TWI825080B - Method for manufacturing semiconductor chip - Google Patents

Abstract

A method for manufacturing semiconductor chip with a first protective film including: applying a thermosetting resin film to a fist surface on a bump side of a semiconductor wafer having a bump, forming the first protective film on the first surface of the semiconductor wafer by thermosetting the thermosetting resin film, half-cut dicing the semiconductor wafer form the side of the first surface on which the first protective film is formed, and removing the residue of the first protective film on the top of the bump and the singulating the semiconductor wafer by irradiating on the side of the first surface of the half-cut diced semiconductor wafer with plasma.

Description

Semiconductor wafer manufacturing method

The invention relates to a method for manufacturing a semiconductor wafer. Specifically, it relates to a method of manufacturing a semiconductor wafer provided with a first protective film that protects a bump formation surface. This application claims priority based on Japanese Patent Application No. 2018-069682 filed in Japan on March 30, 2018, the content of which is incorporated herein by reference.

Traditionally, when multi-pin LSI packages used in MPUs, gate arrays, etc. are mounted on printed wiring boards, flip-chip mounting methods are used, which use eutectic solder and high-temperature solder to form the connection pads. Protruding electrodes made of gold, gold, etc. (hereinafter referred to as "bumps" in this specification) are used as semiconductor wafers, and these bumps are connected to the chip mounting substrate by a so-called face down method. The corresponding terminal portions on the terminals face to face, contact, and are melted/diffused bonded.

The semiconductor wafer used in this mounting method can be made into a single unit by, for example, grinding and cutting the surface of the semiconductor wafer with bumps formed on the circuit surface opposite to the circuit surface (in other words, the bump formation surface). Obtained in pieces. In the process of obtaining such a semiconductor wafer, usually, in order to protect the bump formation surface and the bumps of the semiconductor wafer, a curable resin film is attached to the bump formation surface and the film is hardened, whereby the bumps are A protective film (hereinafter referred to as "first protective film" in this specification) is formed on the block formation surface.

The curable resin film is usually attached to the bump formation surface of the semiconductor wafer in a state softened by heating. In this way, the curable resin film spreads between the bumps to cover the bumps of the semiconductor wafer, and is in close contact with the bump formation surfaces. At the same time, it covers the surfaces of the bumps, especially the vicinity of the bump formation surfaces. surface of the part and embed the bumps. Thereafter, the curable resin film is further cured to cover the bump formation surface of the semiconductor wafer and the surface of the vicinity of the bump formation surface of the bump, thereby becoming a protective film that protects these areas. Furthermore, the semiconductor wafer is solidified into a semiconductor wafer, and finally a semiconductor wafer having a protective film on the bump formation surface (referred to as a "semiconductor wafer with a first protective film" in this specification) is obtained.

Such a semiconductor wafer with a protective film is mounted on a substrate to form a semiconductor package, and the semiconductor package is further used to construct a desired semiconductor device. In order for a semiconductor package and a semiconductor device to function properly, the electrical connection between the bumps of the semiconductor wafer with the protective film and the circuit on the substrate must not be hindered. However, the curable resin film may remain on the top of the bump. If the curable resin film remaining on the top of the bump is cured in the same manner as the curable resin film in other areas, it will become a cured product with the same composition as the protective film (in this specification, it is called "protective film residue"). "thing"). In this way, since the top of the bump is the electrical connection area between the bump and the circuit on the substrate, if there is a large amount of protective film residue, the connection between the bump of the semiconductor wafer with the protective film and the circuit on the substrate will The electrical connection is hindered, resulting in reduced electrical characteristics during reliability testing. That is, in the stage before being mounted on a substrate of a semiconductor wafer with a protective film, it is required that almost no residue of the protective film exists on the top of the bumps of the semiconductor wafer with a protective film.

As a method of removing a protective film on the top of a bump, a method of manufacturing a semiconductor device that performs plasma treatment is disclosed (see Patent Document 1). The semiconductor wafer can be obtained by applying plasma treatment to the protective film on the bump formation surface, removing the resin film covering the top of the bump, and then cutting it into individual pieces with a knife. Since the top of the bump is exposed, the semiconductor wafer can be obtained. There is an electrical connection between the bump and the electrode of the substrate, and a semiconductor device with good connection reliability can be manufactured efficiently.

In addition, the area other than the dicing line of the semiconductor wafer is covered with a barrier layer in advance, and the semiconductor wafer is etched and divided by plasma irradiation on the portion not covered by the barrier film and corresponding to the dicing line ( Patent Document 2, etc.). [Prior technical literature] [Patent Document]

Patent Document 1: International Publication No. 2016/194431 Patent Document 2: Japanese Patent Application Publication No. 2004-193305

However, the cutting method disclosed in Patent Document 1 requires an additional plasma treatment step to remove the resin film on the top of the bump before the cutting step, which is difficult from the viewpoint of productivity. In addition, since the cutting method disclosed in Patent Document 2 requires additional coating, exposure, and development processes of the barrier film before the cutting step, it is difficult from the viewpoint of productivity.

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

The present invention includes the following aspects.

[1] A method of manufacturing a semiconductor wafer with a first protective film, comprising: attaching a thermosetting resin film to a first surface of a semiconductor wafer having bumps on the bump side; and applying the thermosetting resin to The film is thermally cured to form a first protective film on the first surface of the semiconductor wafer; half-cut dicing is performed from the side of the first surface of the semiconductor wafer on which the first protective film is formed; and by performing plasma irradiation on the side of the first surface of the half-cut semiconductor wafer, while removing the residue of the first protective film on the top of the bump, the semiconductor wafer is singulated. change.

[2] A method of manufacturing a semiconductor wafer with a first protective film, including: using a first protective film forming sheet including a first support sheet and a thermosetting resin film provided on the first support sheet The thermosetting resin film of the material is attached to the first surface of the bump side of the semiconductor wafer having the bumps; the first supporting sheet is peeled off from the thermosetting resin film; the thermosetting resin film is The resin film is thermally cured to form a first protective film on the first surface of the semiconductor wafer; half-cutting is performed from the side of the first surface of the semiconductor wafer; and by half-cutting the semiconductor wafer Plasma irradiation is performed on the first surface side to remove residues of the first protective film on the top portions of the bumps and at the same time, the semiconductor wafer is singulated.

[3] The method for manufacturing a semiconductor wafer with a first protective film as described in [1] or [2], wherein, with respect to the half-cut semiconductor wafer, the remaining thickness of the half-cut portion of the semiconductor wafer A (μm), the thickness B (μm) of the first protective film on the first surface of the above-mentioned semiconductor wafer, the thickness C (μm) of the first protective film on the top of the bump, by plasma The etching rate a (μm/min) of the semiconductor wafer irradiated, the etching rate b (μm/min) of the first protective film irradiated by plasma, and the time t (min) of plasma irradiation satisfy the following formula (1), equation (2) and equation (3), A>at…(1) B>bt…(2) C>bt…(3).

[4] A method of manufacturing a semiconductor wafer with a first protective film, including the following steps: attaching a thermosetting resin film to the first surface of the semiconductor wafer having bumps on the bump side; Perform half-cut cutting from the side of the first surface of the semiconductor wafer to which the thermosetting resin film is attached; By performing plasma irradiation on the side of the half-cut first surface of the semiconductor wafer, the thermosetting resin film on the top of the bump is removed and the semiconductor wafer is diced; and The thermosetting resin film attached to the singulated semiconductor wafer is thermally cured to form a first protective film on the first surface of the semiconductor wafer. [5] A method of manufacturing a semiconductor wafer with a first protective film, including the following steps: The thermosetting resin film including the first supporting sheet and the thermosetting resin film provided on the first supporting sheet and the first protective film forming sheet are attached to a semiconductor wafer having bumps. The first surface on the side of the above-mentioned bump; Peeling the first support sheet from the thermosetting resin film; performing half-cut cutting from the side of the first surface of the semiconductor wafer to which the thermosetting resin film is attached; By performing plasma irradiation on the side of the half-cut first surface of the semiconductor wafer, the thermosetting resin film on the top of the bump is removed and the semiconductor wafer is diced into individual pieces; The thermosetting resin film attached to the singulated semiconductor wafer is thermally cured to form a first protective film on the first surface of the semiconductor wafer. [6] The method of manufacturing a semiconductor wafer with a first protective film as described in [4] or [5], wherein, with respect to the half-cut semiconductor wafer, the remaining thickness of the half-cut portion of the semiconductor wafer A (μm), the thickness D (μm) of the thermosetting resin film on the first surface of the semiconductor wafer, the thickness E (μm) of the thermosetting resin film on the top of the bump, by The etching rate a (μm/min) of the semiconductor wafer by plasma irradiation, the etching rate d (μm/min) of the thermosetting resin film by plasma irradiation, and the time t (min) of plasma irradiation satisfy that The relationship between the following formula (1), formula (4) and formula (5), A>at…(1) D>dt…(4) E>dt…(5).

According to the present invention, by cutting the semiconductor wafer in half and then irradiating it with plasma, not only can it be cut by plasma irradiation without covering the barrier film, but also the residue of the first protective film on the top of the bump can be removed at the same time. Semiconductor wafers are diced, so productivity is good. In addition, since plasma irradiation is performed after half-cut cutting, the occurrence of edge chipping can be reduced and the strength of the wafer can be improved.

>>Manufacturing method of semiconductor wafer with first protective film>> >First Embodiment> 1 and 2 are schematic diagrams illustrating a first embodiment of a method for manufacturing a semiconductor wafer with a first protective film according to the present invention. In addition, in the drawings used in the following description, in order to make it easier to understand the characteristics of the present invention and for convenience, main parts may be enlarged in some cases, and the dimensional ratios of each constituent element may not be the same as the actual ones.

The method for manufacturing a semiconductor wafer with a first protective film according to the first embodiment includes: The thermosetting resin film of the first protective film forming sheet 1 ( FIG. 1( a )) including the first supporting sheet 101 and the thermosetting resin film 12 provided on the first supporting sheet 101 12 is attached to the first surface 9a (Fig. 1(c)) of the semiconductor wafer 9 (Fig. 1(b)) having the bump 91 on the bump 91 side; Grinding the second surface 9b on the opposite side to the first surface 9a of the semiconductor wafer 9 (Fig. 1(d)); A dicing tape 14 is attached to the ground second surface 9b of the semiconductor wafer 9 (Fig. 1(e)); Peel the first support sheet 101 from the thermosetting resin film 12 (Fig. 2(f)); The thermosetting resin film 12 is thermally cured to form a first protective film 12' on the first surface of the semiconductor wafer 9 (Fig. 2(g)); The above-mentioned semiconductor wafer 9 is cut in half from the side of the above-mentioned first surface (Fig. 2(h)); Plasma irradiation is performed on the half-cut first surface side of the semiconductor wafer 9 to remove the residues of the first protective film 12' on the top portions 910 of the bumps 91 and at the same time, the semiconductor wafer 9 is cut into pieces. Fragmentation (Figure 2(i)).

First, as shown in FIGS. 1(a) and 1(b) , the first protective film forming sheet 1 with its thermosetting resin film 12 and the first surface 9a (on the bump side) of the semiconductor wafer 9 are (referred to as "bump forming surfaces") are arranged in opposite directions.

The first protective film forming sheet 1 includes the thermosetting resin film 12 on the first support sheet 101 . The first support sheet 101 is preferably provided with the buffer layer 13 on the first base material 11 . That is, the first protective film forming sheet according to the present invention includes, as one aspect thereof, a first support sheet and a thermosetting resin film provided on the first support sheet. As another aspect, the first protective film forming sheet according to 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. . Details of the first protective film forming sheet 1 are as follows.

The height of the bumps 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 addition, in this specification, the "height of the bump" refers to the height of the bump from the bump formation surface to the highest position (that is, from the bump formation surface of the semiconductor wafer) the distance in the vertical direction 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 addition, in this specification, the "width of the bump" refers to the distance between two different points on the surface of the bump when the plan view of the bump is viewed downward from the vertical direction facing the bump formation surface. The maximum value of the line length obtained by connecting straight lines.

The distance between adjacent bumps 91 is not particularly limited, but is preferably 100~350 μm, more preferably 130~300 μm, and particularly preferably 160~250 μm. In addition, in this specification, the "distance between adjacent bumps" refers to the minimum value of the distance between the surfaces of adjacent bumps.

The thickness A ₀ of the semiconductor wafer is not particularly limited, but is preferably 50 to 200 μm, more preferably 65 to 180 μm, and particularly preferably 80 to 150 μm. In addition, in this specification, the "thickness A ₀ of the semiconductor wafer" refers to the thickness of the semiconductor wafer, especially the semiconductor wafer after grinding. In this specification, unless otherwise specified, "thickness" refers to the average value of the values measured by a constant pressure thickness measuring device at 10 randomly selected locations.

Next, the thermosetting resin film 12 is brought into contact with the bumps 91 on the semiconductor wafer 9 , and the first protective film forming sheet 1 is pressed against the semiconductor wafer 9 . In this way, the first surface 12a of the thermosetting resin film 12 is pressed against the surface 91a of the bump 91 and the first surface 9a of the semiconductor wafer 9 in sequence. At this time, by heating the thermosetting resin film 12, the thermosetting resin film 12 softens, spreads between the bumps 91 to cover the bumps 91, and is in close contact with the first surface 9a while covering the bumps 91. The surface 91 a , particularly the surface 91 a of the semiconductor wafer 9 near the first surface 9 a , embeds the bumps 91 .

As a method of press-bonding the first protective film-shaped sheet 1 to the semiconductor wafer 9 , a conventional method of press-bonding various sheets to an object, such as a method using a roller, can be applied.

The heating temperature of the first protective film forming sheet 1 when being pressed onto the semiconductor wafer 9 is sufficient as long as the curing of the thermosetting resin film 12 is completed or does not proceed excessively, and is 80 to 100℃ is better, and 85~95℃ is better.

The pressure when pressing the first protective film forming sheet 1 onto the semiconductor wafer 9 is not particularly limited, but is preferably 0.1 to 1.5 MPa, and more preferably 0.3 to 1 MPa.

As described above, when the first protective film forming sheet 1 is pressed onto the semiconductor wafer 9 , the thermosetting resin film 12 in the first protective film forming sheet 1 receives pressure from the bumps 91 , and initially, The first surface 12a of the thermosetting resin film 12 is deformed into a concave shape. According to the above, the first protective film forming sheet 1 is bonded to the first surface 9 a of the semiconductor wafer 9 via its thermosetting resin film 12 ( FIG. 1( c )).

Next, if necessary, the second surface 9b (that is, the back surface) opposite to the bump formation surface of the semiconductor wafer 9 is ground (Fig. 1(d)), and then, a dicing sheet ( Figure 1(e)). The dicing sheet may be, for example, one provided with a second protective film-forming film that is cured to form a second protective film for protecting the semiconductor wafer and the back surface of the semiconductor wafer.

Next, the first supporting sheet is removed from the first protective film forming sheet 1 bonded to the first surface 9a of the semiconductor wafer 9 so that only the thermosetting resin film 12 remains on the first surface 9a. 101 is peeled off from the thermosetting resin film 12 (Fig. 2(f)). Here, for example, in the case of the first protective film forming sheet 1 as shown in FIG. 1 , the “first support sheet 101 ” is the first base material 11 and the buffer layer 13 . In addition, in the method of manufacturing a semiconductor wafer with a first protective film according to the first embodiment, an embodiment using the first support sheet 101 having the above configuration is exemplified. However, if the method shown in FIG. 2(f) Form, the steps in Figure 1(a)~Figure 1(d) are not necessary, and any method can be used. Next, by curing the thermosetting resin film 12, the first protective film 12' is formed on the bump formation surface of the semiconductor wafer (Fig. 2(g)).

The semiconductor wafer 9 provided with the first protective film 12' is half-cut (Fig. 2(h)). The so-called "half-cut dicing" is a cutting method in which the semiconductor wafer 9 is not completely cut off from the side of the first protective film 12' together with the first protective film 12'. As a method of half-cutting, any method that can half-cut the semiconductor wafer 9 from the side of the first protective film 12' together with the first protective film 12' may be used. Blade dicing may be used, or blade dicing may be used. For laser grooving.

In addition, each step of the manufacturing method of the semiconductor wafer of the present invention and the manufacturing method of the semiconductor wafer with the first protective film of the first embodiment can be performed in the above order. For example, as the manufacturing method of the semiconductor wafer with the first protective film of the first embodiment, Modifications of the method of manufacturing a semiconductor wafer include the above-described method of using the first protective film forming sheet 1 ( FIG. 1( a )) provided with the thermosetting resin film 12 on the first supporting sheet 101 . The thermosetting resin film 12 is attached to the first surface 9a (Fig. 1(c)) of the semiconductor wafer 9 (Fig. 1(b)) on the side of the bump 91 having the bump 91; Grinding the second surface 9b on the opposite side to the first surface 9a of the semiconductor wafer 9 (Fig. 1(d)); A dicing tape 14 is attached to the ground second surface 9b of the semiconductor wafer 9 (Fig. 1(e)); Peel the first support sheet 101 from the thermosetting resin film 12 (Fig. 2(f)); Half-cut the above-mentioned semiconductor wafer 9 from the side of the above-mentioned first surface; The thermosetting resin film 12 is thermally cured to form a first protective film 12' on the first surface of the semiconductor wafer 9 (Fig. 1(h)); and Plasma irradiation is performed on the side of the half-cut first surface of the semiconductor wafer 9 to remove the residue of the first protective film 12 ′ on the top portion 910 of the bump 91 and at the same time, the semiconductor wafer 9 is For the method of monolithization (Fig. 2(i)), the above steps of the above method can also be performed in this order.

In addition, other modifications of the method of manufacturing the semiconductor wafer with the first protective film according to the first embodiment include: attaching the thermosetting resin film 12 to the bumps of the semiconductor wafer 9 having the bumps 91 . The first surface 9a on the block 91 side (Fig. 2(f)); Half-cut the above-mentioned semiconductor wafer 9 from the side of the above-mentioned first surface; The thermosetting resin film 12 is thermally cured to form a first protective film 12' on the first surface of the semiconductor wafer 9 (Fig. 2(h)); and Plasma irradiation is performed on the side of the half-cut first surface of the semiconductor wafer 9 to remove the residue of the first protective film 12 ′ on the top portion 910 of the bump 91 and at the same time, the semiconductor wafer 9 is For the method of monolithization (Fig. 2(i)), the above steps of the above method can also be performed in this order.

The remaining thickness A of the half-cut portion of the semiconductor wafer (that is, the thickness of the half-cut portion is deducted from the thickness of the semiconductor wafer) is not particularly limited, but is 1/5 to ₄ of the thickness A of the semiconductor wafer. /5 is better, 1/4~3/4 of the thickness _A0 is better, and 1/3~2/3 of the thickness _A0 is particularly good. 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.

Plasma irradiation is performed on the half-cut side of the first surface of the semiconductor wafer 9 to remove the residue of the first protective film 12' on the top portion 910 of the bump 91 and at the same time, separate the semiconductor wafer 9 Fragmentation (Figure 2(i)). By performing plasma irradiation after half-cutting the semiconductor wafer 9 , not only can the plasma irradiation and cutting be performed without covering the barrier film, but the first protective film 12 on the top portion 910 of the bump 91 can also be removed at the same time. 'Residues and semiconductor wafer 9 can be diced into single pieces, resulting in good productivity. In addition, because plasma irradiation is performed after half-cut cutting, the occurrence of edge cracking can be reduced and the strength of the wafer can be improved. In addition, the residue of the first protective film 12' on the top portion 910 of the bump 91 may remain in the form of being stuffed into the cavity of the top portion 910 of the bump 91. Since the residues of the first protective film 12' remaining in the recesses on the tops 910 of the bumps 91 can also be removed by plasma irradiation, a semiconductor device with good connection reliability can be effectively manufactured.

The plasma processing device that performs plasma irradiation is not particularly limited, and a conventional plasma processing device can be used. In addition, the conditions of the plasma treatment vary depending on the type of the first protective film 12' and the semiconductor wafer 9, and are not particularly limited. Regarding the half-cut semiconductor wafer, The remaining thickness A (μm) of the portion and the thickness B (μm) of the first protective film on the first surface of the bump side of the semiconductor wafer (that is, the first thickness of the first protective film in the portion without bumps on the semiconductor wafer) The thickness of the protective film), the thickness C (μm) of the first protective film on the top of the bump, the etching speed a (μm/min) of the semiconductor wafer by plasma irradiation, the It is preferable that the etching speed b (μm/min) of the first protective film and the plasma irradiation time t (min) satisfy the following relationships (1), (2) and (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 protective film on the first surface of the bump side of the semiconductor wafer, and the thickness C of the first protective film on the top of the bump can be determined by The value represented by the average value of the thickness measured by a scanning electron microscope is obtained at any five selected places within the range of the obtained semiconductor wafer. In this specification, "etching speed" refers to the speed at which each object is etched when irradiated with plasma.

In the scope of the obtained semiconductor wafer, if the remaining thickness of the half-cut part is uneven, it is better that the maximum value A' of the remaining thickness of the half-cut part satisfies the formula (1)'. If the remaining thickness of the bump side When the thickness of the first protective film on the first surface is uneven, it is better if the minimum value B' of the thickness of the first protective film on the first surface on the bump side satisfies equation (2)'. If the bump side When the thickness of the first protective film on the top of the bump is uneven, it is better if the maximum value C' of the thickness of the first protective film on the top of the bump satisfies equation (3)'. A’>at…(1)’ B’>bt…(2)’ C’>bt…(3)’

Preferably by satisfying the relationship of equation (1), equation (2) and equation (3), more preferably by satisfying the relationship of equation (1)', equation (2)' and equation (3)', time The semiconductor wafer after plasma irradiation at t (min) is singulated so that the thickness of the first protective film on the first surface on the bump side becomes B-bt>0, and additional protection of the bump formation surface can be obtained. First protective film on the semiconductor wafer.

Examples of the radiation gas used in plasma irradiation include fluorine-based stabilizing gases (SF ₆ , CF ₄ , C ₂ F ₆ , C ₂ F ₄ , CHF ₃ , C ₄ F ₈ , NF ₃ , XeF _2, etc.) , O ₂ , Ar, etc., from the viewpoint of good etching properties of the semiconductor wafer, SF ₆ , CF ₄ or CHF ₃ is preferred. As a plasma power condition, 100~8000W is preferred.

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

Since the first protective film on the top of the bump is compressed by the bump, the thickness C (μm) of the first protective film on the top of the bump becomes larger than the first surface on the bump side of the semiconductor wafer. The thickness B (μm) of the first protective film is thinner. The semiconductor wafer is easily etched by plasma irradiation. Since the first protective film is made of a thermosetting resin, the etching speed a (μm/min) of the semiconductor wafer by plasma irradiation is faster than that by plasma irradiation. The etching rate b (μm/min) of the first protective film by plasma irradiation is much higher. Therefore, by adjusting the time t (min) of plasma irradiation, the conditions of plasma irradiation can be easily adjusted to satisfy the relationships of the above equations (1), (2), and (3).

For example, regarding a semiconductor wafer in which the thickness B of the first protective film on the first surface on the bump side is 30 μm, the thickness C of the first protective film on the top of the bump is 3 μm, and the thickness is 100 μm, Half-cut until the remaining thickness A is 50 μm, plasma irradiation is carried out under the conditions of plasma emission gas: SF ₆ and plasma power: 2000W. The etching speed a of the semiconductor wafer can reach 15 μm/min, and the etching speed of the first protective film b can reach 1.5μm/min, satisfying the relationships of the above equations (1), (2) and (3).

Next, the semiconductor device can be manufactured in the same manner as in the past. That is, the semiconductor wafer with the first protective film is picked up, and the picked up semiconductor wafer is flip-chip mounted on the wiring substrate to manufacture the final semiconductor device.

>Second Embodiment> 3 is a schematic diagram illustrating a second embodiment of a method for manufacturing a semiconductor wafer with a first protective film according to the present invention. The method of manufacturing a semiconductor wafer with a first protective film according to the second embodiment includes affixing the thermosetting resin film 12 to the bump-side first surface of the semiconductor wafer 9 having bumps (FIG. 3( f)); Semiconductor wafer 9 is cut in half from the side of the above-mentioned first surface (Fig. 3(g’)); Plasma irradiation is performed on the half-cut first surface side of the semiconductor wafer 9 to remove the thermosetting resin film 12 on the top of the bump, and at the same time, the semiconductor wafer 9 is singulated (Fig. 3 ( h')); and A method for manufacturing a semiconductor wafer with a first protective film by thermally curing the thermosetting resin film 12 to form a first protective film 12' on the first surface of the semiconductor wafer 9 (Fig. 3(i')).

In addition, in the manufacturing method of the semiconductor wafer with the first protective film according to the second embodiment, as a method of the form shown in FIG. 1(c), Figure 1(d) and Figure 3(f), but the steps in Figure 1(a)~Figure 1(d) are not necessary and any method can be used.

Plasma irradiation is performed on the half-cut first surface side of the semiconductor wafer 9 to remove the residues of the thermosetting resin film 12 on the top portions 910 of the bumps 91 and at the same time, the semiconductor wafer 9 is cut into pieces. fragmentation (Figure 3(h')). By dicing the semiconductor wafer 9 in half and then irradiating it with plasma, not only can it be diced by plasma irradiation without covering the barrier film, but the thermosetting resin film on the top portion 910 of the bump 91 can also be removed at the same time. 12 residues and the singulation of semiconductor wafers 9, resulting in good productivity. In addition, because plasma irradiation is performed after half-cut cutting, the occurrence of edge cracking can be reduced and the strength of the wafer can be improved. In addition, the residue of the thermosetting resin film 12 on the top portion 910 of the bump 91 may remain in the cavity of the top portion 910 of the bump 91 . Since the residues of the thermosetting resin film 12 remaining in the recesses on the tops 910 of the bumps 91 can also be removed by plasma irradiation, a semiconductor device with good connection reliability can be effectively manufactured.

The plasma processing device that performs plasma irradiation is not particularly limited, and a conventional plasma processing device can be used. In addition, the conditions of the plasma treatment vary depending on the types of the thermosetting resin film 12 and the semiconductor wafer 9 , and are not particularly limited. However, regarding the half-cut semiconductor wafer, The remaining thickness A (μm) of the portion and the thickness D (μm) of the thermosetting resin film 12 on the first bump-side surface of the semiconductor wafer (that is, the thickness of the portion of the semiconductor wafer without bumps The thickness of the thermosetting resin film 12), the thickness E (μm) of the thermosetting resin film 12 on the top of the bump, the etching rate a (μm/min) of the semiconductor wafer by plasma irradiation, and The etching rate d (μm/min) of the thermosetting resin film 12 irradiated by plasma and the time t (min) of plasma irradiation satisfy the following relationships (1), (4) and (5). Better. 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 first surface of the bump side of the semiconductor wafer, and the thickness E of the first protective film on the top of the bump can be determined by The thickness of the semiconductor wafer is obtained as an average value measured at five selected places within the range of the semiconductor wafer using a scanning electron microscope.

In the scope of the obtained semiconductor wafer, if the remaining thickness of the half-cut part is uneven, it is better that the maximum value A' of the remaining thickness of the half-cut part satisfies the formula (1)'. If the third thickness of the bump side When the thickness of the thermosetting resin film 12 on one side is uneven, it is more preferable that the minimum value D' of the thickness of the thermosetting resin film 12 on the first side of the bump satisfies equation (4)' , if the thickness of the first protective film on the top of the bump is uneven, the maximum value E' of the thickness of the thermosetting resin film 12 on the top of the bump satisfies equation (5)' as good. A’>at…(1)’ D’>bt…(4)’ E’>bt…(5)’

Preferably by satisfying the relationship of equation (1), equation (4) and equation (5), more preferably by satisfying the relationship of equation (1)', equation (4)' and equation (5)', time The semiconductor wafer after plasma irradiation at t (min) is singulated so that the thickness of the first protective film on the first surface on the bump side becomes D-dt>0, and additional protection of the bump formation surface can be obtained. First protective film on the semiconductor wafer.

The etching rate a of the semiconductor wafer by plasma irradiation is preferably 0.3~30 μm/min, preferably 0.4~25 μm/min, and preferably 0.5~20 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 top of the bump is compressed by the bump, the thickness E (μm) of the thermosetting resin film 12 on the top of the bump becomes thicker than the first protective film on the bump side of the semiconductor wafer. The thickness D (μm) of the thermosetting resin film 12 on the surface is smaller. Since the semiconductor wafer is easily etched by plasma irradiation, the etching rate a (μm/min) of the semiconductor wafer by plasma irradiation is higher than the etching rate d (μm/min) of the thermosetting resin film 12 by plasma irradiation. μm/min) is much larger. Therefore, by adjusting the time t (min) of plasma irradiation, the conditions of plasma irradiation can be easily adjusted to satisfy the relationships of the above equations (1), (4), and (5).

For example, the thickness D of the thermosetting resin film 12 on the first surface on the bump side of the semiconductor wafer is 30 μm, the thickness E of the thermosetting resin film 12 on the top of the bump is 3 μm, and the thickness E of the thermosetting resin film 12 on the bump side is 3 μm. Semiconductor wafer is cut in half until the remaining thickness A is 50 μm. Plasma irradiation is carried out under the conditions of plasma emission gas: SF ₆ and plasma power: 2000W. The etching speed a of the semiconductor wafer can reach 15 μm/min. Thermal hardening property The etching speed d of the resin film 12 can reach 1.5 μm/min, and satisfies the relationships of the above equations (1), (4) and (5).

Next, the semiconductor device can be manufactured in the same manner as in the past. That is, the semiconductor wafer with the first protective film is picked up, and the picked up semiconductor wafer is flip-chip mounted on the wiring substrate to manufacture the final semiconductor device.

◎First protective film forming sheet FIG. 1( a ) is a cross-sectional view illustrating an embodiment of the first protective film forming sheet 1 provided with 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 side surface 101 a of the first support sheet 101 . More specifically, the first protective film forming sheet 1 includes a first base material 11, a buffer layer 13 provided on the first base material 11, and a thermosetting resin film 12 provided on the buffer layer 13. The material 11 and the buffer layer 13 constitute the first supporting sheet 101.

The first protective film forming sheet is not limited to the one shown in Figure 1(a). As long as the effect of the present invention is not impaired, part of the structure of the first protective film forming sheet shown in Figure 1(a) may be changed, deleted, or Increase. Next, each layer constituting the first protective film forming sheet will be described.

◎Thermosetting resin film The thermosetting resin film is used to protect the first bump-side surface of the semiconductor wafer (that is, the bump-forming surface) and the bumps provided on the bump-forming surface.

The thermosetting resin film of the present invention is the same as a general resin film in that it is softened by heating. However, the thermosetting resin film that is thermoset by further heating has a thermosetting resin that is at normal temperature (23°C) before thermosetting. Film has the property of hardening when it returns to normal temperature after thermal hardening. In this way, the first protective film formed on the surface having the bumps functions as a protective film.

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

The thermosetting resin film can be only one layer (single layer), or it can be a plurality of two or more layers. If it is a plurality of layers, the plurality of layers can be the same or different from each other. The combination of these plurality of layers can be combined No special restrictions.

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. Since the thickness of the thermosetting resin film is equal to or greater than the above-mentioned lower limit, a first protective film with higher protective capability can be formed. In addition, since the thickness of the thermosetting resin film is equal to or less than the above-mentioned upper limit, excessive thickness is suppressed. Here, the "thickness of the thermosetting resin film" refers to the thickness of the entire thermosetting resin film. For example, the thickness of a thermosetting resin film composed of a plurality of layers refers to all components of the thermosetting resin film. The total thickness of the layers.

◎The first protective film The first protective film is a film that can be thermally cured on the first surface on the bump side of the semiconductor wafer (that is, the bump formation surface) and the bumps provided on the bump formation surface.

The thickness B (μm) of the first protective film on the first bump-side surface of the semiconductor wafer (that is, the thickness of the first protective film on the portion of the semiconductor wafer without bumps) and the thermosetting resin The film thickness is the same. Since the first protective film on the top of the bump is compressed by the bump, the thickness C (μm) of the first protective film on the top of the bump becomes thicker than the thickness of the thermosetting resin film, that is, the semiconductor crystal. The thickness B (μm) of the first protective film on the first surface on the round bump side is smaller. The thickness B of the first protective film on the first surface on the bump side 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 bump is preferably 0.11 to 10 μm, more preferably 0.5 to 7.5 μm, and particularly preferably 1 to 5 μm.

>>Thermosetting resin film forming composition>> The thermosetting resin film can be formed from a thermosetting resin film-forming composition containing its constituent materials. For example, a thermosetting resin film can be formed on a target portion by applying a thermosetting resin film-forming composition to a surface to be formed of a thermosetting resin film and drying it if necessary. A more specific method of forming the thermosetting resin film will be described in detail later together with the method of forming other layers. The content ratio of the components that do not vaporize at normal temperature (23° C.) in the thermosetting resin film-forming composition is generally the same as the content ratio of the above-mentioned components in the thermosetting resin film.

The thermosetting resin film-forming composition may be coated by a conventional method. For example, an air-knife coater, a blade coater, or a rod may be used. Bar-coater, Gravure-coater, Roll-coater, Roll-knife-coater, Curtain coater ( Curtain-coater), die coater (Die-Coater), knife coater, screen coater (Knife-coater), Meyer bar coater (Meyer bar coater), kiss coater (kiss coater) and other methods for various coating machines.

The drying conditions of the thermosetting resin film-forming composition are not particularly limited. However, when the thermosetting resin film-forming composition contains the following solvent, it is preferably heated and dried. In this case, for example, It is better to dry at 70~130℃, 10 seconds to 5 minutes.

>Resin layer forming composition> Examples of the thermosetting resin film-forming composition include, for example, a thermosetting resin film-forming composition containing a polymer component (A) and a thermosetting component (B) (herein referred to as " Resin layer forming composition"), etc.

[Polymer component (A)] The polymer component (A) is a polymer compound for imparting film-forming properties, flexibility, etc. to the thermosetting resin film, and the polymerizable compound is considered to be a component formed by a polymerization reaction. In addition, in this specification, polymerization reaction also includes polycondensation reaction. The polymer component (A) contained in the resin layer-forming composition and the thermosetting resin film may be only one type or two or more types. When there are two or more types, any combination of these may be selected. ratio.

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

Examples of the polyvinyl acetal in the polymer component (A) include those known in the art. Among them, preferred polyvinyl acetals include, for example, polyvinyl formal, polyvinyl butyral, etc., with polyvinyl butyral being more preferred. Examples of polyvinyl butyral include those having structural units represented by the following formulas (i)-1, (i)-2, and (i)-3.

(In the formula, l ₁ , m1 and n ₁ are the content ratio (mol%) of each structural unit relative to the total molar number of all structural units constituting polyvinyl butyral).

The weight average molecular weight (Mw) of polyvinyl acetal is preferably 5,000 to 200,000, and more preferably 8,000 to 100,000.

The content ratio l ₁ (degree of butyralization) of the structural units having a butyral group is preferably 40 to 90 mol%, and 50 to 85 mol% relative to the total molar number of all structural units constituting the polyvinyl butyral. For better results, 60~76 mol% is particularly preferred.

The content ratio m ₁ of the structural unit having an acetyl group is preferably 0.1 to 9 mol%, more preferably 0.5 to 8 mol%, and 1 mol% relative to the total molar number of all structural units constituting the polyvinyl butyral. ~7mol% is particularly good.

The content ratio n ₁ of the structural units having a hydroxyl group is preferably 10 to 60 mol%, more preferably 10 to 50 mol%, and 20 to 40 mol% relative to the total molar number of all structural units constituting the polyvinyl butyral. % is excellent.

The glass transition temperature (Tg) of polyvinyl acetal is preferably 40 to 80°C, and more preferably 50 to 70°C.

For example, the glass transition temperature can be measured using a differential scanning calorimetry device (manufactured by TA Instruments Japan, product name "DSC Q2000") at a heating-lowering rate of 20° C./min.

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

Among the polymer components (A), examples of the acrylic resin include conventional acrylic polymers. The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is equal to or higher than the above lower limit, the shape stability of the thermosetting resin layer (stability over time during storage) is improved. In addition, when the weight average molecular weight of the acrylic resin is equal to or less than the above-mentioned upper limit, the thermosetting resin layer becomes easier to conform to the uneven surface of the adherend, further suppressing holes, etc. between the adherend and the thermosetting resin layer. occurrence. In addition, in this specification, the "weight average molecular weight" refers to the polystyrene-converted value measured by gel permeation chromatography (GPC), unless otherwise specified.

The glass transition temperature (Tg) of the acrylic resin is preferably -50 to 70°C, and more preferably -30 to 50°C. When the Tg of the acrylic resin is equal to or higher than the above-mentioned lower limit, the adhesive force between the first protective film and the first support sheet is suppressed, thereby improving the peelability of the first support sheet. In addition, since the Tg of the acrylic resin is equal to or less than the above-mentioned upper limit, the adhesive force between the thermosetting resin film and the first protective film and the adherend is improved.

Examples of acrylic resins include, for example, polymers of one or more (meth)acrylic acid esters; in addition to (meth)acrylic acid esters, one or two or more types selected from (meth)acrylic acid, Copolymers formed by copolymerization of monomers such as conic acid, vinyl acetate, acrylonitrile, styrene, and N-hydroxymethylacrylamide.

Examples of the (meth)acrylate constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isoacrylate (meth)acrylate. Propyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, ( Hexyl methacrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid n-nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as lauryl (meth)acrylate), Tridecyl (meth)acrylate, Tetradecyl (meth)acrylate (also known as Myristyl (meth)acrylate), Pentadecyl (meth)acrylate, Cetyldecyl (meth)acrylate (also known as The alkyl group constituting alkyl esters such as palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (also known as stearyl (meth)acrylate), etc. is carbon (meth)acrylate alkyl ester with a chain structure of 1 to 18; Cycloalkyl (meth)acrylate such as isocamphenyl (meth)acrylate and dicyclopentyl (meth)acrylate; Aralkyl (meth)acrylate such as benzyl (meth)acrylate; Cycloalkenyl (meth)acrylate such as dicyclopentenyl (meth)acrylate; (Meth)acrylic acid cycloalkenyloxyalkyl esters such as (meth)acrylic acid bicycloalkenyloxyethyl ester; (meth)acrylic acid imide; Glycidyl-containing (meth)acrylates such as glycidyl (meth)acrylate; Hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxy(meth)acrylate Butyl ester, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyl-containing (meth)acrylates; Substituted amine group-containing (meth)acrylates such as N-methylaminoethyl (meth)acrylate, etc. Here, the "substituted amino group" refers to a group in which one or two hydrogen atoms of the amino group are substituted by groups other than hydrogen atoms.

In addition, in this specification, "(meth)acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". Terms similar to (meth)acrylic acid also have the same meaning. For example, "(meth)acrylate" is a concept that includes both "acrylate" and "methacrylate", and "(meth)acrylyl ” is a concept that includes both “acrylyl” and “methacrylyl”.

The monomer constituting the acrylic resin may be only one type, or may be two or more types. If there are two or more types, the combination and ratio of these may be selected arbitrarily.

The acrylic resin may have functional groups that can be bonded to other compounds, such as a vinyl group, a (meth)acryl group, an amine group, a hydroxyl group, a carboxyl group, and an isocyanate group. The above-mentioned functional group of the acrylic resin may be bonded to other compounds through the following cross-linking agent (F), or may be directly bonded to other compounds without passing through the cross-linking agent (F). Since the acrylic resin is bonded to other compounds through the above-mentioned functional groups, 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 acrylic resin (hereinafter referred to as "thermoplastic resin") may be used without using polyvinyl acetal and acrylic resin. It can be used alone or in combination with polyvinyl acetal or acrylic resin. By using the above-mentioned thermoplastic resin, the peelability of the first protective film from the first support sheet is improved, and the thermosetting resin film becomes easy to conform to the uneven surface of the adherend, further suppressing the contact between the adherend and the thermosetting resin. The occurrence of holes between membranes, etc.

The weight average molecular weight of the above-mentioned thermoplastic resin is preferably 1,000 to 100,000, and more preferably 3,000 to 80,000.

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

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

The above-mentioned thermoplastic resin contained in the resin layer forming composition and the thermosetting resin film may be only one type, or may be two or more types. If there are two or more types, the combination and ratio of these may be selected arbitrarily.

The ratio of the content of the polymer component (A) in the resin layer-forming composition to the total content (total mass) of all components except the solvent (that is, the ratio of the polymer component (A) of the thermosetting resin film Content), regardless of the type of polymer component (A), 5 to 85 mass % is preferred, and 5 to 80 mass % is more preferred. For example, it can be 5 to 70 mass %, 5 to 60 mass %, 5 to Any one of 50 mass%, 5 to 40 mass%, and 5 to 30 mass%. However, these contents in the resin layer forming composition are only examples.

The polymer component (A) may also correspond to the thermosetting component (B). In the present invention, when the resin layer-forming composition contains components corresponding to both the polymer component (A) and the thermosetting component (B), it is deemed that the resin layer-forming composition contains the polymer component (A). and thermosetting component (B).

[Thermosetting ingredient (B)] The thermosetting component (B) is a component for hardening a thermosetting resin film and forming a hard first protective film. The thermosetting component (B) contained in the resin layer forming composition and the thermosetting resin film may be only one type, or may be two or more types. If there are two or more types, any combination of these components may be selected. ratio.

Examples of the thermosetting component (B) include epoxy thermosetting resin, thermosetting polyimide, polyurethane, unsaturated polyester, silicone resin, etc., and epoxy thermosetting resin Better.

(Epoxy thermosetting resin) Epoxy thermosetting resin is composed of epoxy resin (B1) and thermosetting agent (B2). The epoxy-based thermosetting resin contained in the resin layer forming composition and the thermosetting resin film may be only one type, or may be two or more types. If there are two or more types, any combination of these may be selected. ratio.

•Epoxy resin(B1) Examples of the epoxy resin (B1) include those known in the art, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, o-cresol novolac epoxy resin, dicyclopentane Diene-type epoxy resin, biphenyl-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenylene skeleton type epoxy resin, etc., bifunctional or higher epoxy compounds.

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can be used. An epoxy resin having an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than an epoxy resin not having an unsaturated hydrocarbon group. Therefore, by using the epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained using the first protective film forming sheet is improved.

Examples of the epoxy resin having an unsaturated hydrocarbon group include, for example, a compound in which a part of the epoxy group of a polyfunctional epoxy resin is converted into a group having an unsaturated hydrocarbon group. Such compounds can be obtained, for example, by the addition reaction of (meth)acrylic acid or its derivatives to an epoxy group. Examples of the epoxy resin having an unsaturated hydrocarbon group include, for example, compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring constituting the epoxy resin. The unsaturated hydrocarbon group is a polymerizable unsaturated group. Specific examples thereof include ethenyl (also called vinyl), 2-propenyl (also called allyl), and (meth)acrylyl. , (meth)acrylamide group, etc., with acrylyl group being preferred.

The weight average molecular weight of the epoxy resin (B1) is preferably 15,000 or less, more preferably 10,000 or less, and particularly preferably 5,000 or less.

The lower limit value of the weight average molecular weight of the epoxy resin (B1) is not particularly limited. However, from the viewpoint of improving the curability of the thermosetting resin film and the strength and heat resistance of the first protective film, the weight average molecular weight of the epoxy resin (B1) is preferably 300 or more, and more preferably 500 or more. good.

The weight average molecular weight of the epoxy resin (B1) can be appropriately adjusted within a set range by arbitrarily combining the above-mentioned preferred lower limit values and upper limit values. For example, the weight average molecular weight of the epoxy resin (B1) is preferably 300 to 15,000, more preferably 300 to 10,000, and particularly preferably 300 to 3,000. In addition, the weight average molecular weight of the epoxy resin (B1) is preferably 500 to 15,000, more preferably 500 to 10,000, and particularly preferably 500 to 3,000. However, these are only examples of preferred weight average molecular weights of the epoxy resin (B1). In this specification, the "number average molecular weight" refers to the number average molecular weight represented by a standard polystyrene-converted value measured by gel permeation chromatography (GPC), unless otherwise specified.

The epoxy equivalent of epoxy resin (B1) is preferably 100~1000g/eq, and more preferably 130~800g/eq. In this specification, "epoxy equivalent" refers to 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 K 7236:2001.

The epoxy resin (B1) is preferably liquid at normal temperature (23° C.) (in this specification, it may be simply referred to as "liquid epoxy resin (B1)").

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

•Thermal hardener (B2) The thermosetting agent (B2) functions as a hardening agent for the epoxy resin (B1). Examples of the thermosetting agent (B2) include compounds having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the above-mentioned functional groups include, for example, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, a group in which an acidic group is anhydride-formed, etc. Preferred are a phenolic hydroxyl group, an amino group, or a group in which an acidic group is anhydride-formed. , phenolic hydroxyl or amino groups are better.

Among the thermal curing agents (B2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenyl, novolak-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-based curing agents. Type phenol resin, etc. Among the thermal curing agents (B2), examples of the amine-based curing agent having an amine group include, for example, dicyanodiamide (abbreviated as “DICY” in this specification).

The thermal hardener (B2) may have an unsaturated hydrocarbon group. Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include, for example, a compound in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, a compound having an aromatic ring of the phenol resin and an unsaturated hydrocarbon group. Compounds formed by direct bonding of groups. The unsaturated hydrocarbon group in the thermosetting agent (B2) may be the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group.

When a phenol-based hardener is used as the thermosetting agent (B2), from the viewpoint of improving the peelability of the first protective film from the first support sheet, the thermosetting agent (B2) has a higher softening point or glass transition temperature. Whichever is better.

Among the thermosetting agents (B2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, aralkyl type phenol resin, etc. is 300 to 30,000. Best, 400~10,000 is better, 500~3,000 is especially good. Among the thermosetting agents (B2), the molecular weight of non-resin components such as biphenyl and dicyandiamine is not particularly limited, but is preferably 60 to 500, for example.

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

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 relative to 100 parts by mass of the epoxy resin (B1), and 1 to 500 parts by mass. 200 parts by mass is more preferred, and for example, it may be 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. When the content of the thermosetting agent (B2) is equal to or higher than the lower limit, curing of the thermosetting resin film becomes easier. In addition, when the content of the thermosetting agent (B2) is below the upper limit, the moisture absorption rate of the thermosetting resin film is reduced, thereby improving the reliability of the package obtained using the first protective film.

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)), relative to the polymer component The content of (A) is preferably 50 to 1,000 parts by mass per 100 parts by mass, more preferably 60 to 950 parts by mass, and particularly preferably 70 to 900 parts by mass. When the content of the thermosetting component (B) is within this range, the adhesive force between the first protective film and the first support sheet is suppressed, thereby improving the peelability of the first support sheet.

[Harding accelerator (C)] The resin layer forming composition and the thermosetting resin film may contain a curing accelerator (C). The hardening accelerator (C) is a component for adjusting the hardening speed of the resin layer forming composition. Preferable hardening accelerators (C) include, for example, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylamineethanol, ginseng(dimethylaminomethyl)phenol, and the like. Grade amines; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl -Imidazoles such as 5-hydroxymethylimidazole (that is, imidazoles in which one or more hydrogen atoms are substituted by groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine, etc. (that is, phosphines in which one or more hydrogen atoms are substituted by organic groups); tetraphenylboron salts of tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, etc.

The curing accelerator (C) contained in the resin layer forming composition and the thermosetting resin film may be only one type, or may be two or more types. If there are two or more types, the combination and ratio of these may be selected arbitrarily. .

When a hardening accelerator (C) is used, the content of the hardening accelerator (C) in the resin layer forming composition and the thermosetting resin film is 0.01 with respect to 100 parts by mass of the thermosetting component (B). ~10 parts by mass is preferred, and 0.1~5 parts by mass is more preferred. When the content of the hardening accelerator (C) is equal to or higher than the lower limit, the effect achieved by using the hardening accelerator (C) can become more significant. In addition, by setting the content of the hardening accelerator (C) below the above upper limit, for example, the highly polar hardening accelerator (C) is suppressed from being combined with the adherend in the thermosetting resin film under high temperature and high humidity conditions. The effect of interfacial side movement and segregation becomes higher, and the reliability of the package obtained by using the first protective film forming sheet is further improved.

[Filling material (D)] The resin layer forming composition and the thermosetting resin film may contain a filler (D). Since the thermosetting resin film contains the filler (D), the thermal expansion coefficient of the first protective film obtained by curing the thermosetting resin film becomes easy to adjust. Then, the thermal expansion coefficient is optimized according to the object to be formed of the first protective film, and the reliability of the package obtained using the first protective film-shaped sheet is further improved. In addition, since the thermosetting resin film contains the filler (D), the moisture absorption rate of the first protective film can be reduced and the heat dissipation performance can be improved.

The filler (D) may be either an organic filler or an inorganic filler, but an inorganic filler is preferred. Preferred inorganic fillers include, for example, powders of silicon oxide, aluminum oxide, talc, calcium carbonate, titanium white, red lead, silicon carbide, boron nitride, etc.; these inorganic fillers are formed by spheroidizing Beads; surface modifications of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. Among these, the inorganic filler is preferably silicon oxide or alumina.

The filler (D) contained in the resin layer forming composition and the thermosetting resin film may be only one type, or may be two or more types. If there are two or more types, the combination and ratio of these may be selected arbitrarily.

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 addition, in this specification, the so-called "average particle size", unless otherwise specified, refers to the particle size at 50% of the cumulative value (D ₅₀ ) value.

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 viewpoint of easy acquisition of the filler (D). As one aspect, the average particle size 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, particularly preferably 0.01 μm or more and 0.1 μm or less.

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

[Coupling agent (E)] The resin layer forming composition and the thermosetting resin film may contain a coupling agent (E). By using one having a functional group that can react with an inorganic compound or an organic compound as the coupling agent (E), the adhesiveness and adhesion of the thermosetting resin film to the adherend can be improved. In addition, by using the coupling agent (E), the first protective film obtained by curing the thermosetting resin film improves the water resistance without impairing the heat resistance.

The coupling agent (E) is preferably a compound having a functional group that can react with the functional group possessed by the polymer component (A), the thermosetting component (B), etc., and more preferably a silane coupling agent. Preferred silane coupling agents include, for example, 3-epoxypropyloxypropyltrimethoxysilane, 3-epoxypropyloxypropylmethyldiethoxysilane, and 3-cyclopropyloxypropyltrimethoxysilane. Oxypropyloxypropyltriethoxysilane, 3-epoxypropyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3 -Methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2- Aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane Ethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane (bis(3-triethoxysilylpropyl) )tetrasulfane), methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethyloxysilane, imidazolesilane, etc.

The coupling agent (E) contained in the resin layer-forming composition and the thermosetting resin film may be only one type, or may be two or more types. If there are two or more types, the combination and ratio of these may be selected arbitrarily.

When a coupling agent (E) is used, the content of the coupling agent (E) in the resin layer forming composition and the thermosetting resin film is determined relative to the total content of the polymer component (A) and the thermosetting component (B). When it is 100 parts by mass, 0.03 to 20 parts by mass is preferred, 0.05 to 10 parts by mass is more preferred, and 0.1 to 5 parts by mass is particularly preferred. When the content of the coupling agent (E) is equal to or above the lower limit, the dispersibility of the filler (D) in the resin, the adhesion between the thermosetting resin film and the adherend, etc. are improved, which is achieved by using the coupling agent (E). The effect becomes more significant. In addition, when the content of the coupling agent (E) is equal to or less than the upper limit, the occurrence of outgassing is further suppressed.

[Crosslinking agent (F)] As the polymer component (A), when using the above-mentioned acrylic resin or the like having functional groups such as a vinyl group, a (meth)acryl group, an amine group, a hydroxyl group, a carboxyl group, and an isocyanate group that can be bonded to other compounds, The resin layer forming composition and the thermosetting resin film may contain a crosslinking agent (F). The cross-linking agent (F) is a component for bonding and cross-linking the above-mentioned functional groups in the polymer component (A) with other compounds. Through such cross-linking, the initial adhesive strength of the thermosetting resin film can be adjusted. and cohesion.

Examples of the cross-linking agent (F) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate-based cross-linking agents (that is, cross-linking agents having a metal chelate structure), aziridine compounds, etc. A pyridine cross-linking agent (that is, a cross-linking agent having an aziridine group), etc.

Examples of the organic polyvalent isocyanate compound include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds are collectively referred to as "aromatic polyvalent isocyanate compounds, etc." "); trimers, isocyanurates and adducts of the above-mentioned aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane polymers obtained by reacting the above-mentioned aromatic polyvalent isocyanate compounds, etc. with polyol compounds. wait. The above-mentioned "adduct" refers to the above-mentioned aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound or alicyclic polyvalent isocyanate compound and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or trimethylolpropane. The reaction product of sesame oil and other low molecular weight active hydrogen-containing compounds. Examples of the adduct include the following diphenyl diisocyanate adduct of trimethylolpropane. In addition, the "terminal isocyanate urethane prepolymer" refers to a prepolymer that has a urethane bond and an isocyanate group at the end of the molecule.

More specific examples of the organic polyvalent isocyanate compound include, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylene diisocyanate; and 1,4-xylene diisocyanate. Isocyanates; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone Diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; 1 type added to all or part of the hydroxyl groups of polyols such as trimethylolpropane Or two or more compounds of any one of toluene diisocyanate, hexamethylene diisocyanate and xylene diisocyanate; lysine diisocyanate, etc.

Examples of the organic polyvalent imine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β -Aziridinyl propionate, tetramethylolmethane-tris-β-aziridinylpropionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide)tris Ethylene melamine, etc.

When an organic polyvalent isocyanate compound is used as the cross-linking agent (F), it is preferable to use a hydroxyl-containing polymer as the polymer component (A). When the cross-linking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the cross-linking agent (F) can be easily introduced into the thermosetting resin film through the reaction between the cross-linking agent (F) and the polymer component (A). connection structure.

The crosslinking agent (F) contained in the resin layer forming composition and the thermosetting resin film may be only one type, or may be two or more types. If there are two or more types, the combination and ratio of these may be selected arbitrarily. .

When a cross-linking agent (F) is used, the content of the cross-linking agent (F) in the resin layer forming composition is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the content of the polymer component (A). It is more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass. When the content of the cross-linking agent (F) is equal to or higher than the lower limit, the effect achieved by using the cross-linking agent (F) becomes more significant. In addition, when the content of the cross-linking agent (F) is equal to or less than the upper limit, excessive use of the cross-linking agent (F) can be suppressed.

[Other ingredients] The composition for forming a resin layer and the thermosetting resin film may further contain the above-mentioned polymer component (A), thermosetting component (B), hardening accelerator (C), filler within the range that does not impair the effects of the present invention. Ingredients other than material (D), coupling agent (E) and cross-linking agent (F). Examples of the above-mentioned other components include energy ray curable resin, photopolymerization initiator, colorant, general-purpose additives, and the like. The above-mentioned general-purpose additives are those commonly used and can be selected arbitrarily according to the purpose, and are not particularly limited. However, preferred ones include, for example, plasticizers, antistatic agents, antioxidants, and colorants (dyes, pigments). , gettering agent, etc.

The above-mentioned other components contained in the resin layer forming composition and the thermosetting resin film may be only one type, or may be two or more types. If there are two or more types, the combination and ratio of these components may be arbitrarily selected. The contents of the above-mentioned other components in the resin layer forming composition and the thermosetting resin film are not particularly limited and may be appropriately selected depending on the purpose.

A composition for forming a resin layer and a thermosetting resin film containing a polymer component (A) and a thermosetting component (B), polyvinyl acetal as the polymer component (A), and a liquid form as epoxy Resin (B1) is preferable, and one which further contains a hardening accelerator (C) and a filler (D) in addition to these components is more preferable. 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 handleability. The above solvent is not particularly limited, but preferred examples include, for example, hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, and isobutanol (also known as 2-methylpropyl-1 Alcohols such as -alcohol) and 1-butanol; esters such as ethyl acetate; ketones such as acetone, methyl ethyl ketone; ethers such as tetrahydrofuran; chelates such as dimethylformamide, N-pyrrolidone, etc. Amines (that is, compounds having amide bonds), etc. The solvent contained in the composition for forming a resin layer may be only one type, or may be two or more types. If there are two or more types, the combination and ratio of these solvents may be selected arbitrarily.

The solvent contained in the resin layer-forming composition is preferably methyl ethyl ketone or the like from the viewpoint that 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. For example, it may be appropriately selected depending on the types of components other than the solvent.

>>Method for producing thermosetting resin film-forming composition>> A thermosetting resin film-forming composition such as a resin layer-forming composition can be obtained by blending each component constituting the composition. When preparing each component, the order of addition is not particularly limited, and two or more components may be added at the same time. When using a solvent, the solvent may be mixed with any preparation ingredients other than the solvent, and the preparation ingredients may be diluted in advance before use, or any preparation ingredients other than the solvent may not be diluted in advance, and the solvent may be mixed with these preparation ingredients before use. . The method of mixing each component during preparation is not particularly limited, and an appropriate selection can be made from known methods such as mixing by rotating a stirrer or a stirring blade, mixing using a mixer, and mixing by applying ultrasonic waves. Can. The temperature and time during the addition and mixing of each component are not particularly limited as long as the components are not deteriorated and can be adjusted appropriately. However, the temperature is preferably 15 to 30°C.

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

◎First base material The first base material is in the form of a sheet or film, and its constituent materials include, for example, various resins. Examples of the resin include polyethylene such as low-density polyethylene (abbreviated as LDPE), linear low-density polyethylene (abbreviated as LLDPE), and high-density polyethylene (abbreviated as HDPE); polypropylene and polybutylene , polyolefins other than polyethylene such as polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth) ) Ethylene-based copolymers (copolymers using ethylene as a monomer) such as acrylate copolymers and ethylene-norbornene copolymers; vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymers (resin obtained using vinyl chloride as a monomer); polystyrene; polycyclic olefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly Polyesters such as fully aromatic polyesters in which all structural units of polyethylene-2,6-naphthalenedicarboxylate have aromatic ring groups; two or more types of the above polyesters copolymer; poly(meth)acrylate; polyurethane; polyurethane acrylate; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polysulfonated benzene; polyacetal Silica; polyetherketone, etc. Examples of the resin include polymer-alloys such as mixtures of the above-mentioned polyester and resins other than the above-mentioned polyester. The blend of the above-mentioned polyester and resins other than the polyester is preferably one in which the amount of the resin other than the polyester is relatively small. Examples of the resin include cross-linked resins obtained by cross-linking one or two or more of the above-mentioned resins exemplified so far; Modified resins such as ionomers.

The resin constituting the first base material may be only one type, or may be two or more types. If there are two or more types, the combination and ratio of these may be selected arbitrarily.

The first base material can be only one layer (single layer), or it can be a plurality of two or more layers. If it is a plurality of layers, the plurality of layers can be the same or different from each other. The combination of these plurality of layers does not matter. Specially limited. Moreover, in this specification, it is not limited to the first base material. The term "the plurality of layers may be the same or different from each other" means "all the layers may be the same, all the layers may be different, or only part of them may be different." "The layers are the same". Furthermore, "the plurality of layers are different from each other" means that "at least one of the constituent materials and thickness of each layer is different from each other."

The thickness of the first base material is preferably 5 to 1000 μm, more preferably 10 to 500 μm, further preferably 15 to 300 μm, and particularly preferably 20 to 150 μm. Here, the "thickness of the first base material" refers to the thickness of the entire first base material. For example, the thickness of the first base material composed of a plurality of layers refers to all the layers constituting the first base material. Total thickness.

The first base material is preferably one that has high thickness accuracy, that is, one that has suppressed variations in thickness at any location. Among the above-mentioned constituent materials, materials that can be used to constitute the first base material with such a high accuracy in thickness include, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene- Vinyl acetate copolymer, etc.

In addition to the main constituent materials such as the above-mentioned resin, the first base material may also contain various conventional additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, softeners (plasticizers), etc. .

The first substrate can be transparent or opaque, it can also be colored according to the purpose, and it can also be deposited with other layers. When the thermosetting resin film is energy ray curable, the first base material is preferably one that can be penetrated by energy rays.

The first base material can be manufactured by conventional methods. For example, the first base material containing a resin can be produced by molding a resin composition containing the above resin.

◎Peel-off film The above-mentioned release film may be one known in the art. Preferable examples of the above-mentioned release film include, for example, those in which at least one surface of a resin film such as polyethylene terephthalate is subjected to a release treatment by silicone treatment or the like; at least one surface of the film is The side surface becomes a peeling surface made of polyolefin. The thickness of the release film is preferably the same as the thickness of the first base material.

◎Buffer layer The buffer layer 13 has a buffering effect on the force exerted on the buffer layer 13 and the layers adjacent thereto. Here, the "layer adjacent to the buffer layer" is represented by the thermosetting resin film 12.

The buffer layer 13 is preferably in the form of a sheet or a film, and has energy ray curability. The energy ray-curable buffer layer 13 is hardened by energy rays and can be easily peeled off from the thermosetting resin film 12 described below.

Examples of the constituent material of the buffer layer 13 include various adhesive resins. Examples of the adhesive resin include adhesive resins such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, and polycarbonate. Acrylic resin is preferred. When the buffer layer 13 is energy ray hardenable, its constituent materials include various components necessary for energy ray hardening.

In addition, in the present invention, the so-called "adhesive resin" refers to a concept that includes both adhesive resin and adhesive resin. For example, not only the resin itself has adhesiveness, but also includes those with additives. Resins that exhibit adhesiveness when used in combination with other components such as heat or water, resins that exhibit adhesiveness due to the presence of triggers such as heat or water, etc.

The buffer layer 13 can be only one layer (single layer), or it can be a plurality of two or more layers. If it is a plurality of layers, the plurality of layers can be the same or different from each other. There is no special combination of the plurality of layers. 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. For example, the thickness of the buffer layer 13 composed of a plurality of layers refers to the total thickness of all the layers constituting the buffer layer 13.

>>Adhesive resin composition>> The buffer layer 13 can be formed of an adhesive resin composition containing an adhesive resin. For example, the buffer layer 13 can be formed on the target site by applying an adhesive resin composition to the surface to be formed of the buffer layer 13 and drying it if necessary.

The adhesive resin composition can be coated by a conventional method. For example, an air knife coater, a blade coater, a rod coater, a gravure coater, and a roll coater can be used. , roller knife coater, curtain coater, die coater, knife coater, screen coater, Myler rod coater, dovetailing coater, etc. Various coating machine methods.

The drying conditions of the adhesive resin composition are not particularly limited, but it is preferable to heat and dry the adhesive resin composition containing a solvent described below. For example, the adhesive resin composition containing a solvent is preferably dried at 70 to 130°C for 10 seconds to 5 minutes.

When the buffer layer 13 is energy ray curable, examples of the adhesive resin composition containing the energy ray curable adhesive, that is, the energy ray curable adhesive resin composition include, for example, non-energy ray curable adhesive resin compositions. adhesive resin (I-1a) (hereinafter referred to as "adhesive resin (I-1a)") and an adhesive resin composition (I-1) containing an energy ray curable compound; The adhesiveness of energy-beam-curable adhesive resin (I-2a) (hereinafter referred to as "adhesive resin (I-2a)") in which an unsaturated group is introduced into the side chain of the adhesive resin (I-1a) Resin composition (I-2); adhesive resin composition (I-3) containing the above-mentioned adhesive resin (I-2a), energy ray curable low molecular weight compound, etc.

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

>>Manufacturing method of adhesive resin composition>> The above-mentioned adhesive resin compositions such as the adhesive resin compositions (I-1) to (I-4) can be composed of the above-mentioned adhesive resin and, if necessary, components other than the above-mentioned adhesive resin. Each component of the resin composition is prepared by blending. When preparing each component, the order of addition is not particularly limited, and two or more components can be added at the same time. When using a solvent, the solvent may be mixed with any prepared ingredients other than the solvent, and the prepared ingredients may be diluted in advance before use, or any prepared ingredients other than the solvent may not be diluted in advance, and the solvent may be mixed with these prepared ingredients. reuse. The method of mixing each component during preparation is not particularly limited, and an appropriate selection can be made from known methods such as mixing by rotating a stirrer or a stirring blade, mixing using a mixer, and mixing by applying ultrasonic waves. Can. The temperature and time during the addition and mixing of each component are not particularly limited as long as the components are not deteriorated and can be adjusted appropriately. However, the temperature is preferably 15 to 30°C.

◇Method for manufacturing the first protective film forming sheet The above-mentioned first protective film forming sheet can be manufactured by sequentially stacking layers so as to correspond to the positional relationship of the above-mentioned layers. The formation method of each layer is as described previously.

For example, a first protective film forming sheet in which a buffer layer and a thermosetting resin film are laminated in this order on a first base material in the thickness direction can be produced by the method shown below. That is, the buffer layer is laminated on the first base material by extrusion molding the adhesive resin composition for forming the buffer layer. Furthermore, the thermosetting resin film is laminated by applying the thermosetting resin film-forming composition to the release-treated surface of the release film and drying it if necessary. Then, by laminating the thermosetting resin film on the release film and the buffer layer on the first base material, the buffer layer, the thermosetting resin film and the release film on the first base material can be obtained. A first protective film forming sheet that is laminated sequentially. The release film may be removed when using the first protective film forming sheet.

The first protective film-forming sheet provided with layers other than the above-mentioned layers can be appropriately added with the steps of forming and laminating the other layers so that the lamination positions of the other layers become appropriate positions in the above-mentioned manufacturing method. any or both of the steps.

For example, a first protective film-forming sheet in which an adhesion layer, a buffer layer, and a thermosetting resin film are laminated in this order on a first base material in the thickness direction can be formed by the following method: Made according to the method shown. That is, with respect to the first base material, the adhesion layer-forming composition and the buffer layer-forming adhesive resin composition are co-extruded, and the adhesion layer and the buffer layer are formed on the first base material accordingly. Sequential layering. Then, in the same method as described above, a thermosetting resin film is separately laminated on the release film. Next, by laminating the thermosetting resin film on the release film to the first base material and the buffer layer on the adhesion layer, it is possible to obtain the adhesion layer, buffer layer, and thermosetting layer on the first base material. A first protective film forming sheet in which a flexible resin film and a release film are laminated in this order. The release film on the thermosetting resin film may be removed when using the first protective film forming sheet. [Industrial Availability]

The present invention provides a method for manufacturing a semiconductor wafer, which can simultaneously remove the residue of the first protective film on the top of the bumps and singulate the semiconductor wafer into individual wafers. The method has good productivity and is therefore extremely useful in industry.

1‧‧‧Sheet for forming the first protective film 11‧‧‧First base material 12‧‧‧Thermosetting resin film 12a‧‧‧The first side of the thermosetting resin film 12a’‧‧‧First protective film 13‧‧‧Buffer layer 14‧‧‧Cutting sheets 101‧‧‧First support sheet 9‧‧‧Semiconductor wafer 9a‧‧‧The first surface of the semiconductor wafer (bump formation surface) 9b‧‧‧The second side (back side) of the semiconductor wafer 91‧‧‧Bump 91a‧‧‧Bump surface 910‧‧‧The top of the bump

1 is a schematic diagram illustrating a first embodiment of a method for manufacturing a semiconductor wafer with a first protective film according to the present invention. 2 is a schematic diagram illustrating a first embodiment of a method for manufacturing a semiconductor wafer with a first protective film according to the present invention. 3 is a schematic diagram illustrating a second embodiment of a method for manufacturing a semiconductor wafer with a first protective film according to the present invention.

1‧‧‧Sheet for forming the first protective film

9‧‧‧Semiconductor wafer

9a‧‧‧The first surface of the semiconductor wafer (bump formation surface)

9b‧‧‧The second side (back side) of the semiconductor wafer

11‧‧‧First base material

12‧‧‧Thermosetting resin film

12a‧‧‧The first side of the thermosetting resin film

13‧‧‧Buffer layer

14‧‧‧Cutting sheets

91‧‧‧Bump

91a‧‧‧Bump surface

101‧‧‧First support sheet

910‧‧‧The top of the bump

Claims (10)

A method of manufacturing a semiconductor wafer with a first protective film, including: attaching a thermosetting resin film to a first surface of a semiconductor wafer having bumps on the bump side; and thermosetting the thermosetting resin film , forming a first protective film on the first surface of the semiconductor wafer; performing half-cut cutting from the side of the first surface of the semiconductor wafer on which the first protective film is formed; and by cutting the half-cut above-mentioned The side of the first surface of the semiconductor wafer is irradiated with plasma to remove the residue of the first protective film on the top of the bump and at the same time, the semiconductor wafer is singulated; wherein the thermosetting resin film It contains a polymer component A and a thermosetting component B, and the polymer component A contains polyvinyl acetal; the half-cut cutting is performed so that the remaining thickness A of the half-cut portion of the semiconductor wafer is the thickness A of the semiconductor wafer _{. 0} 1/5~4/5. A method of manufacturing a semiconductor wafer with a first protective film, including: combining the above-mentioned first protective film-forming sheet including a first support sheet and a thermosetting resin film provided on the first support sheet A thermosetting resin film is attached to the first surface on the bump side of a semiconductor wafer having bumps; the first support sheet is peeled off from the thermosetting resin film; and the thermosetting resin film is heated Curing and forming a first protective film on the first surface of the semiconductor wafer; performing half-cutting from the side of the first surface of the semiconductor wafer; and by forming a first protective film on the first side of the half-cut semiconductor wafer. Plasma irradiation is performed on one side to remove the residue of the first protective film on the top of the bump and at the same time, the semiconductor wafer is singulated; wherein the thermosetting resin film contains polymer component A and Thermosetting component B, the above-mentioned polymer component A contains polyvinyl acetal; the above-mentioned half-cutting is performed so that the remaining thickness A of the half-cut portion of the above-mentioned semiconductor wafer is 1/5 to 4 of the thickness _A0 of the semiconductor wafer. /5. The method for manufacturing a semiconductor wafer with a first protective film as described in item 1 or 2 of the patent application, wherein the polyvinyl acetal is polyvinyl formal or polyvinyl butyral. The manufacturing method of a semiconductor wafer with a first protective film as described in claim 1 or 2, wherein the polyvinyl acetal has the following formulas (i)-1, (i)-2 and (i) -3 represents the structural unit:

In the formula, l ₁ , m ₁ and n ₁ are the content ratio (mol%) of each structural unit relative to the total molar number of all the structural units constituting polyvinyl butyral. The manufacturing method of a semiconductor wafer with a first protective film as described in claim 1 or 2, wherein, with respect to the half-cut semiconductor wafer, the remaining thickness A of the half-cut portion of the semiconductor wafer is ( μm), the thickness B (μm) of the first protective film on the first surface of the semiconductor wafer, the thickness C (μm) of the first protective film on the top of the bump, the thickness of the first protective film by plasma irradiation The etching rate a (μm/min) of the above-mentioned semiconductor wafer, the etching rate of the above-mentioned first protective film by plasma irradiation, The engraving speed b (μm/min) and the plasma irradiation time t (min) satisfy the following relationships (1), (2) and (3): A<at…(1) B>bt…( 2) C<bt…(3). A method of manufacturing a semiconductor wafer with a first protective film, including: attaching a thermosetting resin film to a first surface of a semiconductor wafer having bumps on the bump side; The film is half-cut from the side of the first surface of the semiconductor wafer; by plasma irradiation on the side of the first surface of the half-cut semiconductor wafer, the above-mentioned top portion of the bump is removed. The above-mentioned semiconductor wafer is singulated together with the thermosetting resin film; and the above-mentioned thermosetting resin film attached to the above-mentioned singulated semiconductor wafer is thermally cured, and the above-mentioned third part of the above-mentioned semiconductor wafer is A first protective film is formed on one side; the thermosetting resin film contains a polymer component A and a thermosetting component B, and the polymer component A contains polyvinyl acetal; the half-cutting is performed to make the semiconductor wafer The remaining thickness A of the half-cut portion is 1/5 to 4/5 of the thickness A ₀ of the semiconductor wafer. A method of manufacturing a semiconductor wafer with a first protective film, including the following steps: forming a first protective film-forming sheet including a first support sheet and a thermosetting resin film provided on the first support sheet The above-mentioned thermosetting resin film is attached to the first surface of the bump side of the semiconductor wafer having bumps; the above-mentioned first support sheet is peeled off from the above-mentioned thermosetting resin film; The curable resin film is half-cut from the first surface side of the semiconductor wafer; and the bumps are removed by plasma irradiation on the first surface side of the half-cut semiconductor wafer. while the thermosetting resin film on the top of the head is singulated into individual pieces; and the thermosetting resin film attached to the individualized semiconductor wafer is thermally cured, and the semiconductor wafer is placed on the top of the head. The first surface of the circle forms a first protective film; wherein the thermosetting resin film contains a polymer component A and a thermosetting component B, and the polymer component A contains polyvinyl acetal; the half-cutting is performed to make the semiconductor The remaining thickness A of the half-cut portion of the wafer is 1/5 to 4/5 of the thickness A ₀ of the semiconductor wafer. The method for manufacturing a semiconductor wafer with a first protective film as described in item 6 or 7 of the patent application, wherein the polyvinyl acetal is polyvinyl formal or polyvinyl butyral. The manufacturing method of a semiconductor wafer with a first protective film as described in item 6 or 7 of the patent application, wherein the polyvinyl acetal has the following formulas (i)-1, (i)-2 and (i) -3 represents the structural unit:

In the formula, l ₁ , m ₁ and n ₁ are the content ratio (mol%) of each structural unit relative to the total molar number of all the structural units constituting polyvinyl butyral. Semiconductor crystal with first protective film as described in item 6 or 7 of the patent application A method of manufacturing a wafer, wherein with respect to the half-cut semiconductor wafer, a remaining thickness A (μm) of the half-cut portion of the semiconductor wafer, a thermosetting resin film on the first surface of the semiconductor wafer thickness D (μm), thickness E (μm) of the thermosetting resin film on the top of the bump, etching rate a (μm/min) of the semiconductor wafer by plasma irradiation, The etching rate d (μm/min) of the thermosetting resin film irradiated with plasma, the time t (min) of plasma irradiation, etc. satisfy the relationships of the following formulas (1), formula (4) and formula (5), A <at…(1) D>dt…(4) E<dt…(5).