KR20200138154A - Semiconductor chip manufacturing method - Google Patents

Abstract

Attaching a thermosetting resin film to the first surface on the bump side of a semiconductor wafer having bumps, and forming a first protective film on this first surface of the semiconductor wafer by thermosetting the thermosetting resin film. Half-cut dicing the semiconductor wafer from the first surface side on which the first protective film is formed, and plasma irradiation on the half-cut diced first surface side of the semiconductor wafer, whereby the residue of the first protective film at the top of the bump A method for manufacturing a semiconductor chip in which a first protective film is formed, comprising removing the semiconductor wafer into pieces.

Description

Semiconductor chip manufacturing method

The present invention relates to a method of manufacturing a semiconductor chip. More specifically, it relates to a method of manufacturing a semiconductor chip in which a first protective film for protecting a bump formation surface is formed.

This application claims priority based on Japanese Patent Application No. 2018-069682 for which it applied to Japan on March 30, 2018, and uses the content here.

Conventionally, in the case of mounting a LSI package of many pins used in MPUs or gate arrays on a printed wiring board, as a semiconductor chip, a convex electrode made of eutectic solder, high temperature solder, gold, etc. to the connection pad portion thereof (hereinafter, In the present specification, a flip chip mounting method in which the bumps are formed (referred to as ``bumps'') and melt/diffusion bonding by making these bumps face to each other on the chip mounting substrate by a so-called face-down method Was being employed.

The semiconductor chip used in this mounting method is obtained, for example, by grinding or dicing the rear surface of a semiconductor wafer on which bumps are formed on the circuit surface opposite to the circuit surface (that is, the bump formation surface) or dicing into pieces. In the process of obtaining such a semiconductor chip, usually, for the purpose of protecting the bump formation surface and the bump of the semiconductor wafer, a curable resin film is affixed to the bump formation surface, the film is cured, and a protective film (in this specification) In this case, hereinafter, it may be referred to as "the first protective film").

The curable resin film is usually affixed to the bump formation surface of a semiconductor wafer in a state softened by heating. In this way, the curable resin film covers the bumps of the semiconductor wafer, spreads between the bumps, adheres to the bump formation surface, covers the surface of the bump, particularly the surface near the bump formation surface, and embeds the bump. . 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 to form a protective film for protecting these regions. In addition, the semiconductor wafer is subdivided into semiconductor chips, and finally, a semiconductor chip provided with a protective film on the bump formation surface (in this specification, it may be referred to as a "semiconductor chip with a first protective film").

The semiconductor chip on which such a protective film is formed is mounted on a substrate to form a semiconductor package, and further, a semiconductor device of interest is constructed using this semiconductor package. In order for the semiconductor package and the semiconductor device to function normally, it is necessary that the bump of the semiconductor chip on which the protective film is formed and the electrical connection of the circuit on the substrate are not hindered. By the way, the curable resin film may remain at the top of the bump. The curable resin film remaining on the top of the bump is cured in the same manner as in the case of the curable resin film in other regions, and a cured product having the same composition as the protective film (in this specification, it may be referred to as ``protective film residue'') Becomes. Then, since the top of the bump is an electrical connection region between the bump and the circuit on the substrate, when the amount of the protective film residue is large, the electrical connection between the bump of the semiconductor chip on which the protective film is formed and the circuit on the substrate is inhibited, and in the reliability test It leads to deterioration of electrical properties.

That is, in the step before mounting of the semiconductor chip on which the protective film is formed onto the substrate, it is required that almost no protective film residue exists at the top of the bump of the semiconductor chip on which the protective film is formed.

As a method of removing the protective film at the top of the bump, a method of manufacturing a semiconductor device in which plasma treatment is performed has been proposed (see Patent Document 1). Plasma treatment is applied to the protective film on the bump formation surface to remove the resin film covering the top of the bump, and then dicing with a dicing blade to separate it into pieces to obtain a semiconductor chip. By electrically connecting, a semiconductor device having excellent connection reliability can be efficiently manufactured.

In addition, a method of etching and dividing a semiconductor wafer by previously covering a region other than the cut line of the semiconductor wafer with a resist layer and plasma irradiating a portion corresponding to the cut line not covered with the resist film is known (Patent Document 2, etc. ).

International Publication No. 2016/194431 Japanese Unexamined Patent Publication No. 2004-193305

However, in the dicing method disclosed in Patent Literature 1, a plasma treatment step for removing the resin film at the top of the bump is separately required before the dicing step, and thus there is a difficulty in terms of productivity. In addition, in the dicing method disclosed in Patent Literature 2, since application, exposure, and development treatment of a resist film are separately required before the dicing step, there is a difficulty in terms of productivity.

Accordingly, an object of the present invention is to provide a method for manufacturing a semiconductor chip having excellent productivity, since it is possible to simultaneously achieve the removal of the residue of the first protective film on the top of the bump and the segmentation of the semiconductor wafer.

The present invention includes the following aspects.

[1] attaching a thermosetting resin film to the bump-side first surface of a semiconductor wafer having bumps,

Thermosetting the thermosetting resin film to form a first protective film on the first surface of the semiconductor wafer,

Half-cut dicing the semiconductor wafer on which the first protective film is formed from the first surface side, and

And removing the residue of the first protective film at the top of the bump by irradiating plasma to the first surface side of the semiconductor wafer that has been half-cut diced, and dividing the semiconductor wafer into pieces.

A method of manufacturing a semiconductor chip with a first protective film formed thereon.

[2] The thermosetting resin film of the sheet for forming a first protective film comprising a first support sheet and a thermosetting resin film provided on the first sheet is applied to the first surface of the bump side of a semiconductor wafer having bumps. Sticking,

Peeling the first support sheet from the thermosetting resin film,

Thermosetting the thermosetting resin film to form a first protective film on the first surface of the semiconductor wafer,

Dicing the semiconductor wafer half cut from the first surface side, and

And removing the residue of the first protective film at the top of the bump by irradiating plasma to the side of the first half-cut surface of the semiconductor wafer, and dividing the semiconductor wafer into pieces.

A method of manufacturing a semiconductor chip with a first protective film formed thereon.

[3] With respect to the half-cut diced semiconductor wafer, the remaining thickness A (µm) of the half-cut portion of the semiconductor wafer, and the thickness B (µm) of the first protective film on the first surface of the semiconductor wafer, and , The thickness C (µm) of the first protective film on the top of the bump, the etching rate a (µm/min) of the semiconductor wafer by plasma irradiation, and the etching rate b (µm) of the first protective film by plasma irradiation /min) and the plasma irradiation time t(min) satisfying the relationship of the following formulas (1), (2) and (3), a semiconductor in which the first protective film described in [1] or [2] is formed How to make a chip.

A<at… (One)

B＞bt… (2)

C<bt… (3)

[4] attaching a thermosetting resin film to the bump-side first surface of a semiconductor wafer having bumps,

Half-cut dicing the semiconductor wafer to which the thermosetting resin film is affixed from the first surface side,

Plasma irradiation on the side of the first half-cut surface of the semiconductor wafer to remove the thermosetting resin film at the top of the bump, and to separate the semiconductor wafer, and

Comprising forming a first protective film on the first surface of the semiconductor wafer by thermosetting the thermosetting resin film affixed to the segmented semiconductor wafer

A method of manufacturing a semiconductor chip with a first protective film formed thereon.

[5] The thermosetting resin film of the sheet for forming a first protective film including a first support sheet and a thermosetting resin film provided on the first support sheet is provided with a first surface on the bump side of a semiconductor wafer having bumps. Attaching to,

Peeling the first support sheet from the thermosetting resin film,

Half-cut dicing the semiconductor wafer to which the thermosetting resin film is affixed from the first surface side,

Plasma irradiation on the side of the first half-cut surface of the semiconductor wafer to remove the thermosetting resin film at the top of the bump and to separate the semiconductor wafer,

And forming a first protective film on the first surface of the semiconductor wafer by thermosetting the thermosetting resin film affixed to the individualized semiconductor wafer.

[6] For the half-cut diced semiconductor wafer, the remaining thickness A (µm) of the half-cut portion of the semiconductor wafer, and the thickness D (µm) of the thermosetting resin film on the first side of the semiconductor wafer, and , The thickness E (μm) of the thermosetting resin film 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) of the thermosetting resin film by plasma irradiation /min) and the plasma irradiation time t(min) satisfying the relationship of the following formulas (1), (4) and (5), a semiconductor having the first protective film according to [4] or [5] How to make a chip.

A<at… (One)

D＞dt… (4)

E<dt… (5)

According to the present invention, by half-cut dicing a semiconductor wafer and then plasma irradiation, not only it becomes possible to dicing by plasma irradiation without covering the resist film, but also to remove the residue of the first protective film at the top of the bump, and the semiconductor wafer The reorganization of the product can be achieved at the same time, so the productivity is excellent. Further, after half-cut dicing, plasma irradiation and dicing are performed, so that the occurrence of chipping can be reduced, and chip strength can be improved.

1 is a schematic diagram schematically showing a first embodiment of a method for manufacturing a semiconductor chip with a first protective film of the present invention.
Fig. 2 is a schematic diagram schematically showing a first embodiment of a method for manufacturing a semiconductor chip with a first protective film of the present invention.
3 is a schematic diagram schematically showing a second embodiment of the method for manufacturing a semiconductor chip with a first protective film of the present invention.

<<Method of manufacturing semiconductor chip with first protective film>>

<First embodiment>

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

Meanwhile, in the drawings used in the following description, for convenience, in order to make it easier to understand the features of the present invention, the main part may be enlarged and shown, and the dimensional ratio of each component is not limited to the same as in reality. .

A method of manufacturing a semiconductor chip with a first protective film according to the first embodiment is a first protective film comprising a first support sheet 101 and a thermosetting resin film 12 provided on the first support sheet 101 The thermosetting resin film 12 of the forming sheet 1 (Fig. 1(a)) is formed on the side of the bump 91 of the semiconductor wafer 9 (Fig. 1(b)) having a bump 91. Attaching to one side (9a) (Fig. 1(c)),

Grinding the second surface 9b of the semiconductor wafer 9 opposite to the first surface 9a (Fig. 1(d)),

Attaching a dicing tape 14 to the ground second surface 9b of the semiconductor wafer 9 (Fig. 1(e)),

Peeling the first support sheet 101 from the thermosetting resin film 12 (Fig. 2(f)),

Thermosetting the thermosetting resin film 12 to form a first protective film 12' on the first surface of the semiconductor wafer 9 (Fig. 2(g)),

Half-cut dicing the semiconductor wafer 9 from the first surface side (Fig. 2(h)),

Plasma irradiation on the side of the first half-cut surface of the semiconductor wafer 9 removes the residue of the first protective film 12 ′ of the top 910 of the bump 91, and the semiconductor wafer 9 ) To reorganize (Fig. 2(i)).

First, as shown in Figs. 1(a) and 1(b), the first sheet 1 for forming a protective film is formed, and the thermosetting resin film 12 is applied to the first surface of the semiconductor wafer 9 on the bump side ( Arrange it so that it faces 9a) (it may be called a "bump formation surface").

The first protective film forming sheet 1 includes a thermosetting resin film 12 on the first support sheet 101. It is preferable that the first support sheet 101 includes a buffer layer 13 on the first substrate 11. That is, the sheet for forming a first protective film according to the present invention, as one side surface, includes a first support sheet and a thermosetting resin film provided on the first support sheet. As another aspect, the sheet for forming a first protective film according to the present invention includes a first substrate, a buffer layer provided on the first substrate, and a thermosetting resin film provided on the buffer layer.

Details of the first protective film forming sheet 1 will be described later.

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

In the meantime, in this specification, the ``height of the bump'' refers to the height at a portion of the bump that is at the highest position from the bump formation surface (that is, the vertical direction from the bump formation surface of the semiconductor wafer to the highest position of the bump). Means distance).

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.

On the other hand, in this specification, ``the width of a bump'' is the maximum of a line segment obtained by connecting two different points on the bump surface in a straight line when viewed in a plan view from a direction perpendicular to the bump formation surface. Means value.

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

In addition, in this specification, the "distance between mutually adjacent bumps" means the minimum value of the distance between the mutually adjacent bumps and between surfaces.

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 a semiconductor wafer" means the thickness of a semiconductor wafer, especially a semiconductor wafer after grinding.

"Thickness" in this specification is an average value of values measured by a static pressure thickness measuring device at 10 randomly selected locations, unless otherwise noted.

Next, the thermosetting resin film 12 is brought into contact with the bumps 91 on the semiconductor wafer 9, and the first sheet for forming a protective film 1 is pressed onto the semiconductor wafer 9. Thereby, the first surface 12a of the thermosetting resin film 12 is sequentially pressed against the surface 91a of the bump 91 and the first surface 9a of the semiconductor wafer 9. At this time, by heating the thermosetting resin film 12, the thermosetting resin film 12 is softened and spreads between the bumps 91 by covering the bumps 91, while being in close contact with the first surface 9a. , The surface 91a of the bump 91, in particular, the surface 91a in the vicinity of the first surface 9a of the semiconductor wafer 9 is covered, and the bump 91 is embedded.

As a method of compressing the first protective film-forming sheet 1 onto the semiconductor wafer 9, a known method in which various sheets are compressed and adhered to an object can be applied, for example, a method using a laminate roller. And the like.

The heating temperature of the first protective film-forming sheet 1 when it is pressed onto the semiconductor wafer 9 may be a temperature such that curing of the thermosetting resin film 12 does not proceed completely or excessively, and is 80 to 100°C. It is preferable that it is, and it is more preferable that it is 85-95 degreeC.

The pressure for 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 bump 91, Initially, the first surface 12a of the thermosetting resin film 12 is deformed into a concave shape.

As described above, the first protective film-forming sheet 1 is bonded to the first surface 9a of the semiconductor wafer 9 with the thermosetting resin film 12 (Fig. 1(c)).

Subsequently, if necessary, the second surface 9b (that is, the back surface) on the opposite side to the bump formation surface of the semiconductor wafer 9 is ground (Fig. 1(d)), and thereafter, a dicing sheet is applied to the back surface. Is attached (Fig. 1(e)). The dicing sheet may be provided with a second protective film forming film for forming a second protective film for protecting the semiconductor wafer and the back surface of the semiconductor chip by curing, for example.

Next, of the sheet 1 for forming a first protective film bonded to the first surface 9a of the semiconductor wafer 9, only the thermosetting resin film 12 is left on the first surface 9a, and the first support sheet 101 ) Is peeled from the thermosetting resin film 12 (Fig. 2(f)). Here, the "first support sheet 101" is, for example, the first substrate 11 and the buffer layer 13 in the case of the first protective film forming sheet 1 shown in FIG. 1.

On the other hand, in the manufacturing method of the semiconductor chip with the first protective film of the first embodiment, the embodiment using the first support sheet 101 as described above is shown, but if it can be in the form shown in Fig. 2(f) In addition, the process of FIGS. 1(a) to 1(d) is not essential, and any method may be employed.

Subsequently, the thermosetting resin film 12 is cured to form the first protective film 12' 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 diced (Fig. 2(h)). "Half-cut dicing" is a dicing method in which the semiconductor wafer 9 is not completely cut from the first protective film 12' side together with the first protective film 12'. The half-cut dicing method may be a method capable of half-cut dicing the semiconductor wafer 9 from the first protective film 12' side together with the first protective film 12', or blade dicing may be used. , Laser grooving may be used.

On the other hand, in the semiconductor chip manufacturing method of the present invention, each step of the semiconductor chip manufacturing method in which the first protective film of the first embodiment is formed may be performed in the above order, for example, the first protective film of the first embodiment. As a modification of the manufacturing method of the formed semiconductor chip, the thermosetting resin film of the first protective film forming sheet 1 (Fig. 1(a)) provided with a thermosetting resin film 12 on the first support sheet 101 (12) is affixed to the first surface 9a on the side of the bump 91 of the semiconductor wafer 9 having the bump 91 (Fig. 1(b)) (Fig. 1(c)),

Grinding the second surface 9b of the semiconductor wafer 9 opposite to the first surface 9a (Fig. 1(d)),

Attaching a dicing tape 14 to the ground second surface 9b of the semiconductor wafer 9 (Fig. 1(e)),

Peeling the first support sheet 101 from the thermosetting resin film 12 (Fig. 2(f)),

Dicing the semiconductor wafer (9) by half cut from the first surface side,

Thermosetting the thermosetting resin film 12 to form a first protective film 12' on the first surface of the semiconductor wafer 9 (Fig. 1(h)), and

Plasma irradiation on the side of the first half-cut surface of the semiconductor wafer 9 removes the residue of the first protective film 12 ′ of the top 910 of the bump 91, and the semiconductor wafer 9 ) Can be divided into pieces (Fig. 2(i)), and the method may perform each of the above steps in this order.

In addition, as a further modification of the method of manufacturing a semiconductor chip with the first protective film of the first embodiment, a thermosetting resin film 12 is used on the side of the bump 91 of the semiconductor wafer 9 having the bump 91. Attaching to one side (9a) (Fig. 2(f)),

Dicing the semiconductor wafer (9) by half cut from the first surface side,

Thermosetting the thermosetting resin film 12 to form a first protective film 12' on the first surface of the semiconductor wafer 9 (FIG. 2(h)), and

Plasma irradiation on the side of the first half-cut surface of the semiconductor wafer 9 removes the residue of the first protective film 12 ′ of the top 910 of the bump 91, and the semiconductor wafer 9 ) Can be divided into pieces (Fig. 2(i)), and the method may perform each of the above steps in this order.

The remaining thickness A of the half-cut portion of the semiconductor wafer (that is, the thickness excluding the half-cut portion from the thickness of the semiconductor wafer) is not particularly limited, but is preferably 1/5 to 4/5 of the thickness A ₀ of the semiconductor wafer. , more preferably from 1 / 4~3 / 4 of the thickness a _0, particularly preferably 1 / 3~2 / 3 of the thickness a _0. 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 on the side of the first half-cut surface of the semiconductor wafer 9 removes the residue of the first protective film 12 ′ of the top 910 of the bump 91, and the semiconductor wafer 9 ) Is reorganized (Fig. 2(i)). By half-cut dicing the semiconductor wafer 9 and then plasma irradiation, not only can dicing by plasma irradiation without covering the resist film, but also the first protective film 12 of the top portion 910 of the bump 91 ') residue removal and the individualization of the semiconductor wafer 9 can be achieved at the same time, and the productivity is excellent. Further, after half-cut dicing, plasma irradiation is applied to dicing, so that the occurrence of chipping can be reduced, and chip strength can be improved. In addition, the residue of the first protective film 12 ′ of the top portion 910 of the bump 91 may remain to be drawn into the recess formed in the top portion 910 of the bump 91. Since the residue of the first protective film 12' remaining in the concave portion of the top portion 910 of the bump 91 can also be removed by plasma irradiation, a semiconductor device having excellent connection reliability can be efficiently manufactured.

The plasma processing apparatus for performing plasma irradiation is not particularly limited, and a known plasma processing apparatus can be used. In addition, the plasma processing conditions are different depending on the type of the first protective film 12' and the semiconductor wafer 9, and are not particularly limited, but the half-cut portion of the semiconductor wafer with respect to the half-cut diced semiconductor wafer The remaining thickness A (µm) of the semiconductor wafer, and the thickness B (µm) of the first protective film on the first surface on the bump side of the semiconductor wafer (that is, the thickness of the first protective film in the bump-free portion on the semiconductor wafer) And, the thickness C (µm) of the first protective film on the top of the bump, the etching rate a (µm/min) of the semiconductor wafer by plasma irradiation, and the etching rate b (µm/m) of the first protective film by plasma irradiation. It is preferable that min) and the plasma irradiation time t(min) satisfy the relationship of the following formulas (1), (2), and (3).

A<at… (One)

B＞bt… (2)

C<bt… (3)

On the other hand, the remaining thickness A of the half-cut portion, the thickness B of the first protective film on the first surface on the bump side of the semiconductor wafer, and the thickness C of the first protective film on the top of the bump are within the range of the semiconductor chip to be obtained, It can be acquired as a value represented by the average of measuring the thickness by a scanning electron microscope at arbitrary five points.

In the present specification, the "etching rate" means the rate at which each object is etched when plasma is irradiated.

In the range of the semiconductor chip to be acquired, when there is a deviation in the thickness of the remaining half-cut portion, it is more preferable that the maximum value A'of the remaining thickness of the half-cut portion satisfies the equation (1)', and When there is a variation in the thickness of the first protective film on the first surface, it is more preferable that the minimum value B'of the thickness of the first protective film on the first surface on the bump side satisfies Equation (2)', and on the top of the bump When there is a variation in the thickness of the first protective film, it is more preferable that the maximum value C'of the thickness of the first protective film on the top of the bump satisfies the equation (3)'.

A'<at… (One)'

B'＞bt… (2)'

C'<bt… (3)'

Preferably, by satisfying the relationship of formula (1), formula (2) and formula (3), more preferably, the relationship of formula (1)', formula (2)' and formula (3)', time The semiconductor wafer after the plasma irradiation of t(min) is divided into pieces, the thickness of the first protective film on the first surface on the bump side becomes B-bt>0, and a semiconductor chip on which the first protective film protecting the bump formation surface is formed is formed. Can be obtained.

As the irradiation gas in plasma irradiation, a fluorine-based stable gas (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. And SF ₆ , CF ₄ or CHF ₃ are preferred from the viewpoint of excellent etching properties of a semiconductor wafer.

The plasma power condition is preferably 100 to 8000 W.

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

Since the first 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 is the thickness B (µm) of the first protective film on the first surface on the bump side of the semiconductor wafer It becomes thinner. The semiconductor wafer is easily etched by plasma irradiation, whereas the first protective film is made of a thermosetting resin, so the etching rate a (µm/min) of the semiconductor wafer by plasma irradiation is the first protective film by plasma irradiation. Is sufficiently larger than the etching rate b (µm/min) of. Therefore, by adjusting the plasma irradiation time t(min), it is possible to easily adjust the conditions of plasma irradiation satisfying the relationship of the above equations (1), (2) and (3).

For example, the thickness B of the first protective film on the first surface on the bump side of the semiconductor wafer is 30 µm, the thickness C of the first protective film on the top of the bump is 3 µm, and the remaining thickness for a semiconductor wafer having a thickness of 100 µm. A half-cut to 50 µm and plasma irradiation under the conditions of plasma irradiation gas: SF ₆ and plasma power: 2000 W enables the etching rate a of the semiconductor wafer to be 15 μm/min, and the etching rate b of the first protective film Can be set to 1.5 µm/min, and the relationship of the above formulas (1), (2) and (3) is satisfied.

Thereafter, the semiconductor device can be manufactured by the same method as the conventional method. That is, the semiconductor chip on which the first protective film is formed is picked up, the picked up semiconductor chip is flip-chip mounted on the wiring board, and finally a semiconductor device is manufactured.

<2nd embodiment>

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

The manufacturing method of the semiconductor chip with the 1st protective film of 2nd embodiment is attaching the thermosetting resin film 12 to the bump side 1st surface of the semiconductor wafer 9 which has bumps (FIG. 3(f)) ),

Half-cut dicing the semiconductor wafer 9 from the first surface side (Fig. 3(g')),

Plasma irradiation on the side of the first half-cut surface of the semiconductor wafer 9 to remove the thermosetting resin film 12 at the top of the bump and to separate the semiconductor wafer 9 (Fig. 3(h')) ), and

A semiconductor in which a first protective film is formed, including forming a first protective film 12' on the first surface of the semiconductor wafer 9 by thermosetting the thermosetting resin film 12 (Fig. 3(i')) It is a method of manufacturing a chip.

On the other hand, in the method of manufacturing a semiconductor chip with a first protective film according to the second embodiment, as a method in the form shown in Fig. 3(f), Figs. 1(a), 1(b), and 1(c) , The process passing through FIGS. 1(d) and 3(f) is mentioned, but the process of FIGS. 1(a) to 1(d) is not essential, and any method may be employed.

Plasma irradiation on the side of the first half-cut surface of the semiconductor wafer 9 to remove the residue of the thermosetting resin film 12 on the top 910 of the bump 91, and the semiconductor wafer 9 It is reorganized (Fig. 3(h')). By half-cut dicing the semiconductor wafer 9 and then plasma irradiation, not only can dicing by plasma irradiation without covering the resist film, but also the thermosetting resin film 12 of the top 910 of the bump 91 It is possible to simultaneously achieve the removal of the residue of the semiconductor wafer and the reorganization of the semiconductor wafer 9, which is excellent in productivity. Further, after half-cut dicing, plasma irradiation and dicing are performed, so that the occurrence of chipping can be reduced, and chip strength can be improved. In addition, the residue of the thermosetting resin film 12 of the top portion 910 of the bump 91 may remain so as to be drawn into a recess formed in the top portion 910 of the bump 91. Since the residue of the thermosetting resin film 12 remaining in the concave portion of the top portion 910 of the bump 91 can also be removed by plasma irradiation, a semiconductor device having excellent connection reliability can be efficiently manufactured.

The plasma processing apparatus for performing plasma irradiation is not particularly limited, and a known plasma processing apparatus can be used. In addition, the plasma processing conditions are different depending on the type of the thermosetting resin film 12 and the semiconductor wafer 9, and are not particularly limited, but for the half-cut diced semiconductor wafer, the half-cut portion of the semiconductor wafer The remaining thickness A (µm) and the thickness D (µm) of the thermosetting resin film 12 on the first side of the bump side of the semiconductor wafer (that is, the thermosetting resin film in the bump-free portion on the semiconductor wafer) Thickness), 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 thermosetting resin film 12 by plasma irradiation. It is preferable that the etching rate d (µm/min) of) and the plasma irradiation time t (min) satisfy the relationship of the following formulas (1), (4), and (5).

A<at… (One)

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 are within the range of the semiconductor chip to be obtained. It can be acquired as a value represented by the average of measuring thickness by a scanning electron microscope at arbitrary five places.

In the range of the semiconductor chip to be acquired, when there is a deviation in the thickness of the remaining half-cut portion, it is more preferable that the maximum value A'of the remaining thickness of the half-cut portion satisfies the equation (1)', and When there is a variation in the thickness of the thermosetting resin film 12 on the first side, it is more preferable that the minimum value D'of the thickness of the thermosetting resin film 12 on the first side on the bump side satisfies the formula (4)', and , When there is a variation in the thickness of the first protective film on the top of the bump, it is more preferable that the maximum value E'of the thickness of the thermosetting resin film 12 on the top of the bump satisfies the formula (5)'.

A'<at… (One)'

D'＞bt… (4)'

E'<bt… (5)'

Preferably, by satisfying the relationship of formula (1), formula (4) and formula (5), more preferably, by satisfying the relationship of formula (1)', formula (4)' and formula (5)', time The semiconductor wafer after the plasma irradiation of t(min) is divided into pieces, the thickness of the first protective film on the first surface on the bump side becomes D-dt>0, and a semiconductor chip on which the first protective film protecting the bump formation surface is formed is formed. Can be obtained.

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

Since the first protective film on the 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 is the thermosetting resin film 12 on the first side of the bump side of the semiconductor wafer. It becomes thinner than the thickness D (㎛). Since the semiconductor wafer is easily etched by plasma irradiation, the etching rate a (µm/min) of the semiconductor wafer by plasma irradiation is sufficiently higher than the etching rate d (µm/min) of the thermosetting resin film 12 by plasma irradiation. Big. Therefore, by adjusting the plasma irradiation time t(min), it is possible to easily adjust the conditions of plasma irradiation satisfying the relationship of the above equations (1), (4) and (5).

For example, the thickness D of the thermosetting resin film 12 on the first surface of 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 is 100 µm. With respect to the wafer, the remaining thickness A is half-cut to 50 µm, and plasma irradiation under the conditions of plasma irradiation gas: SF ₆ and plasma power: 2000 W allows the etching rate a of the semiconductor wafer to be 15 µm/min, The etching rate d of the thermosetting resin film 12 can be set to 1.5 µm/min, and the relationship of the above formulas (1), (4) and (5) is satisfied.

Thereafter, the semiconductor device can be manufactured by the same method as the conventional method. That is, the semiconductor chip on which the first protective film is formed is picked up, the picked up semiconductor chip is flip-chip mounted on the wiring board, and finally a semiconductor device is manufactured.

◎ Sheet for forming the first protective film

1(a) is a cross-sectional view schematically showing 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 surface 101a of the first support sheet 101 Includes. More specifically, the first protective film forming sheet 1 includes a first substrate 11, a buffer layer 13 provided on the first substrate 11, and a thermosetting resin provided on the buffer layer 13. The film 12 is included, and the first base material 11 and the buffer layer 13 constitute the first support sheet 101.

The first protective film-forming sheet is not limited to that shown in Fig. 1(a), and within the range not impairing the effects of the present invention, in Fig. 1(a), some configurations are changed, deleted, or It may be added.

Next, each layer constituting the first protective film-forming sheet will be described.

◎ Thermosetting resin film

The thermosetting resin film is used to protect a first surface (ie, a bump formation surface) on the bump side of a semiconductor wafer, and a bump formed on the bump formation surface.

The thermosetting resin film of the present invention is the same as a conventional resin film, and softens by heating, but is thermosetting by further heating, and the thermosetting resin film is returned to room temperature after thermosetting than the thermosetting resin film at room temperature (23°C) before thermosetting. When it has the property of becoming solid. Accordingly, 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 the constituent material is not particularly limited.

The thermosetting resin film may have only one layer (single layer), or may be a plurality of layers of two or more layers, and in the case of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.

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 lower limit, the first protective film having a higher protective ability can be formed.

Further, since the thickness of the thermosetting resin film is less than or equal to the above upper limit, excessive thickness is suppressed.

Here, the "thickness of the thermosetting resin film" means the thickness of the entire thermosetting resin film, for example, the thickness of the thermosetting resin film consisting of multiple layers means the total thickness of all layers constituting the thermosetting resin film. .

◎First protective film

The first protective film is a film formed by heat curing on a first surface (ie, a bump formation surface) on the bump side of a semiconductor wafer, and a bump formed on the bump formation surface.

The thickness B (µm) of the first protective film on the first surface on the bump side of the semiconductor wafer (that is, the thickness of the first protective film in the bump-free portion on the semiconductor wafer) is the same as the thickness of the thermosetting resin film. 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 is the thickness of the thermosetting resin film, that is, the first protective film on the first surface on the bump side of the semiconductor wafer. 1 It becomes thinner than the thickness B (㎛) of the protective film. 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.

<<Composition for thermosetting resin film formation>>

The thermosetting resin film can be formed from a composition for forming a thermosetting resin film containing the constituent material. For example, by coating a composition for forming a thermosetting resin film on a surface to be formed of a thermosetting resin film and drying as necessary, a thermosetting resin film can be formed at a target site. A more specific formation method of the thermosetting resin film will be described in detail next together with the formation method of other layers. In the composition for forming a thermosetting resin film, the ratio of the content of the components that do not vaporize at room temperature (23°C) is usually the same as the ratio of the content of the components of the thermosetting resin film.

Coating of the composition for forming a thermosetting resin film may be performed by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater , A screen coater, a Mayer bar coater, and a method of using various coaters such as a kiss coater.

Drying conditions of the composition for forming a thermosetting resin film are not particularly limited, but when the composition for forming a thermosetting resin film contains a solvent to be described later, it is preferable to heat-dry. In this case, for example, at 70 to 130°C. It is preferable to dry under the conditions of 10 seconds to 5 minutes.

<Composition for resin layer formation>

As a composition for forming a thermosetting resin film, for example, a composition for forming a thermosetting resin film containing a polymer component (A) and a thermosetting component (B) (in this specification, simply abbreviated as ``resin layer forming composition'' There are cases) and the like.

[Polymer component (A)]

The polymer component (A) is a polymer compound for imparting film-forming properties or flexibility to the thermosetting resin film, and is a component that can be considered to have been formed by a polymerization reaction of the polymerizable compound. In addition, in this specification, a polycondensation reaction is also included in a polymerization reaction.

The composition for forming a resin layer and the polymer component (A) contained in the thermosetting resin film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

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

As said polyvinyl acetal in the polymer component (A), a well-known thing is mentioned.

Among these, examples of preferable polyvinyl acetal include polyvinyl formal, polyvinyl butyral, and more, and polyvinyl butyral is more preferable.

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 , m ₁ and n ₁ are the content ratio (mol%) of each structural unit to the total number of moles of all structural units constituting polyvinyl butyral)

It is preferable that it is 5000-200000, and, as for the weight average molecular weight (Mw) of polyvinyl acetal, it is more preferable that it is 8000-100000.

The content ratio l ₁ (degree of butyralization) of the structural unit having a butyral group is preferably 40 to 90 mol%, more preferably 50 to 85 mol%, based on the total number of moles of all the structural units constituting polyvinyl butyral. , 60 to 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 to 7 mol% with respect to the total number of moles of all the structural units constituting polyvinyl butyral. It is particularly preferred.

The content ratio n ₁ of the structural unit having a hydroxyl group is preferably 10 to 60 mol%, more preferably 10 to 50 mol%, and 20 to 40 mol% with respect to the total number of moles of all the structural units constituting polyvinyl butyral. It is particularly preferred.

It is preferable that it is 40-80 degreeC, and, as for the glass transition temperature (Tg) of polyvinyl acetal, it is more preferable that it is 50-70 degreeC.

The glass transition temperature can be, for example, measured by a differential scanning calorimetry device (manufactured by TA Instruments Japan, product name "DSC Q2000") at a rate of temperature increase and decrease of 20°C/min. .

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

Known acrylic polymers can be mentioned as the acrylic resin in the polymer component (A).

It is preferable that it is 10000-2000000, and, as for the weight average molecular weight (Mw) of an acrylic resin, it is more preferable that it is 100000-150,000. Since the weight average molecular weight of the acrylic resin is more than the above lower limit, the shape stability of the thermosetting resin layer (stability with time during storage) is improved. Further, since the weight average molecular weight of the acrylic resin is less than or equal to the above upper limit, the thermosetting resin layer is easily followed by the uneven surface of the adherend, and the occurrence of voids and the like between the adherend and the thermosetting resin layer is more suppressed.

In addition, in this specification, a "weight average molecular weight" means a polystyrene conversion value measured by a gel permeation chromatography (GPC) method, unless otherwise noted.

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

Examples of the acrylic resin include polymers of one or two or more (meth)acrylic acid esters; In addition to (meth)acrylic acid ester, copolymers obtained by copolymerization of one or two or more monomers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene and N-methylolacrylamide, etc. are mentioned. have.

Examples of the (meth)acrylic acid ester constituting the acrylic resin include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n (meth)acrylate. -Butyl, (meth) isobutyl acrylate, (meth) acrylate sec-butyl, (meth) acrylate tert-butyl, (meth) acrylate, (meth) hexyl acrylate, (meth) heptyl acrylate, (meth) acrylate 2- Ethylhexyl, (meth) acrylate isooctyl, (meth) acrylate n-octyl, (meth) acrylate n-nonyl, (meth) acrylate isononyl, (meth) acrylate, (meth) acrylate, (meth) Dodecyl acrylate (also referred to as (meth) lauryl acrylate), Tridecyl (meth) acrylate, tetradecyl (meth) acrylate (also referred to as myristol (meth) acrylate), pentadecyl (meth) acrylate, hexa (meth) acrylate An alkyl group constituting an alkyl ester such as decyl (also referred to as palmityl ((meth)acrylate), heptadecyl (meth)acrylate, and octadecyl (meth)acrylate (also referred to as stearyl (meth)acrylate)) has 1 to 18 carbon atoms. (Meth)acrylate alkyl ester having a phosphorus chain structure;

(Meth)acrylic acid cycloalkyl esters such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate;

(Meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate;

(Meth) acrylate cycloalkenyl ester, such as (meth) acrylate dicyclopentenyl ester;

(Meth)acrylate cycloalkenyloxyalkyl esters such as dicyclopentenyloxyethyl (meth)acrylate;

Imide (meth)acrylate;

Glycidyl group-containing (meth)acrylic acid esters such as glycidyl (meth)acrylate;

Hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth) ) Hydroxyl group-containing (meth)acrylic acid esters such as 3-hydroxybutyl acrylic acid and 4-hydroxybutyl (meth)acrylate;

And substituted amino group-containing (meth)acrylic acid esters such as N-methylaminoethyl (meth)acrylate.

Here, the "substituted amino group" means a group obtained by substituting one or two hydrogen atoms of an amino group with a group other than a hydrogen atom.

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

The number of monomers constituting the acrylic resin may be only one, or may be two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

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

In the present invention, for example, as the polymer component (A), thermoplastic resins other than polyvinyl acetal and acrylic resin (hereinafter, simply abbreviated as ``thermoplastic resin'' may be used), polyvinyl acetal and acrylic resin It is not used and may be used alone, or may be used in combination with polyvinyl acetal or acrylic resin. By using the thermoplastic resin, the peelability of the first protective film from the first support sheet is improved, or the thermosetting resin film is easily followed by the uneven surface of the adherend, and voids, etc. are generated between the adherend and the thermosetting resin film. It may be suppressed more than this.

It is preferable that it is 1000-100000, and, as for the weight average molecular weight of the said thermoplastic resin, it is more preferable that it is 3000-80000.

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

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

The thermoplastic resins contained in the composition for forming a resin layer and the thermosetting resin film may be one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

In the composition for forming a resin layer, the ratio of the content of the polymer component (A) to the total content (total mass) of all components other than the solvent (that is, the content of the polymer component (A) of the thermosetting resin film) is the polymer component Regardless of the kind of (A), it is preferably 5 to 85% by mass, more preferably 5 to 80% by mass, for example, 5 to 70% by mass, 5 to 60% by mass, and 5 to 50% by mass Any of 5 to 40 mass%, and 5 to 30 mass% may be used. However, these contents in the composition for resin layer formation are an example.

The polymer component (A) is also applicable to the thermosetting component (B) in some cases. In the present invention, when the composition for forming a resin layer contains components corresponding to both of such a polymer component (A) and a thermosetting component (B), the composition for forming a resin layer is a polymer component (A) and a thermosetting component ( It is considered to contain B).

[Thermosetting component (B)]

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

The composition for forming a resin layer and the thermosetting component (B) contained in the thermosetting resin film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

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

(Epoxy thermosetting resin)

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

The composition for forming a resin layer and the epoxy-based thermosetting resin contained in the thermosetting resin film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

Epoxy resin (B1)

Examples of the epoxy resin (B1) include known ones, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ethers and their hydrogenated products, orthocresol novolac epoxy resins, dicyclopenta A diene type epoxy resin, a biphenyl type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a phenylene skeleton type epoxy resin, and other bifunctional or higher epoxy compounds.

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group may be used. The epoxy resin having an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. For this reason, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the first composite sheet for forming a protective film is improved.

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

Further, examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to the aromatic ring constituting the epoxy resin, for example.

The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (also referred to as vinyl group), 2-propenyl group (also referred to as allyl group), (meth)acryloyl group, (meth)acrylamide group, etc. And acryloyl groups are preferred.

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

The lower limit of the weight average molecular weight of the epoxy resin (B1) is not particularly limited. However, from the viewpoint of further 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.

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

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

In the present specification, the "number average molecular weight" means a number average molecular weight expressed in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method unless otherwise noted.

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

In this specification, "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing 1 equivalent of an epoxy group, and can be measured by the method of JIS K 7236: 2001.

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

Epoxy resin (B1) may be used individually by 1 type, may use 2 or more types together, and when 2 or more types are used together, these combinations and ratios can be selected arbitrarily.

·Heat curing agent (B2)

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

Examples of the thermosetting agent (B2) include a compound having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, a group in which an acid group is anhydride, and the like, and a phenolic hydroxyl group, an amino group, or an acid group is preferably an anhydride group. It is more preferable that it is a sexual hydroxyl group or an amino group.

Among the thermal curing agents (B2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenols, novolac phenolic resins, dicyclopentadiene phenolic resins, aralkyl phenolic resins, etc. Can be lifted.

Among the thermal curing agents (B2), examples of the amine curing agent having an amino group include dicyandiamide (in this specification, abbreviated as "DICY" in some cases) and the like.

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

As the thermosetting agent (B2) having an unsaturated hydrocarbon group, for example, a compound obtained by substituting a group having an unsaturated hydrocarbon group in a part of the hydroxyl group of the phenol resin, a compound obtained by directly bonding a group having an unsaturated hydrocarbon group to the aromatic ring of the phenol resin, Can be lifted.

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

When a phenolic curing agent is used as the thermal curing agent (B2), it is preferable that the thermal curing agent (B2) has a high softening point or glass transition temperature from the viewpoint of improving the peelability of the first protective film from the first support sheet.

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, and aralkyl type phenol resin is preferably 300 to 30000. And, it is more preferable that it is 400-10000, and it is especially preferable that it is 500-3000.

Among the thermosetting agents (B2), for example, the molecular weight of the non-resin component such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

The thermosetting agent (B2) may be used singly or in combination of two or more, and when two or more of them are used in combination, combinations and ratios thereof can be arbitrarily selected.

In the composition for forming a resin layer and the thermosetting resin film, the content of the thermosetting agent (B2) is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass, based on 100 parts by mass of the epoxy resin (B1). It is preferable and, for example, 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 may be used. Since the content of the thermosetting agent (B2) is equal to or greater than the lower limit, curing of the thermosetting resin film is more likely to proceed. Further, since the content of the thermosetting agent (B2) is less than or equal to the upper limit, the moisture absorption rate of the thermosetting resin film is reduced, and the reliability of the package obtained by using the first protective film is further improved.

In the composition for forming a resin layer and the thermosetting resin film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is 100 mass of the polymer component (A). It is preferably 50 to 1000 parts by mass, more preferably 60 to 950 parts by mass, and particularly preferably 70 to 900 parts by mass with respect to parts. When the content of the thermosetting component (B) is within such a range, the adhesive force between the first protective film and the first support sheet is suppressed, and the peelability of the first support sheet is improved.

[Hardening accelerator (C)]

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

Preferred curing accelerators (C) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 -Imidazoles such as hydroxymethylimidazole (that is, imidazole in which at least one hydrogen atom is substituted with a group other than a hydrogen atom); Organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (that is, phosphine in which at least one hydrogen atom is substituted with an organic group); And tetraphenyl boron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate.

The composition for forming a resin layer and the curing accelerator (C) contained in the thermosetting resin film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

When using a curing accelerator (C), in the composition for forming a resin layer and a thermosetting resin film, the content of the curing accelerator (C) is 0.01 to 10 parts by mass based on 100 parts by mass of the thermosetting component (B). It is preferable and it is more preferable that it is 0.1-5 mass parts. Since the content of the curing accelerator (C) is more than the lower limit, the effect of using the curing accelerator (C) is more remarkably obtained. In addition, since the content of the curing accelerator (C) is less than or equal to the above upper limit, for example, the curing accelerator (C) of high polarity moves to the side of the adhesion interface with the adherend in the thermosetting resin film under high temperature and high humidity conditions and segregates. The effect of suppressing the formation of the first protective film is enhanced, and the reliability of the package obtained using the first sheet for forming a protective film is further improved.

[Filling material (D)]

The composition for resin layer formation and the thermosetting resin film may contain a filler (D). When the thermosetting resin film contains the filler (D), the first protective film obtained by curing the thermosetting resin film becomes easy to adjust the thermal expansion coefficient. And, by optimizing this coefficient of thermal expansion for the object for which the first protective film is to be formed, the reliability of the package obtained by using the first protective film-forming sheet is further improved. In addition, when the thermosetting resin film contains the filler (D), the moisture absorption rate of the first protective film can be reduced or the heat dissipation property can be improved.

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

Preferred inorganic fillers include, for example, powders such as silica, alumina, talc, calcium carbonate, titanium white, bengala, silicon carbide and boron nitride; Beads in which these inorganic fillers are spheroidized; Surface modified products of these inorganic fillers; Single crystal fibers of these inorganic fillers; Glass fiber, etc. are mentioned.

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

The composition for forming a resin layer and the filler (D) contained in the thermosetting resin film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

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

In addition, in this specification, the "average particle diameter" means the value of the particle diameter (D ₅₀ ) in the integrated value 50% in the particle size distribution curve calculated by the laser diffraction scattering method, unless otherwise noted. .

The lower limit of the average particle diameter of the filler (D) is not particularly limited. For example, the average particle diameter of the filler (D) is preferably 0.01 µm or more from the point that the filler (D) is more readily available. As an aspect, the average particle diameter of the filler (D) is preferably 0.01 μm or more and 1 μm or less, more preferably 0.01 μm or more and 0.5 μm or less, and particularly preferably 0.01 μm or more and 0.1 μm or less.

When using the filler (D), in the composition for forming a resin layer, the ratio of the content of the filler (D) to the total content (total mass) of all components other than the solvent (that is, the filler (D) of the thermosetting resin film) It is preferable that it is 3 to 60 mass %, and, as for content), it is more preferable that it is 3 to 55 mass %.

[Coupling agent (E)]

The composition for resin layer formation and the thermosetting resin film may contain a coupling agent (E). As the coupling agent (E), by using an inorganic compound or a functional group capable of reacting with an organic compound, the adhesiveness and adhesion of the thermosetting resin film to the adherend can be improved. Further, by using the coupling agent (E), the first protective film obtained by curing the thermosetting resin film does not impair heat resistance and improves water resistance.

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

Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3- Glycidyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyl Triethoxysilane, vinyl trimethoxysilane, vinyl triacetoxysilane, imidazole silane, etc. are mentioned.

The composition for forming a resin layer and the coupling agent (E) contained in the thermosetting resin film may be one type or may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

When using the coupling agent (E), in the composition for forming a resin layer and the thermosetting resin film, the content of the coupling agent (E) was 100 parts by mass as the total content of the polymer component (A) and the thermosetting component (B). In this case, it is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass.

Since the content of the coupling agent (E) is greater than or equal to the lower limit, the use of the coupling agent (E), such as improving the dispersibility of the filler (D) in the resin, and improving the adhesion of the thermosetting resin film to the adherend, etc. The effect is obtained more remarkably. Further, since the content of the coupling agent (E) is less than or equal to the upper limit, generation of outgas is more suppressed.

[Crosslinking agent (F)]

In the case of using a polymer component (A) having a functional group such as a vinyl group, (meth)acryloyl group, amino group, hydroxyl group, carboxyl group, isocyanate group, etc. that can be bonded to other compounds such as acrylic resin described above is used, for forming a resin layer The composition and the thermosetting resin film may contain a crosslinking agent (F). The crosslinking agent (F) is a component for crosslinking by combining the functional group with another compound in the polymer component (A), and by crosslinking in this manner, the initial adhesive force and cohesive force of the thermosetting resin film can be adjusted.

As the crosslinking agent (F), for example, an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate type crosslinking agent (ie, a crosslinking agent having a metal chelate structure), an aziridine type crosslinking agent (ie, a crosslinking agent having an aziridinyl group), etc. Can be lifted.

As the organic polyvalent isocyanate compound, for example, an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds may be included and abbreviated as "aromatic polyvalent isocyanate compound etc." in some cases); Trimers, isocyanurates, and adducts such as the aromatic polyvalent isocyanate compounds; And a terminal isocyanate urethane prepolymer obtained by reacting the above aromatic polyvalent isocyanate compound and the like with a polyol compound. The ``adduct body'' is an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound or an alicyclic polyvalent isocyanate compound, a low molecular weight active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, and Means the reactant of. Examples of the adduct body include a xylylene diisocyanate adduct of trimethylolpropane described later, and the like. In addition, the "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the terminal portion of the molecule.

As the organic polyvalent isocyanate compound, more specifically, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; Diphenylmethane-4,4'-diisocyanate; Diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; Hexamethylene diisocyanate; Isophorone diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; Compounds in which any one or two or more of tolylene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate are added to all or part of the hydroxyl groups of polyols such as trimethylolpropane; Lysine diisocyanate, etc. are mentioned.

As the organic polyvalent imine compound, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxyamide), trimethylolpropane-tri-β-aziridinylpropionate , Tetramethylolmethane-tri-β-aziridinylpropionate, N,N'-toluene-2,4-bis(1-aziridinecarboxyamide)triethylene melamine, and the like.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A). When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the crosslinking structure can be conveniently introduced into the thermosetting resin film by reaction of the crosslinking agent (F) and the polymer component (A).

The composition for forming a resin layer and the crosslinking agent (F) contained in the thermosetting resin film may be one type or may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

When using the crosslinking agent (F), in the composition for forming a resin layer, the content of the crosslinking agent (F) is preferably 0.01 to 20 parts by mass, and 0.1 to 10 parts by mass based on 100 parts by mass of the polymer component (A). It is more preferable that it is a mass part, and it is especially preferable that it is 0.5-5 mass parts. Since the content of the crosslinking agent (F) is more than the lower limit, the effect of using the crosslinking agent (F) is more remarkably obtained. Further, since the content of the crosslinking agent (F) is less than or equal to the upper limit, excessive use of the crosslinking agent (F) is suppressed.

[Other ingredients]

The composition for forming a resin layer and the thermosetting resin film are the polymer component (A), thermosetting component (B), curing accelerator (C), filler (D), and coupling agent described above within a range that does not impair the effects of the present invention. You may further contain components other than (E) and a crosslinking agent (F).

As said other component, an energy ray-curable resin, a photoinitiator, a colorant, a general-purpose additive, etc. are mentioned, for example. The general-purpose additives are known and may be arbitrarily selected according to the purpose, and are not particularly limited, but preferred ones include, for example, plasticizers, antistatic agents, antioxidants, coloring agents (dyes, pigments), gettering agents, etc. Can be lifted.

The composition for forming a resin layer and the other components contained in the thermosetting resin film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

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

The composition for forming a resin layer and the thermosetting resin film contain a polymer component (A) and a thermosetting component (B), contain polyvinyl acetal as a polymer component (A), and contain a liquid as an epoxy resin (B1). It is preferable to do, and it is more preferable to contain a hardening accelerator (C) and a filler (D) in addition to these components. And, it is preferable that the filler (D) in this case has the average particle diameter mentioned above.

[menstruum]

It is preferable that the composition for resin layer formation further contains a solvent. The composition for forming a resin layer containing a solvent has good handleability.

The solvent is not particularly limited, but preferred examples thereof include, for example, hydrocarbons such as toluene and xylene; Alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (also referred to as 2-methylpropan-1-ol), and 1-butanol; Esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran; And amides such as dimethylformamide and N-methylpyrrolidone (that is, a compound having an amide bond).

The number of solvents contained in the composition for forming a resin layer may be only one type, or may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

The solvent contained in the composition for forming a resin layer is preferably methyl ethyl ketone or the like from the viewpoint that the components contained in the composition for forming a resin layer can be more uniformly mixed.

The content of the solvent in the composition for forming a resin layer is not particularly limited, and for example, it may be appropriately selected according to the kind of components other than the solvent.

<<The manufacturing method of the composition for thermosetting resin film formation>>

A composition for forming a thermosetting resin film, such as a composition for forming a resin layer, is obtained by blending each component for constituting it.

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

In the case of using a solvent, the solvent may be mixed with any compounding component other than the solvent, and the compounded component may be used by diluting it in advance, and the solvent is not previously diluted with any of the compounding components other than the solvent. You may use by mixing with.

A method of mixing each component during mixing is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc.; Mixing using a mixer; What is necessary is just to select appropriately from known methods, such as a method of applying ultrasonic waves and mixing.

The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30°C.

◎First support sheet

In the first sheet 1 for forming a protective film, a known one can be used as the first support sheet 101. For example, the first support sheet 101 is configured with a first base material 11 and a buffer layer 13 formed on the first base material 11. That is, the 1st protective film formation sheet 1 is comprised by the 1st base material 11, the buffer layer 13, and the thermosetting resin film 12 laminated|stacked in these thickness directions in this order.

◎First description

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

Examples of the resin include polyethylenes such as low-density polyethylene (sometimes abbreviated as LDPE), linear low-density polyethylene (sometimes abbreviated as LLDPE), and high-density polyethylene (sometimes abbreviated as HDPE); Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene and norbornene resin; Ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, and ethylene-norbornene copolymer (copolymer obtained using ethylene as a monomer) ; Vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymer (resins obtained using vinyl chloride as a monomer); polystyrene; Polycycloolefin; Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, and wholly aromatic polyesters in which all structural units have aromatic cyclic groups; A copolymer of two or more of the above polyesters; Poly(meth)acrylic acid ester; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluororesin; Polyacetal; Modified polyphenylene oxide; Polyphenylene sulfide; Polysulfone; Polyether ketone, etc. are mentioned.

Moreover, as said resin, polymer alloys, such as a mixture of said polyester and resin other than that, are also mentioned, for example. It is preferable that the polymer alloy of the polyester and other resins has a relatively small amount of resin other than polyester.

Further, as the resin, for example, a crosslinked resin in which one or two or more of the resins exemplified so far is crosslinked; Modified resins such as ionomers using one or two or more of the resins exemplified so far can also be mentioned.

The resin constituting the first base material may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

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

On the other hand, in the present specification, it is not limited to the case of the first substrate, and "the multiple layers may be the same or different from each other" means "all the layers may be the same, all layers may be different, and only some of the layers are the same. It means "may be good", and further "the multiple layers are different from each other" means "at least one of the constituent materials and thicknesses of each layer are different from each other".

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

Here, the "thickness of the first substrate" means the thickness of the entire first substrate, for example, the thickness of the first substrate consisting of a plurality of layers means the total thickness of all the layers constituting the first substrate. .

It is preferable that the 1st base material has high precision of thickness, that is, the variation in thickness is suppressed irrespective of a part. Among the above-described constituent materials, examples of materials that can be used for constituting the first substrate with such a high accuracy in thickness include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymer. have.

The first substrate may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers) in addition to the main constituent materials such as the resin.

The first substrate may be transparent or opaque, may be colored depending on the purpose, or may be deposited with another layer.

When the thermosetting resin film is energy ray-curable, it is preferable that the first substrate transmits energy rays.

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

◎ Peel film

The release film may be known in this field.

As a preferable release film, for example, at least one surface of a resin film such as polyethylene terephthalate has been subjected to a release treatment by silicone treatment or the like; At least one surface of the film is a peeling surface composed of polyolefin, and the like.

It is preferable that the thickness of the release film is the same as that of the first substrate.

◎Buffer layer

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

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

As a constituent material of the buffer layer 13, various adhesive resins are mentioned, for example. Examples of the adhesive resin include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers and polycarbonates, and acrylic resins are preferable. When the buffer layer 13 is energy ray-curable, the constituent material includes various components required for energy ray curing.

On the other hand, in the present invention, the "adhesive resin" is a concept including both a resin having adhesiveness and a resin having adhesiveness, for example, not only the resin itself has adhesiveness, but also other components such as additives A resin that exhibits adhesiveness when used in combination with, and a resin that exhibits adhesiveness by the presence of a trigger such as heat or water are also included.

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

It is preferable that the thickness of the buffer layer 13 is 30 to 500 μm.

Here, the "thickness of the buffer layer 13" means the total thickness of the buffer layer 13, for example, the thickness of the buffer layer 13 made of a plurality of layers is the sum of all layers constituting the buffer layer 13 Means thickness.

<<adhesive resin composition>>

The buffer layer 13 can be formed from an adhesive resin composition containing an adhesive resin. For example, by coating the adhesive resin composition on the surface to be formed of the buffer layer 13 and drying it as necessary, the buffer layer 13 can be formed on a target site.

Coating of the adhesive resin composition may be performed by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater , A method of using various coaters such as a Mayer bar coater and a kiss coater.

Although drying conditions of the adhesive resin composition are not particularly limited, it is preferable to heat-dry the adhesive resin composition containing a solvent described later. It is preferable to dry the adhesive resin composition containing a solvent under the conditions of 10 seconds-5 minutes at 70-130 degreeC, for example.

When the buffer layer 13 is energy ray-curable, the adhesive resin composition containing the energy ray-curable adhesive, that is, the energy ray-curable adhesive resin composition, includes, for example, a non-energy ray-curable adhesive resin (I-1a) (hereinafter , An adhesive resin composition (I-1) containing an energy ray-curable compound (may be abbreviated as "adhesive resin (I-1a)"); Containing an energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the non-energy ray-curable adhesive resin (I-1a) (hereinafter, it may be abbreviated as ``adhesive resin (I-2a)'') Adhesive resin composition (I-2); The adhesive resin (I-2a) and the adhesive resin composition (I-3) containing an energy ray-curable low molecular weight compound, and the like can be mentioned.

As an adhesive resin composition, in addition to an energy ray-curable adhesive resin composition, a non-energy ray-curable adhesive resin composition is also mentioned.

Examples of the non-energy ray-curable adhesive resin composition include non-energy ray-curable adhesive resins such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin, etc. The adhesive resin composition (I-4) containing -1a) is mentioned, and it is preferable to contain an acrylic resin.

<<the manufacturing method of an adhesive resin composition>>

The adhesive resin composition, such as adhesive resin composition (I-1) to (I-4), contains the adhesive resin and, if necessary, each component for constituting an adhesive resin composition such as components other than the adhesive resin. It is obtained by doing.

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

In the case of using a solvent, the solvent may be mixed with any compounding component other than the solvent, and the compounded component may be used by diluting it in advance, and the solvent is not previously diluted with any of the compounding components other than the solvent. You may use by mixing with.

A method of mixing each component at the time of mixing is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc.; Mixing using a mixer; What is necessary is just to select suitably from well-known methods, such as a method of adding ultrasonic waves and mixing.

The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each component is not deteriorated, and may be appropriately adjusted, but the temperature is preferably 15 to 30°C.

◇Method of manufacturing the first protective film-forming sheet

The first sheet for forming a protective film can be manufactured by sequentially stacking each of the layers described above so as to have a corresponding positional relationship. The method of forming each layer is as described above.

For example, a first sheet for forming a protective film formed by laminating a buffer layer and a thermosetting resin film on the first substrate in this order in the thickness direction thereof can be produced by the method shown below. That is, a buffer layer is laminated on the first substrate by extrusion molding the pressure-sensitive adhesive resin composition for forming a buffer layer with respect to the first substrate. Moreover, the thermosetting resin film is laminated by coating the above-described composition for forming a thermosetting resin film on the peeling treatment surface of the release film and drying as necessary. And by bonding the thermosetting resin film on this release film with the buffer layer on the first base material, a buffer layer, a thermosetting resin film, and a release film on the first base material are laminated in this order in order to obtain a sheet for forming a first protective film. The release film may be removed when the first sheet for forming a protective film is used.

In the above-described manufacturing method, the first protective film-forming sheet provided with layers other than each of the above-described layers is either one of the forming step and the stacking step of the other layer so that the stacking position of the other layer is an appropriate position. It can be manufactured by adding both as appropriate.

For example, the first sheet for forming a protective film obtained by laminating an adhesion layer, a buffer layer, and a thermosetting resin film on the first substrate in this order in these thickness directions can be produced by the method shown below. That is, by coextrusion molding the composition for forming an adhesive layer and the adhesive resin composition for forming a buffer layer on the first substrate, the adhesive layer and the buffer layer are laminated in this order on the first substrate. And, in the same manner as described above, a thermosetting resin film is separately laminated on the release film. Next, by bonding the thermosetting resin film on the release film with the buffer layer on the first substrate and the adhesion layer, the first protective film obtained by laminating the adhesion layer, the buffer layer, the thermosetting resin film and the release film on the first substrate in this order A forming sheet is obtained. The release film on the thermosetting resin film may be removed when the first sheet for forming a protective film is used.

The present invention is extremely useful industrially because it can simultaneously achieve the removal of the residue of the first protective film at the top of the bump and the segmentation of the semiconductor wafer, and provide a method for manufacturing a semiconductor chip excellent in productivity.

One… A sheet for forming a first protective film,
11... First substrate,
12... Thermosetting resin film,
12a... The first side of the thermosetting resin film,
12'... First protective film,
13... Buffer layer,
14... Dicing sheet,
101... First support sheet,
9... Semiconductor wafer,
9a... The first side of the semiconductor wafer (bump formation side),
9b... The second side (back side) of the semiconductor wafer,
91... Bump,
91a... The surface of the bump,
910... The top of the bump

Claims (6)

Affixing a thermosetting resin film to the first surface on the bump side of a semiconductor wafer having bumps,
Thermosetting the thermosetting resin film to form a first protective film on the first surface of the semiconductor wafer,
Half-cut dicing the semiconductor wafer on which the first protective film is formed from the first surface side, and
And removing the residue of the first protective film at the top of the bump by irradiating plasma to the first surface side of the semiconductor wafer that has been half-cut diced, and dividing the semiconductor wafer into pieces.
A method of manufacturing a semiconductor chip with a first protective film formed thereon. Attaching the thermosetting resin film of the sheet for forming a first protective film comprising a first support sheet and a thermosetting resin film provided on the first support sheet to the first surface of the bump side of a semiconductor wafer having bumps that,
Peeling the first support sheet from the thermosetting resin film,
Thermosetting the thermosetting resin film to form a first protective film on the first surface of the semiconductor wafer,
Dicing the semiconductor wafer half cut from the first surface side, and
And removing the residue of the first protective film at the top of the bump by irradiating plasma to the side of the first half-cut surface of the semiconductor wafer, and dividing the semiconductor wafer into pieces.
A method of manufacturing a semiconductor chip with a first protective film formed thereon. The method according to claim 1 or 2,
For the half-cut diced semiconductor wafer, the remaining thickness A (µm) of the half-cut portion of the semiconductor wafer, the thickness B (µm) of the first protective film on the first surface of the semiconductor wafer, and the bump The thickness C (㎛) of the first protective film on the top of the, the etching rate a (µm/min) of the semiconductor wafer by plasma irradiation, and the etching rate b (µm/min) of the first protective film by plasma irradiation And, the plasma irradiation time t(min) satisfies the relationship of the following formulas (1), (2), and (3), a method of manufacturing a semiconductor chip with a first protective film formed thereon:
A<at… (One)
B＞bt… (2)
C<bt… (3). Affixing a thermosetting resin film to the first surface on the bump side of a semiconductor wafer having bumps,
Half-cut dicing the semiconductor wafer to which the thermosetting resin film is affixed from the first surface side,
Plasma irradiation on the side of the first half-cut surface of the semiconductor wafer to remove the thermosetting resin film at the top of the bump, and to separate the semiconductor wafer, and
Comprising forming a first protective film on the first surface of the semiconductor wafer by thermosetting the thermosetting resin film affixed on the individualized semiconductor wafer
A method of manufacturing a semiconductor chip with a first protective film formed thereon. Attaching the thermosetting resin film of the sheet for forming a first protective film comprising a first support sheet and a thermosetting resin film provided on the first support sheet to the first surface of the bump side of a semiconductor wafer having bumps that,
Peeling the first support sheet from the thermosetting resin film,
Half-cut dicing the semiconductor wafer to which the thermosetting resin film is affixed from the first surface side,
Plasma irradiation on the side of the first half-cut surface of the semiconductor wafer to remove the thermosetting resin film at the top of the bump, and to separate the semiconductor wafer, and
Comprising forming a first protective film on the first surface of the semiconductor wafer by thermosetting the thermosetting resin film affixed on the individualized semiconductor wafer
A method of manufacturing a semiconductor chip with a first protective film formed thereon. The method according to claim 4 or 5,
For the half-cut diced semiconductor wafer, the remaining thickness A (µm) of the half-cut portion of the semiconductor wafer, the thickness D (µm) of the thermosetting resin film on the first side of the semiconductor wafer, and the bump The thickness E (µm) of the thermosetting resin film on the top of the, 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 by plasma irradiation And, the plasma irradiation time t (min) satisfies the relationship of the following formula (1), formula (4), and formula (5), a method of manufacturing a semiconductor chip with a first protective film formed thereon:
A<at… (One)
D＞dt… (4)
E<dt… (5).

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