within a range set by arbitrarily combining the above preferable lower limit and upper limit.

For example, the weight average molecular weight of the epoxy resin (B1) is preferably 300 to 15000, more preferably 300 to 10000, and particularly preferably 300 to 3000. The weight average molecular weight of the epoxy resin (B1) is preferably 500 to 15000, more preferably 500 to 10000, and particularly preferably 500 to 3000. However, these are only one example of a preferable weight average molecular weight of the epoxy resin (B1).

In the present specification, unless otherwise specified, "number average molecular weight" refers to a number average molecular weight expressed as a standard polystyrene conversion value measured by a Gel Permeation Chromatography (GPC) method.

The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000g/eq, more preferably 130 to 800 g/eq.

In the present specification, "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing 1 equivalent of an epoxy group, and can be measured according to the method of JIS K7236: 2001.

The epoxy resin (B1) is preferably liquid at room temperature (23 ℃) (in the present specification, this may be simply referred to as "liquid epoxy resin (B1)").

The epoxy resins (B1) may be used singly or in combination of two or more, and when two or more are used simultaneously, the combination and ratio thereof may be arbitrarily selected.

Heat-curing agent (B2)

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

Examples of the thermosetting agent (B2) include compounds having 2 or more functional groups reactive with an epoxy group in 1 molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, a group in which an acid group is anhydrified, and the like, and a phenolic hydroxyl group, an amino group, or a group in which an acid group is anhydrified is preferable, and a phenolic hydroxyl group or an amino group is more preferable.

Examples of the phenol curing agent having a phenolic hydroxyl group in the heat curing agent (B2) include polyfunctional phenol resins, bisphenols, novolak-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol resins.

As the amine-based curing agent having an amino group in the thermosetting agent (B2), dicyandiamide (which may be abbreviated as "DICY" in the present specification) and the like are exemplified.

The thermosetting agent (B2) may have an unsaturated hydrocarbon group.

Examples of the unsaturated hydrocarbon group-containing thermosetting agent (B2) include a compound in which a part of the hydroxyl groups of a phenol resin is substituted with an unsaturated hydrocarbon group-containing group, a compound in which an unsaturated hydrocarbon group-containing group is directly bonded to an aromatic ring of a phenol resin, and the like.

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

When a phenol-based curing agent is used as the thermal curing agent (B2), the thermal curing agent (B2) is preferably high in softening point or glass transition temperature in order to improve the peelability of the first protective film from the first support sheet.

Among the thermosetting agents (B2), the number average molecular weight of the resin component such as a polyfunctional phenol resin, a novolak-type phenol resin, a dicyclopentadiene-type phenol resin, or an aralkyl-type phenol resin is preferably 300 to 30000, more preferably 400 to 10000, and particularly preferably 500 to 3000.

The molecular weight of the non-resin component such as bisphenol and dicyandiamide in the thermosetting agent (B2) is not particularly limited, and is preferably 60 to 500, for example.

The heat-curing agent (B2) may be used alone or in combination of two or more, and when two or more are used simultaneously, the combination and ratio thereof may be arbitrarily selected.

In the resin layer forming composition and the thermosetting resin film, the content of the thermosetting agent (B2) is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass, and may be, for example, any one of 1 to 150 parts by mass, 1 to 100 parts by mass, 1 to 75 parts by mass, 1 to 50 parts by mass, and 1 to 30 parts by mass, based on 100 parts by mass of the content of the epoxy resin (B1). By setting the content of the thermosetting agent (B2) to the lower limit or more, it becomes easier to cure the thermosetting resin film. Further, by setting the content of the thermosetting agent (B2) to the upper limit or less, the moisture absorption rate of the thermosetting resin film is reduced, and the reliability of the package obtained using the first protective film is further improved.

In the resin layer-forming composition and the thermosetting resin film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is preferably 50 to 1000 parts by mass, more preferably 60 to 950 parts by mass, and particularly preferably 70 to 900 parts by mass, relative to 100 parts by mass of the content of the polymer component (a). When the content of the thermosetting component (B) is in the above range, the adhesion between the first protective film and the first support sheet is suppressed, and the peelability of the first support sheet is improved.

[ curing Accelerator (C) ]

The composition for forming a resin layer and the thermosetting resin film may contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing speed of the resin layer-forming composition.

Examples of the preferable curing accelerator (C) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole (i.e., imidazoles in which at least 1 hydrogen atom is replaced with a group other than a hydrogen atom); organophosphines (i.e., phosphines in which at least 1 hydrogen atom is substituted with an organic group), such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylboron ester and triphenylphosphine tetraphenylboron ester.

The curing accelerator (C) contained in the resin layer forming composition and the thermosetting resin film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof 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, based on 100 parts by mass of the content of the thermosetting component (B) in the resin layer-forming composition and the thermosetting resin film. By setting the content of the curing accelerator (C) to the lower limit or more, the effect of using the curing accelerator (C) can be more remarkably obtained. Further, by setting the content of the curing accelerator (C) to the upper limit or less, for example, the effect of suppressing the occurrence of segregation of the highly polar curing accelerator (C) in the thermosetting resin film by moving to the side of the adhesive interface with the adherend under high temperature and high humidity conditions becomes high, and the reliability of the package obtained using the first protective film forming sheet is further improved.

[ Filler (D) ]

The composition for forming a resin layer and the thermosetting resin film may contain a filler (D). By containing the filler (D) in the thermosetting resin film, it becomes easy to adjust the thermal expansion coefficient of the first protective film obtained by curing the thermosetting resin film. By optimizing the thermal expansion coefficient of the object to be formed with the first protection film, the reliability of the package obtained using the first protection film forming sheet is further improved. Further, by containing the filler (D) in the thermosetting resin film, the moisture absorption rate of the first protective film can be reduced or the heat release property can be improved.

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

Examples of preferable inorganic fillers include powders of silica, alumina, talc, calcium carbonate, titanium white, iron oxide, silicon carbide, boron nitride, and the like; beads obtained by spheroidizing these inorganic fillers; surface modifications of these inorganic filler materials; single crystal fibers of these inorganic filler materials; glass fibers, and the like.

Among them, the inorganic filler is preferably silica or alumina.

The filler (D) contained in the resin layer forming composition and the thermosetting resin film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.

The average particle diameter of the filler (D) is preferably 1 μm or less, more preferably 0.5 μm or less, and particularly preferably 0.1 μm or less.

In the present specification, unless otherwise specified, the "average particle diameter" refers to the particle diameter (D) at which the cumulative value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method is calculated₅₀) The value of (c).

The lower limit of the average particle diameter of the filler (D) is not particularly limited. For example, the average particle diameter of the filler (D) is preferably 0.01 μm or more, from the point where the filler (D) is more easily obtained. As one side, the average particle diameter of the filler (D) is preferably 0.01 μm or more and 1 μm or less, more preferably 0.01 μm or more and 0.5 μm or less, and particularly preferably 0.01 μm or more and 0.1 μm or less.

When the filler (D) is used, the content of the filler (D) in the resin layer-forming composition is preferably 3 to 60% by mass, and more preferably 3 to 55% by mass, relative to the total content (total mass) of all the components except the solvent (i.e., the content of the filler (D) in the thermosetting resin film).

[ coupling agent (E) ]

The resin layer forming composition and the thermosetting resin film may contain a coupling agent (E). By using a coupling agent having a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (E), the adhesiveness and adhesion of the thermosetting resin film to an adherend can be improved. Further, the first protective film obtained by curing the thermosetting resin film using the coupling agent (E) is improved in water resistance without impairing heat resistance.

The coupling agent (E) is preferably a compound having a functional group capable of reacting with a functional group of the polymer component (a), the thermosetting component (B), or the like, and more preferably a silane coupling agent.

Examples of the preferable silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, and the like, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane and the like.

The coupling agent (E) contained in the resin layer forming composition and the thermosetting resin film may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When the coupling agent (E) is used, the content of the coupling agent (E) is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the total content of the polymer component (a) and the thermosetting component (B) in the resin layer forming composition and the thermosetting resin film.

When the content of the coupling agent (E) is not less than the lower limit, the effects of using the coupling agent (E) such as improvement of dispersibility of the filler (D) in the resin and improvement of adhesion between the thermosetting resin film and the adherend can be more remarkably obtained. Further, by setting the content of the coupling agent (E) to the upper limit value or less, the occurrence of degassing is further suppressed.

[ crosslinking agent (F) ]

When the polymer component (a) is a component having a functional group such as a vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group, or isocyanate group which can be bonded to another compound, such as the acrylic resin described above, the resin layer forming composition and the thermosetting resin film may contain a crosslinking agent (F). The crosslinking agent (F) is a component for bonding and crosslinking the functional group in the polymer component (a) with another compound, and by performing crosslinking in this way, the initial adhesive force and cohesive force of the thermosetting resin film can be adjusted.

Examples of the crosslinking agent (F) include an organic polyisocyanate compound, an organic polyimine compound, a metal chelate crosslinking agent (i.e., a crosslinking agent having a metal chelate structure), an aziridine crosslinking agent (i.e., a crosslinking agent having an aziridine group), and the like.

Examples of the organic polyisocyanate compound include an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, and an alicyclic polyisocyanate compound (hereinafter, these compounds are collectively abbreviated as "aromatic polyisocyanate compound and the like"); trimers, isocyanurate bodies and adducts of the aromatic polyisocyanate compounds and the like; and isocyanate-terminated urethane prepolymers obtained by reacting the aromatic polyisocyanate compound and the like with a polyol compound. The "adduct" refers to a reactant of the aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound with a low-molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. As examples of the adduct, xylylene diisocyanate adduct of trimethylolpropane described later and the like can be cited. The "isocyanate-terminated urethane prepolymer" refers to a prepolymer having a urethane bond and an isocyanate group at the terminal of the molecule.

More specific examples of the organic polyisocyanate compound include 2, 4-tolylene diisocyanate; 2, 6-toluene diisocyanate; 1, 3-xylylene diisocyanate; 1, 4-xylene diisocyanate; diphenylmethane-4, 4' -diisocyanate; diphenylmethane-2, 4' -diisocyanate; 3-methyl diphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4, 4' -diisocyanate; dicyclohexylmethane-2, 4' -diisocyanate; a compound obtained by adding one or more of toluene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate to all or a part of the hydroxyl groups of a polyhydric alcohol such as trimethylolpropane; lysine diisocyanate, and the like.

Examples of the organic polyimine compound include N, N ' -diphenylmethane-4, 4 ' -bis (1-aziridinecarboxamide), trimethylolpropane-tri- β -aziridinylpropionate, tetramethylolmethane-tri- β -aziridinylpropionate, and N, N ' -toluene-2, 4-bis (1-aziridinecarboxamide) triethylenemelamine.

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

The crosslinking agent (F) contained in the resin layer forming composition and the thermosetting resin film may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When the crosslinking agent (F) is used, the content of the crosslinking agent (F) in the resin layer-forming composition is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the polymer component (a). By setting the content of the crosslinking agent (F) to the lower limit or more, the effect of using the crosslinking agent (F) can be more remarkably obtained. Further, by making the content of the crosslinking agent (F) the upper limit value or less, the excessive use of the crosslinking agent (F) is suppressed.

[ other ingredients ]

The resin layer forming composition and the thermosetting resin film may contain other components than the polymer component (a), the thermosetting component (B), the curing accelerator (C), the filler (D), the coupling agent (E) and the crosslinking agent (F) as long as the effects of the present invention are not impaired.

Examples of the other components include an energy ray-curable resin, a photopolymerization initiator, a colorant, and a general-purpose additive. The general-purpose additive is a known additive, can be arbitrarily selected according to the purpose, and is not particularly limited, and preferable components include, for example, a plasticizer, an antistatic agent, an antioxidant, a colorant (dye, pigment), a gettering agent (gelling agent), and the like.

The other component contained in the resin layer forming composition and the thermosetting resin film may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

The content of the other components in the resin layer forming composition and the thermosetting resin film is not particularly limited, and may be appropriately selected according to the purpose.

The resin layer forming composition and the thermosetting resin film contain a polymer component (a) and a thermosetting component (B), preferably contain polyvinyl acetal as the polymer component (a) and a liquid resin as the epoxy resin (B1), and may further preferably contain a curing accelerator (C) and a filler (D) in addition to these components. In this case, the filler (D) preferably has the above-mentioned average particle diameter.

[ solvent ]

The resin layer-forming composition preferably further contains a solvent. The composition for forming a resin layer containing a solvent has good workability.

The solvent is not particularly limited, but preferable examples thereof include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (also referred to as 2-methylpropan-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (i.e., compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone, and the like.

The resin layer-forming composition may contain only one kind of solvent, or two or more kinds of solvents, and when two or more kinds of solvents are contained, the combination and ratio of these solvents can be arbitrarily selected.

The solvent contained in the resin layer-forming composition is preferably methyl ethyl ketone or the like, since the components contained in the resin layer-forming composition can be mixed more uniformly.

The content of the solvent in the resin layer-forming composition is not particularly limited, and may be appropriately selected depending on the kind of the component other than the solvent, for example.

Preparation method of composition for Forming thermosetting resin film

The composition for forming a thermosetting resin film such as a composition for forming a resin layer can be obtained by blending the components constituting the composition.

The order of addition of the components in blending is not particularly limited, and two or more components may be added simultaneously.

When a solvent is used, the solvent may be mixed with any of the components other than the solvent and the mixture may be diluted in advance, or the solvent may be mixed with any of the components other than the solvent without diluting them in advance.

In the blending, the method for mixing the components is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirrer, a stirring blade, or the like; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves, and the like.

The temperature and time for adding and mixing the components are not particularly limited and may be appropriately adjusted as long as the components are not deteriorated, but the temperature is preferably 15 to 30 ℃.

Very good first supporting sheet

In the first protective film forming sheet 1, a known support sheet can be used as the first support sheet 101. For example, the first support sheet 101 includes a first base material 11 and a cushion layer 13 formed on the first base material 11. That is, the first protective film forming sheet 1 is configured by sequentially laminating the first base material 11, the buffer layer 13, and the thermosetting resin film 12 along the thickness direction thereof.

Very good first base material

The first base material is in the form of a sheet or a film, and examples of the constituent material include various resins.

Examples of the resin include polyethylene such as low density polyethylene (which may be abbreviated as LDPE), linear low density polyethylene (which may be abbreviated as LLDPE), and high density polyethylene (which may be abbreviated as HDPE); polyolefins other than polyethylene, such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resins; ethylene copolymers (copolymers obtained using ethylene as a monomer) such as ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid ester copolymers, and ethylene-norbornene copolymers; vinyl chloride-based resins (resins obtained by using vinyl chloride as a monomer) such as polyvinyl chloride and vinyl chloride copolymers; polystyrene; a polycycloolefin; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2, 6-naphthalenedicarboxylate, and wholly aromatic polyesters having an aromatic ring group in all the structural units; copolymers of two or more of said polyesters; poly (meth) acrylates; a polyurethane; a urethane acrylate; a polyimide; a polyamide; a polycarbonate; a fluororesin; a polyacetal; modified polyphenylene ether; polyphenylene sulfide; polysulfones; polyether ketones, and the like.

Examples of the resin include a polymer alloy such as a mixture of the polyester and a resin other than the polyester. The polymer alloy of the polyester and the resin other than the polyester is preferably in a small amount.

Examples of the resin include crosslinked resins obtained by crosslinking one or two or more of the above-exemplified resins; modified resins such as ionomers using one or more of the above-exemplified resins.

The resin constituting the first base material may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

The first substrate may be composed of 1 layer (single layer) or a plurality of layers of 2 or more, and when composed of a plurality of layers, these plurality of layers may be the same or different from each other, and the combination of these plurality of layers is not particularly limited.

In the present specification, the phrase "a plurality of layers may be the same or different from each other" means "all the layers may be the same or different from each other, or only a part of the layers may be the same", and "a plurality of layers are different from each other" means "at least one of the constituent materials and the thicknesses of the respective layers are different from each other", in addition to the case of not being limited to the first base material.

The thickness of the first base material is preferably 5 to 1000 μm, more preferably 10 to 500 μm, still more preferably 15 to 300 μm, and particularly preferably 20 to 150 μm.

Here, the "thickness of the first substrate" refers to the thickness of the entire first substrate, and for example, the thickness of the first substrate formed of a plurality of layers refers to the total thickness of all layers constituting the first substrate.

The first base material is preferably a material having high accuracy of thickness, that is, a material in which thickness unevenness is suppressed regardless of the position. Among the above-mentioned constituent materials, examples of the material that can be used to form the first base material having a high thickness accuracy include polyethylene, polyolefin other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymer.

The first base material may contain known various additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent material such as the resin.

The first substrate may be transparent or opaque, and may be colored according to the purpose, or may be vapor-deposited with another layer.

When the thermosetting resin film is energy ray-curable, the first substrate is preferably a material that transmits energy rays.

The first substrate can be manufactured by a known method. For example, the first base material containing a resin can be produced by molding a resin composition containing the resin.

Very good peeling film

As the release film, a film known in the art can be used.

Examples of the preferable release film include a release film obtained by subjecting at least one surface of a resin film such as polyethylene terephthalate to a release treatment such as a silicone treatment; a release film having a release surface made of polyolefin on at least one surface of the film.

The thickness of the release film is preferably the same as the thickness of the first substrate.

Very good buffer layer

The buffer layer 13 has a buffering action against a force applied to the buffer layer 13 and a layer adjacent to the buffer layer 13. Here, as "a layer adjacent to the cushion layer", the thermosetting resin film 12 is shown.

The buffer layer 13 is sheet-shaped or film-shaped, and is preferably energy ray-curable. The energy ray-curable buffer layer 13 is more easily peeled from the thermosetting resin film 12 described later by energy ray curing.

Examples of the material constituting the cushion layer 13 include various adhesive resins. Examples of the adhesive resin include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, and polycarbonates, and acrylic resins are preferred. When the buffer layer 13 is energy ray-curable, various components necessary for energy ray curing can be used as the constituent material.

In the present invention, the "adhesive resin" is a concept including both a resin having adhesiveness and a resin having adhesiveness, and includes, for example, not only a resin having adhesiveness of the resin itself but also a resin exhibiting adhesiveness by being used together with other components such as an additive or a resin exhibiting adhesiveness due to the presence of trigger inducement such as heat or water.

The buffer layer 13 may be a single layer (single layer) or a plurality of layers of 2 or more, and in the case of a plurality of layers, these plurality of layers may be the same or different from each other, and the combination of these plurality of layers is not particularly limited.

The thickness of the buffer layer 13 is preferably 30 to 500 μm.

Here, the "thickness of the buffer layer 13" refers to the thickness of the entire buffer layer 13, and for example, the thickness of the buffer layer 13 formed of a plurality of layers refers to the total thickness of all the layers constituting the buffer layer 13.

Adhesive resin composition

The cushion layer 13 is formed of an adhesive resin composition containing an adhesive resin. For example, the adhesive resin composition is applied to the surface to be formed of the cushion layer 13, and dried as necessary, thereby forming the cushion layer 13 on the target portion.

The adhesive composition may be applied by a known method, and examples thereof include a method using various coating machines such as a knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a curtain coater, a die coater, a knife coater, a screen coater, a meyer bar coater, and a kiss coater.

The drying conditions of the adhesive resin composition are not particularly limited, but the adhesive resin composition containing a solvent described later is preferably dried by heating. The adhesive resin composition containing a solvent is preferably dried at 70 to 130 ℃ for 10 seconds to 5 minutes, for example.

When the buffer layer 13 is energy ray-curable, examples of the energy ray-curable adhesive resin composition containing an energy ray-curable adhesive, i.e., the energy ray-curable adhesive resin composition, include: an adhesive resin composition (I-1) comprising a non-energy-ray-curable adhesive resin (I-1a) (hereinafter, this may be abbreviated as "adhesive resin (I-1 a)") and an energy-ray-curable compound; an adhesive resin composition (I-2) comprising an energy ray-curable adhesive resin (I-2a) having an unsaturated group introduced into a side chain of a non-energy ray-curable adhesive resin (I-1a) (hereinafter, this may be abbreviated as "adhesive resin (I-2 a)"); an adhesive resin composition (I-3) comprising the adhesive resin (I-2a) and an energy ray-curable low-molecular-weight compound.

Examples of the adhesive resin composition include an energy ray-curable adhesive resin composition and a non-energy ray-curable adhesive resin composition.

Examples of the non-energy ray-curable adhesive resin composition include an adhesive resin composition (I-4) containing a non-energy ray-curable adhesive resin (I-1a) such as an acrylic resin, a urethane resin, a rubber resin, a silicone resin, an epoxy resin, a polyvinyl ether, a polycarbonate, or an ester resin, and preferably an acrylic resin.

Process for producing adhesive resin composition

The adhesive resin compositions such as the adhesive resin compositions (I-1) to (I-4) can be obtained by blending the adhesive resin with components constituting the adhesive resin composition such as components other than the adhesive resin, if necessary.

When the solvent is used, the solvent may be used by mixing the solvent with any of the blend components other than the solvent and diluting the blend components in advance, or the solvent may be used by mixing the solvent with any of the blend components other than the solvent without diluting the blend components in advance.

In the blending, the method for mixing the components is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves, and the like.

Manufacturing method of first protective film forming sheet

The first protective film forming sheet can be manufactured by sequentially laminating the respective layers so that the respective layers have corresponding positional relationships. The formation method of each layer is as described above.

For example, a first protective film forming sheet in which a buffer layer and a thermosetting resin film are sequentially laminated in the thickness direction thereof on a first base material can be manufactured by the following method. That is, the buffer layer is laminated on the first substrate by extrusion molding the adhesive resin composition for forming the buffer layer on the first substrate. The thermosetting resin film is laminated by applying the above-mentioned composition for forming a thermosetting resin film on the release-treated surface of the release film and drying it as necessary. Next, the thermosetting resin film on the release film is laminated to the buffer layer on the first substrate, thereby obtaining a first protective film forming sheet in which the buffer layer, the thermosetting resin film, and the release film are sequentially laminated on the first substrate. The release film may be removed when the first protective film-forming sheet is used.

The first protective film forming sheet including the other layers than the above-described respective layers can be manufactured by appropriately adding one or both of the step of forming the other layers and the step of laminating the other layers in the above-described manufacturing method so that the lamination position of the other layers is an appropriate position.

For example, a first protective film-forming sheet in which an adhesion layer, a cushion layer, and a thermosetting resin film are sequentially laminated in the thickness direction thereof on a first base material can be produced by the following method. That is, the composition for forming the adhesive layer and the adhesive resin composition for forming the buffer layer are co-extruded on the first base material, and the adhesive layer and the buffer layer are sequentially laminated on the first base material. Then, a thermosetting resin film was additionally laminated on the release film by the same method as described above. Next, the thermosetting resin film on the release film is bonded to the first base material and the buffer layer on the adhesion layer, thereby obtaining a first protective film-forming sheet in which the adhesion layer, the buffer layer, the thermosetting resin film, and the release film are sequentially stacked on the first base material. The release film on the thermosetting resin film may be removed when the first protective film-forming sheet is used.

Industrial applicability

The present invention is industrially useful because it can provide a method for manufacturing a semiconductor chip, which can simultaneously remove the residue of the first protective film on the top of the head of the bump and singulate the semiconductor wafer, and which has excellent productivity.

Description of the reference numerals

1: a first protective film forming sheet; 11: a first substrate; 12: a thermosetting resin film; 12 a: a first side of a thermosetting resin film; 12': a first protective film; 13: a buffer layer; 14: cutting the slices; 101: a first support sheet; 9: a semiconductor wafer; 9 a: a first surface (bump formation surface) of the semiconductor wafer; 9 b: a second side (back side) of the semiconductor wafer; 91: a bump; 91 a: the surface of the bump; 910: the top of the head of the bump.

Claims

1. A method of manufacturing a semiconductor chip with a first protective film, the method comprising:

performing half-cut dicing on the semiconductor wafer on which the first protective film is formed from one side of the first surface; and

2. A method of manufacturing a semiconductor chip with a first protective film, the method comprising:

peeling the first support sheet from the thermosetting resin film;

3. The method for manufacturing a semiconductor chip with a first protective film according to claim 1 or 2, wherein, for the semiconductor wafer half-cut, a remaining thickness a (μm) of a half-cut portion of the semiconductor wafer, a thickness B (μm) of the first protective film on the first surface of the semiconductor wafer, a thickness C (μm) of the first protective film on a top of a head of the bump, an etching speed a (μm/min) of the semiconductor wafer based on plasma irradiation, an etching speed B (μm/min) of the first protective film based on plasma irradiation, and a time t (min) of plasma irradiation satisfy the relationship of the following expression (1), expression (2), and expression (3):

A<at···(1)；

B>bt···(2)；

C<bt···(3)。

4. a method of manufacturing a semiconductor chip with a first protective film, the method comprising:

5. A method of manufacturing a semiconductor chip with a first protective film, the method comprising:

peeling the first support sheet from the thermosetting resin film;

6. The method for manufacturing a semiconductor chip with a first protective film according to claim 4 or 5, wherein, with respect to the semiconductor wafer half-cut, a remaining thickness A (μm) of a half-cut portion of the semiconductor wafer, a thickness D (μm) of the thermosetting resin film on the first surface of the semiconductor wafer, a thickness E (μm) of the thermosetting resin film on a top of a head of the bump, an etching rate a (μm/min) of the semiconductor wafer based on plasma irradiation, an etching rate D (μm/min) of the thermosetting resin film based on plasma irradiation, and a time t (min) of plasma irradiation satisfy the relationship of the following expression (1), expression (4), and expression (5):

A<at···(1)；

D>dt···(4)；

E<dt···(5)。