KR20230109100A - Sheet for forming first protective film, method for manufacturing semiconductor device, and use of sheet - Google Patents

Abstract

A first sheet for forming a protective film (1) for forming a first protective film on at least a surface having bumps of a semiconductor wafer, the first sheet for forming a protective film (1) comprising a first substrate (11), a buffer layer (12) and , The intermediate peeling layer 13 and the first protective film forming film 14 are laminated in this order in their thickness direction, and the intermediate peeling with respect to the shear storage modulus ( _GA ') of the buffer layer 12 The ratio (G _x '/ _GA ') of the shear storage modulus (G _x ') of the layer 13 is less than 0.6.

Description

Sheet for forming a first protective film, method for manufacturing a semiconductor device, and use of the sheet

The present invention relates to a sheet for forming a first protective film, a method for manufacturing a semiconductor device, and use of the sheet.

This application claims priority based on Japanese Patent Application No. 2022-003124 for which it applied to Japan on January 12, 2022, and uses the content here.

Conventionally, when a multi-pin LSI package used for MPUs, gate arrays, etc. is mounted on a printed wiring board, protruding electrodes made of process solder, high-temperature solder, gold, etc. In this case, a flip chip mounting method is employed in which what is referred to as a "bump") is formed, and by a so-called face-down method, these bumps face each other on the chip mounting substrate and bring them into contact with the terminal portions corresponding to each other, thereby melting/diffusion bonding. has been

The semiconductor chip used in this mounting method is obtained, for example, by grinding or dicing the surface of a semiconductor wafer on the opposite side to the circuit surface (in other words, the bump formation surface) of a semiconductor wafer having bumps formed on the circuit surface, and separating it into pieces. In the process of obtaining such a semiconductor chip, for example, for the purpose of protecting the bump formation surface and bumps of a semiconductor wafer, a curable protective film formation film is applied to the bump formation surface, and the film is cured to form a protective film on the bump formation surface. form In the present specification, such a protective film-forming film and protective film may be referred to as a "first protective film-forming film" and a "first protective film", respectively. At this time, the bumps on the bump forming surface need to penetrate the protective film forming film (first protective film forming film) so that the tops of the bumps protrude from the protective film forming film.

1 is a cross-sectional view schematically showing an example of a state in which a protective film forming film remains on top of a bump, contrary to this case. A conventional protective film forming film 82 is attached to the surface (bump formation surface) 9a of the semiconductor wafer 9 having the bumps 91 shown here, but the top portion 9101 of the bump 91 is It does not protrude from the protective film forming film 82, and the protective film forming film 82 remains on the upper part 910 of the bump 91. Here, an example in which the entire surface 91a of the bump 91 is covered with the protective film forming film 82 is shown, but this is an example of the remaining state of the protective film forming film 82. For example, the bump In the upper part 910 of 91, a part of the surface 91a may be exposed without being covered with the protective film forming film 82. In this way, the semiconductor wafer in which the protective film formation film remains on the upper part of the bump cannot be used for flip chip mounting in this state.

On the other hand, when attaching a protective film formation film to the bump formation surface, the sheet|seat for forming a protective film in which the protective film formation film, the adhesive layer, and the base material are laminated|stacked in this order may be used. In this specification, such a sheet for forming a protective film is sometimes referred to as a "sheet for forming a first protective film". In that case, the adhesive layer and the substrate are removed from the protective film-forming film after being applied to the bump formation surface, and the protective film-forming film is cured.

Such a sheet for forming a protective film has a base material, an energy ray-curable pressure-sensitive adhesive layer, a buffer layer, and a curable protective film-forming film in this order, and has the shear storage modulus of the protective film-forming film before curing and the tensile strength of the pressure-sensitive adhesive layer after energy ray curing. A sheet for forming a protective film having a storage modulus set within a specific range is disclosed (see Patent Literature 1). By using this sheet for forming a protective film (sheet for forming a first protective film), the adhesive layer and the substrate can be easily removed from the protective film forming film (first protective film forming film) after being applied to the bump formation surface, and bump formation A protective film (first protective film) can be favorably formed on the surface. Moreover, when a protective film formation film is affixed on the bump formation surface, the protective effect of a bump is improved by a buffer layer.

International Publication No. 2020/189447

On the other hand, in recent years, in order to efficiently form a protective film on the bump formation surface, it has been studied to attach the protective film formation film in the sheet for forming a protective film to the bump formation surface at a higher speed than before. However, when attaching the protective film forming film to the bump formation surface, not only is the sticking itself difficult, but also it is difficult to protrude the top of the bump from the protective film forming film. It becomes easy for the film to remain. In this way, if the protective film formation film remains on the upper part of the bump, the protective film will remain attached to the upper part of the bump, and in this state, the semiconductor chip is not suitable for flip chip mounting. On the other hand, the sheet for forming a protective film disclosed in Patent Literature 1 is excellent in adhesion of the protective film forming film to the bump formation surface, but is not intended for high-speed adhesion.

The present invention is a sheet for forming a protective film having a protective film forming film for forming a protective film on the surface having bumps of a semiconductor wafer, wherein the sheet for forming a protective film is formed on the surface of a semiconductor wafer at high speed by means of the protective film forming film therein. An object of the present invention is to provide a sheet for forming a protective film capable of protruding the tops of the bumps from the protective film forming film even when applied, and suppressing the remaining of the protective film forming film in the upper part including the tops of the bumps.

In order to solve the above problem, the inventors of the present invention have repeatedly studied and found that the elastic modulus of the pressure-sensitive adhesive layer and the elastic modulus of the buffer layer in the conventional sheet for forming a protective film are substantially the same, but the shear storage modulus ( _GA ') of the buffer layer On the other hand, the lower the shear storage modulus (G _x ′) of the intermediate peeling layer corresponding to the pressure-sensitive adhesive layer, the more the bumps remain at the top of the first protective film forming film, and the bumps easily protrude. and found something that could achieve that goal.

That is, the present invention adopts the following configuration.

[1] A first protective film-forming sheet for forming a first protective film on at least a surface having bumps of a semiconductor wafer, wherein the first protective film-forming sheet comprises a first substrate, a buffer layer, an intermediate peeling layer, and a first protective film forming sheet. The protective film-forming films are laminated in this order in their thickness direction, and the ratio of the shear storage modulus (G _x ′) of the intermediate release layer to the shear storage modulus (GA _′ ) of the buffer layer (G _x A sheet for forming a first protective film, wherein '/ _GA ') is less than 0.6.

[2] The first sheet for forming a protective film according to [1], wherein the intermediate release layer contains an ethylene-vinyl acetate copolymer.

[3] The first sheet for forming a protective film according to [2], wherein the ratio of the amount of structural units derived from vinyl acetate to the total amount of the structural units in the ethylene-vinyl acetate copolymer is 16 to 40% by mass .

[4] The first sheet for forming a protective film according to [2] or [3], wherein the ethylene-vinyl acetate copolymer has a weight average molecular weight of 200,000 or less.

[5] The first sheet for forming a protective film according to any one of [1] to [4], wherein the intermediate release layer has a shear storage modulus ( _Gx ') of 10000 Pa or less.

[6] A method for manufacturing a semiconductor device using the sheet for forming a first protective film according to any one of [1] to [5], wherein the manufacturing method includes the first protective film forming film in the sheet for forming a first protective film. An attaching step of forming the sheet for forming the first protective film on the semiconductor wafer by attaching it to a surface of a semiconductor wafer having bumps and protruding the tops of the bumps from the first protective film forming film;

After the sticking step, in the first sheet for forming a protective film, layers other than the first protective film forming film are removed from the first protective film forming film, and when the first protective film forming film is curable, the first 1 Curing the protective film-forming film to form a first protective film, and when the first protective film-forming film is non-curable, the first protective film-forming film after removing layers other than the first protective film-forming film is treated as the first protective film. A first protective film forming step of forming the first protective film on the surface having the bumps by doing so;

a division step of fabricating a semiconductor chip by dividing the semiconductor wafer after the first protective film formation step;

A cutting step of cutting the first protective film after the first protective film forming step;

A first protective film comprising the semiconductor chip obtained after the dividing process and the cutting process, and the first protective film formed on a surface having the bumps of the semiconductor chip, wherein tops of the bumps protrude from the first protective film A semiconductor device manufacturing method comprising a mounting step of flip-chip connecting the formed semiconductor chip to a substrate at the top of the bump.

[7] The method for manufacturing a semiconductor device according to [6], wherein, in the attaching step, the first protective film-forming film is attached to the bump-bearing surface of the semiconductor wafer at an attaching speed of 4 mm/s or higher.

[8] As a use of a sheet for forming a first protective film on at least the surface having bumps of a semiconductor wafer,

The sheet is formed by laminating a first substrate, a buffer layer, an intermediate release layer, and a first protective film forming film in this order in their thickness direction,

The use of the sheet, wherein the ratio (G _x '/GA ') of the shear storage modulus (G _x ') of the intermediate release layer to the shear storage modulus (GA _' ) of the buffer layer is less _than 0.6.

According to the present invention, a sheet for forming a protective film having a protective film forming film for forming a protective film on a surface having bumps of a semiconductor wafer, wherein the sheet for forming a protective film is formed on the surface of a semiconductor wafer by the protective film forming film therein. A sheet for forming a protective film capable of protruding the tops of the bumps from the protective film forming film even when applied at high speed and suppressing the remaining of the protective film forming film on the upper portion including the tops of the bumps is provided.

1 is a cross-sectional view schematically showing an example of a state in which a protective film forming film remains on top of a bump.
2 is a cross-sectional view schematically showing an example of a sheet for forming a first protective film according to an embodiment of the present invention.
FIG. 3A is a cross-sectional view for schematically explaining a part of an example of a method for manufacturing a semiconductor device in the case of using the first sheet for forming a protective film shown in FIG. 2 .
FIG. 3B is a cross-sectional view schematically illustrating a part of an example of a method for manufacturing a semiconductor device in the case of using the first sheet for forming a protective film shown in FIG. 2 .
FIG. 3C is a cross-sectional view schematically illustrating a part of an example of a method for manufacturing a semiconductor device in the case of using the first sheet for forming a protective film shown in FIG. 2 .
FIG. 3D is a cross-sectional view for schematically explaining a part of an example of a method for manufacturing a semiconductor device in the case of using the first sheet for forming a protective film shown in FIG. 2 .
FIG. 3E is a cross-sectional view for schematically explaining a part of an example of a method for manufacturing a semiconductor device in the case of using the first sheet for forming a protective film shown in FIG. 2 .
FIG. 4A is a cross-sectional view for schematically explaining a part of another example of a method for manufacturing a semiconductor device in the case of using the first sheet for forming a protective film shown in FIG. 2 .
FIG. 4B is a cross-sectional view schematically illustrating a part of another example of a method for manufacturing a semiconductor device in the case of using the first sheet for forming a protective film shown in FIG. 2 .
FIG. 4C is a cross-sectional view schematically illustrating a part of another example of a method for manufacturing a semiconductor device in the case of using the first sheet for forming a protective film shown in FIG. 2 .
4D is a cross-sectional view for schematically explaining a part of another example of a method for manufacturing a semiconductor device in the case of using the first sheet for forming a protective film shown in FIG. 2 .

◇ Sheet for forming the first protective film

A first sheet for forming a protective film according to an embodiment of the present invention is a first sheet for forming a protective film for forming a first protective film on at least a surface having bumps of a semiconductor wafer, wherein the first sheet for forming a protective film is a first sheet for forming a protective film. A substrate, a buffer layer, an intermediate release layer, and a first protective film forming film are laminated in this order in their thickness direction, and the intermediate release layer with respect to the shear storage modulus ( _GA ') of the buffer layer is The ratio (G _x '/ _GA ') of the shear storage modulus (G _x ') is less than 0.6.

The first sheet for forming a protective film of the present embodiment has such a structure, so that even if it is affixed to the surface having bumps of a semiconductor wafer at high speed by the protective film forming film therein, the tops of the bumps can protrude from the protective film forming film. There is, and the survival|survival of the protective film formation film in the upper part including the top part of a bump can be suppressed.

In the present specification, the shear storage modulus (G _x ′) of the intermediate peeling layer means a test piece of the disc-shaped intermediate peeling layer using a shear viscosity measuring device under the conditions of a temperature of 90° C., a measurement frequency of 1 Hz, and a shear strain of 1%. It refers to the shear storage modulus (G _x ') [Pa] measured in

In the present specification, the shear storage modulus ( _GA ') of the buffer layer means the shear shear rate measured by a shear viscosity measuring device on a test piece of a disk-shaped buffer layer under the conditions of a temperature of 90 ° C., a measurement frequency of 1 Hz, and a shear strain of 1%. It refers to the storage modulus ( _GA ') [Pa].

For example, the shear storage modulus of the intermediate peeling layer or buffer layer is measured by laminating a plurality of intermediate peeling layers or buffer layers to prepare a disk-shaped test piece with a diameter of 25 mm and a thickness of 400 μm, and using a shear viscosity measuring device (for example, Antonfa Co., Ltd.: MCR301), the shear strain generated under the conditions of a temperature of 90 ° C. and a measurement frequency of 1 Hz was raised stepwise to 0.01% to 10%, and the shear storage modulus of the test piece at a shear strain of 1% was measured. can be measured and obtained.

The ratio of the shear storage modulus (G _{x ′} ) of the intermediate release layer to the shear storage modulus (GA _′ ) of the buffer layer (G _x ′/GA _′ ) is the shear storage modulus (G _{x ′} ) of the test piece of the intermediate release layer. ') [Pa] is obtained by dividing the value of the shear storage modulus ( _GA ') [Pa] of the test piece of the buffer layer.

In the first sheet for forming a protective film of the present embodiment, the ratio (G _x '/ _GA ') is less than 0.6, preferably 0.4 or less, more preferably 0.3 or less, still more preferably 0.10 or less, and 0.05 It is especially preferable that it is below. When the ratio ( _Gx '/ _GA ') is equal to or less than the upper limit, both the high-speed sticking property of the sheet for forming a first protective film and the penetrability of the bumps of the first protective film-forming film are enhanced.

In the first sheet for forming a protective film of the present embodiment, the ratio ( _Gx '/ _GA ') may be 0.00001 or more, or 0.0001 or more.

In the first sheet for forming a protective film of the present embodiment, the shear storage modulus ( _Gx ') of the intermediate release layer may be 50000 Pa or less, preferably 10000 Pa or less, more preferably 7000 Pa or less, still more preferably 1000 or less , it is particularly preferably 300 or less. When the shear storage modulus ( _Gx ') of the intermediate peeling layer is equal to or less than the upper limit, it is easy to adjust the ratio ( _Gx '/ _GA ') to less than 0.6, and the sheet for forming the first protective film is easily attached. performance, and the penetrability of bumps of the first protective film-forming film are all increased.

In the first sheet for forming a protective film of the present embodiment, the shear storage modulus ( _Gx ') of the intermediate release layer may be 1 Pa or more or 5 Pa or more.

In the first sheet for forming a protective film of the present embodiment, the shear storage modulus ( _GA ') of the buffer layer is preferably 10000 to 400000 Pa, more preferably 50000 to 300000 Pa, particularly preferably 100000 to 200000 Pa. When the shear storage modulus ( _GA ') of the buffer layer is equal to or greater than the lower limit, the effect of the buffer layer is further enhanced. When the shear storage modulus ( _GA ') of the buffer layer is equal to or less than the above upper limit, the buffer layer is suppressed from becoming excessively hard.

In this specification, in any of a semiconductor wafer and a semiconductor chip, a surface having bumps may be referred to as a "bump formation surface". In some cases, the surface opposite to the bump formation surface of semiconductor wafers and semiconductor chips is referred to as "rear surface".

In this specification, the protective film formed on the surface (ie, back surface) opposite to the bump formation surface of a semiconductor wafer or semiconductor chip is called a "second protective film."

In order to form a second protective film on the surface (rear surface) of a semiconductor wafer or semiconductor chip opposite to the bump formation surface, a sheet for forming a second protective film comprising a second protective film forming film for forming a second protective film is used. do. Examples of the sheet for forming the second protective film include a dicing sheet and a sheet formed with a second protective film formed on the dicing sheet. When the dicing sheet is provided with the same substrate as the first substrate, this substrate is referred to as a "second substrate".

In the sheet for forming the first protective film of the present embodiment, the first protective film can be formed not only on the bump formation surface of the semiconductor chip but also on the side surface as will be described later. That is, the sheet for forming a first protective film of the present embodiment can be used as a sheet for forming a first protective film on at least the bump formation surface of a semiconductor wafer.

2 is a cross-sectional view schematically showing an example of the sheet for forming a first protective film of the present embodiment.

On the other hand, in the drawings used in the following description, in order to make it easy to understand the features of the present invention, for convenience, the main parts are sometimes enlarged and shown, and the dimensional ratio of each component is not limited to being the same as the actual one. don't

The first sheet 1 for forming a protective film shown here includes a first substrate 11, a buffer layer 12 formed on one surface 11a of the first substrate 11, and a first substrate of the buffer layer 12. The intermediate peeling layer 13 formed on the surface 12a on the opposite side to the side (11), and the surface of the intermediate peeling layer 13 on the opposite side to the buffer layer 12 side (in this specification, the "first surface It is configured by providing a first protective film-forming film 14 formed on 13a). That is, the first sheet for forming a protective film 1 includes the first substrate 11, the buffer layer 12, the intermediate peeling layer 13, and the first protective film forming film 14 in this order, It is structured by being laminated in the direction.

The first protective film-forming sheet 1 further has a surface on the side opposite to the intermediate peeling layer 13 side of the first protective film-forming film 14 (in this specification, it may be referred to as a “first surface”) ) (14a) is provided with a release film (15).

In the first sheet 1 for forming a protective film, the intermediate release layer 13 preferably contains an ethylene-vinyl acetate copolymer (sometimes referred to as "EVA" in this specification).

The peeling film 15 is not specifically limited, A well-known thing may be sufficient as it.

In the first sheet 1 for forming a protective film, the release film 15 has an arbitrary configuration, and the sheet 1 for forming a first protective film does not need to include the release film 15 .

The first sheet for forming a protective film of the present embodiment is not limited to the one shown in FIG. 2 , but within a range that does not impair the effect of the present invention, in the one shown in FIG. 2 , a part of the configuration is changed, deleted, or added It could be anything.

For example, the first sheet for forming a protective film of the present embodiment further includes a first substrate, a buffer layer, an intermediate peeling layer, a first protective film forming film, and other layers that do not correspond to any of the peeling films. You can do it. However, in the first sheet for forming a protective film not provided with a release film, it is preferable that the first protective film forming film is one outermost layer, that is, a layer disposed on the outermost side in the lamination direction of each layer. do. Further, in the first sheet for forming a protective film of the present embodiment, the first substrate and the buffer layer are formed in direct contact, the buffer layer and the intermediate peeling layer are formed in direct contact, and the intermediate peeling layer and the first protective film forming film are formed in direct contact. It is preferable to contact and form.

Next, each layer constituting the first sheet for forming a protective film of the present embodiment will be described.

◎First protective film formation film

The first protective film-forming film may be curable or non-curable. For example, the first protective film-forming film may function as a first protective film by curing, or may function as a first protective film in an uncured state.

The curable first protective film-forming film may be either thermosetting or energy ray curable, or may have both thermosetting and energy ray curing properties.

It is preferable that the 1st protective film formation film is curable at the point which can form the 1st protective film with a higher protective ability.

In this specification, an "energy ray" means one having energy quanta in an electromagnetic wave or a charged particle beam. Examples of energy rays include ultraviolet rays, radiation, and electron beams. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, or an LED lamp as an ultraviolet source. Electron beams generated by an electron beam accelerator or the like can be irradiated.

In the present specification, "energy ray curability" means a property that is cured by irradiation with energy rays, and "non-energy ray curability" means a property that is not cured even when irradiated with energy rays.

"Non-curable" means a property that does not cure by any means such as heating or irradiation with energy rays.

The first protective film-forming film contains a resin component and may or may not contain components other than the resin component.

The first protective film-forming film is soft and has high conformability to concave-convex surfaces such as bump formation surfaces of semiconductor wafers. As a result, the first protective film-forming film and the first protective film exhibit high adhesion to concave-convex surfaces such as the bump formation surface of a semiconductor wafer, and the first protective film exhibits high adhesion to concavo-convex surfaces such as the bump formation surface of a semiconductor chip. .

When the 1st protective film formation film in the 1st protective film formation sheet of this embodiment is affixed on the bump formation surface of a semiconductor wafer, heating, the bump on the bump formation surface penetrates the 1st protective film formation film, and the top part of the bump It protrudes from the first protective film forming film. Then, the softened first protective film-forming film spreads between the bumps so as to cover the bumps, adheres to the bump formation surface, covers the surface of the bump, especially the surface of the vicinity of the bump formation surface, and embeds the base of the bump do. In this state, the remaining of the first protective film forming film is suppressed in the upper part of the bump. When the first protective film-forming film is curable, the first protective film-forming film in this state (the base of the bump is embedded) is then cured to finally form a first protective film, and the first protective film-forming film is In the case of non-curing, the first protective film-forming film after this state (the state in which the base of the bump is embedded) functions as a first protective film. And, of course, the adhesion of the first protective film to the upper part of the bump is suppressed. In particular, in the case of using the first protective film-forming sheet of the present embodiment, even if the first protective film-forming film in the first protective film-forming sheet is affixed to the bump formation surface of the semiconductor wafer at high speed, the top portion of the bump is the first protective film-forming film protrudes from the bump, and in the upper part of the bump, the remaining of the first protective film forming film and the adhesion of the first protective film are suppressed. The reason why the first sheet for forming a protective film of the present embodiment has such excellent properties is that the first sheet for forming a protective film includes a first substrate, a buffer layer, an intermediate peeling layer, and a first protective film forming film in this order. This is because the ratio of the shear storage modulus (G _x ′) of the intermediate release layer to the shear storage modulus (GA _′ ) of the buffer layer (G _{x ′} /GA _′ ) is less than 0.6.

The existence or nonexistence of the first protective film forming film on the upper part of the bump on the bump formation surface and the presence or absence of adhesion of the first protective film are, for example, obtained by scanning electron microscope (SEM) imaging data for the upper part of the bump You can check it by doing

Regardless of whether the first protective film-forming film is curable or non-curable, and in the case of curing, regardless of whether it is thermosetting or energy ray-curable, the first protective film-forming film may consist of one layer (single layer). , It may consist of a plurality of layers of two or more layers. When the first protective film-forming film consists of a plurality of layers, these plurality of layers may be the same as or different from each other, and the combination of these plurality of layers is not particularly limited.

In this specification, not limited to the case of the first protective film forming film, "a plurality of layers may be the same or different from each other" means "all layers may be the same, all layers may be different, and only some layers may be It may be the same,” and “a plurality of layers are different from each other” means that “at least one of the constituent materials and thicknesses of each layer is different from each other.”

The thickness of the first protective film-forming film is preferably 1 to 200 μm regardless of whether the first protective film-forming film is curable or non-curable, and in the case of curing, regardless of whether it is thermosetting or energy ray-curable. It is more preferably 10 to 150 μm, and particularly preferably 20 to 130 μm. When the thickness of the first protective film-forming film is equal to or greater than the lower limit, the effect of the first protective film-forming film is higher. For example, when forming a protective film using the 1st protective film formation film, a protective film with a higher protective ability can be formed. When the thickness of the first protective film-forming film is equal to or less than the above upper limit, it is suppressed that the first protective film becomes excessively thick.

As will be described later, in the case where the first protective film is formed not only on the bump formation surface of the semiconductor chip but also on the side surface, it is necessary to use a semiconductor wafer in which grooves are formed on the bump formation surface. In this way, in the case of forming the first protective film on the side surface of the semiconductor chip, in addition to the same reason as above, the first protective film forming film can be sufficiently filled in the groove, the thickness of the first protective film forming film is It is preferably 2 to 200 μm, more preferably 30 to 150 μm, and particularly preferably 30 to 130 μm.

On the other hand, in the case where the first protective film is formed on the bump formation surface of the semiconductor chip but no protective film is formed on the side surface, a semiconductor wafer having no grooves formed on the bump formation surface may be used. In that case, the thickness of the first protective film-forming film is 1 to 100 µm for the same reasons as above (the effect of the first protective film-forming film is higher; the first protective film is suppressed from becoming excessively thick). It is preferably 20 to 75 μm, more preferably, and particularly preferably 35 to 55 μm.

In this specification, "thickness of the first protective film-forming film" means the thickness of the entire first protective film-forming film, for example, the thickness of the first protective film-forming film composed of a plurality of layers It means the total thickness of all the layers constituting the

In this specification, "thickness" is not limited to the case of the first protective film forming film, and unless otherwise specified, means the average value of the thickness measured at five randomly selected locations in the object, and conforms to JIS K7130 Thus, it can be acquired using a constant pressure thickness meter.

<<Composition for Forming First Protective Film>>

The first protective film-forming film may be formed using a composition for forming a first protective film containing the constituent materials. For example, the first protective film-forming film can be formed by coating the composition for forming the first protective film on the surface to be formed and drying it, if necessary. The ratio of the contents of the components that do not vaporize at normal temperature in the first protective film-forming composition is usually the same as the ratio of the contents of the components in the first protective film-forming film. In this specification, “normal temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25°C.

The thermosetting first protective film-forming film may be formed using a thermosetting first protective film-forming composition, and the energy ray-curable first protective film-forming film may be formed using an energy ray-curable first protective film-forming composition. The first protective film forming film may be formed using a non-curing composition for forming a first protective film.

In the present specification, when the first protective film-forming film has both thermosetting properties and energy ray curing properties, in forming the first protective film, the contribution of thermal curing of the first protective film-forming film is greater than that of energy ray curing. In this case, the first protective film-forming film is treated as a thermosetting film. Conversely, in the formation of the first protective film, when the contribution of energy ray curing of the first protective film forming film is greater than that of thermal curing, the first protective film forming film is treated as an energy ray curable film.

In the first protective film-forming film, the ratio of the total content of one or two or more of the following components in the first protective film-forming film to the total mass of the first protective film-forming film does not exceed 100% by mass.

Similarly, in the first protective film-forming composition, the ratio of the total content of one or two or more of the following components in the first protective film-forming composition to the total mass of the first protective film-forming composition exceeds 100 mass%. I never do that.

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

Regardless of whether the first protective film-forming film is curable or non-curable, and if curable, regardless of whether it is thermosetting or energy ray curable, the drying conditions of the first protective film-forming composition are not particularly limited. However, when the composition for forming the first protective film contains a solvent described later, it is preferable to heat-dry the composition. Then, it is preferable to heat-dry the first protective film-forming composition containing a solvent under conditions of, for example, 70 to 130°C for 10 seconds to 5 minutes. However, it is preferable to heat-dry the composition for forming the first thermosetting protective film so that the composition itself and the thermosetting first protective film-forming film formed from the composition are not thermally cured.

Hereinafter, a thermosetting first protective film-forming film, an energy ray-curable first protective film-forming film, and a non-curable first protective film-forming film will be further described in detail.

○ Thermosetting first protective film forming film

Examples of the thermosetting first protective film-forming film include those containing a polymer component (A), a thermosetting component (B), a curing accelerator (C), a filler (D), and an additive (I). .

The curing conditions for forming the first protective film by curing the thermosetting first protective film-forming film are not particularly limited as long as the curing degree is such that the first protective film sufficiently exhibits its function, and the type of the thermosetting first protective film-forming film What is necessary is just to select suitably according to etc.

For example, the heating temperature at the time of thermal curing of the thermosetting first protective film-forming film is preferably 100 to 200°C, and may be, for example, 110 to 170°C or 120 to 150°C. It is preferable that the heating time at the time of said thermosetting is 0.5 to 5 hours, and, for example, either 0.5 to 4 hours or 1 to 3 hours may be sufficient.

<Composition for Forming a Thermosetting First Protective Film>

As the composition for forming a first thermosetting protective film, for example, a first thermosetting composition containing a polymer component (A), a thermosetting component (B), a curing accelerator (C), a filler (D), and an additive (I). and the composition (III) for forming a protective film (in this specification, it may be simply referred to as “composition (III)”) and the like.

[Polymer component (A)]

The polymer component (A) is a polymer compound for imparting film-formability, flexibility, and the like to the thermosetting first protective film-forming film. On the other hand, in this specification, the product of polycondensation reaction is also contained in a polymer compound.

The polymer component (A) contained in the composition (III) and the thermosetting first protective film-forming film may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

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

Among these, it is preferable that the polymer component (A) is polyvinyl acetal.

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

Especially, as a preferable polyvinyl acetal, polyvinyl formal, polyvinyl butyral, etc. are mentioned, for example, 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, m, and n are each independently an integer of 1 or more)

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. When the weight average molecular weight of polyvinyl acetal is within this range, when the thermosetting first protective film-forming film is attached to the bump formation surface, the effect of suppressing the remaining of the thermosetting first protective film-forming film on the upper part of the bump is higher.

In this specification, "weight average molecular weight" is a polystyrene conversion value measured by the gel permeation chromatography (GPC) method unless otherwise specified.

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. When the Tg of polyvinyl acetal is within this range, when the thermosetting first protective film-forming film is applied to the bump formation surface, the effect of suppressing the remaining of the thermosetting first protective film-forming film on the top of the bump is higher.

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

A well-known acrylic polymer is mentioned as said acrylic resin in a polymer component (A).

It is preferable that it is 5000-1000000, and, as for the weight average molecular weight (Mw) of an acrylic resin, it is more preferable that it is 8000-800000. When the weight average molecular weight of the acrylic resin is within this range, when the thermosetting first protective film-forming film is attached to the bump formation surface, the effect of suppressing the remaining of the thermosetting first protective film-forming film on the upper part of the bump is higher.

It is preferable that it is -50-70 degreeC, and, as for the glass transition temperature (Tg) of an acrylic resin, it is more preferable that it is -30-60 degreeC. When the Tg of the acrylic resin is within this range, when the thermosetting first protective film-forming film is affixed to the bump formation surface, the effect of suppressing the remaining of the thermosetting first protective film-forming film on the top of the bump is higher.

When an acrylic resin has 2 or more types of structural units, the glass transition temperature (Tg) of the acrylic resin is computable using Fox's formula. As the Tg of the monomer that derives the structural unit used at this time, a value described in the Polymer Data Handbook or the Adhesion Handbook can be used.

1 type of the monomer which comprises an acrylic resin may be sufficient as it, and 2 or more types may be sufficient as it, and in the case of 2 or more types, these combination and ratio can be arbitrarily selected.

As an acrylic resin, For example, polymer of 1 type, or 2 or more types of (meth)acrylic acid ester;

copolymers of two or more monomers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide;

Air of one or two or more (meth)acrylic acid esters and one or two or more monomers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, etc. A synthesis etc. are mentioned.

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 "acryloyl group" and "methacryloyl group".

Examples of the (meth)acrylic acid ester constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n- (meth)acrylate. Butyl, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, (meth)acrylic acid Dodecyl (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate ((meth)acrylate) palmityl acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc., the alkyl group constituting the alkyl ester has a chain structure of 1 to 18 carbon atoms (meth)acrylic acid. alkyl ester;

(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)acrylic acid cycloalkenyl esters such as (meth)acrylic acid dicyclopentenyl ester;

(meth)acrylic acid cycloalkenyloxyalkyl esters such as (meth)acrylic acid dicyclopentenyloxyethyl ester;

(meth)acrylic acid imide;

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)acrylate ) Hydroxyl group-containing (meth)acrylic acid esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth)acrylate;

and substituted amino group-containing (meth)acrylic acid esters such as N-methylaminoethyl (meth)acrylic acid. Here, "substituted amino group" means a group having a structure in which one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms.

The acrylic resin may have a functional group bondable to other compounds such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxy group, and an isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a crosslinking agent (F) described below, or directly bonded to another compound without a crosslinking agent (F). Reliability of a package obtained by using, for example, a thermosetting first protective film forming film tends to be improved when the acrylic resin is bonded to other compounds by the functional group.

In the composition (III), the ratio of the content of the polymer component (A) to the total content of all components other than the solvent is preferably 5 to 25% by mass, regardless of the type of the polymer component (A). It is more preferable that it is -15 mass %.

In this content, the ratio of the content of the polymer component (A) to the total mass of the thermosetting first protective film-forming film in the thermosetting first protective film-forming film is 5 to 25% by mass, regardless of the type of the polymer component (A). It is the same as that which is preferable, and it is more preferable that it is 5-15 mass %.

This is based on the fact that in the process of removing the solvent from the resin composition containing the solvent to form the resin film, the amount of components other than the solvent usually does not change, and the ratio of the contents of components other than the solvent in the resin composition and the resin film. is the same Therefore, in this specification, hereafter, the content of components other than the solvent is not limited to the case of the thermosetting first protective film forming film, and only the content in the resin film obtained by removing the solvent from the resin composition is described.

The polymer component (A) also corresponds to the thermosetting component (B) in some cases. In the present embodiment, when the composition (III) contains components corresponding to both the polymer component (A) and the thermosetting component (B), the composition (III) includes the polymer component (A) and the thermosetting component (B) is considered to contain

[Thermosetting component (B)]

The thermosetting component (B) has thermosetting properties and is a component for thermosetting the thermosetting first protective film-forming film.

The thermosetting component (B) contained in the composition (III) and the thermosetting first protective film-forming film may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

Examples of the thermosetting component (B) include epoxy thermosetting resins, thermosetting polyimide resins, and unsaturated polyester resins, and epoxy thermosetting resins are preferable.

In this specification, a thermosetting polyimide resin is a general term for a polyimide precursor that forms a polyimide resin by thermosetting, and a thermosetting polyimide.

(epoxy-based thermosetting resin)

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

The epoxy-type thermosetting resin contained in the composition (III) and the thermosetting first protective film-forming film may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

・Epoxy resin (B1)

Examples of the epoxy resin (B1) include known epoxy resins, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether, and hydrogenated products thereof, orthocresol novolak epoxy resins, and dicyclo and bifunctional or higher functional epoxy compounds such as pentadiene type epoxy resins, biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and phenylene skeleton type epoxy resins.

The epoxy resin (B1) may be an epoxy resin having an unsaturated hydrocarbon group. An 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 a package obtained by using, for example, a thermosetting first protective film forming film tends to be improved.

Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound having a structure in which a part of the epoxy groups of a multifunctional epoxy resin is converted 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.

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

The unsaturated hydrocarbon group is an unsaturated group having polymerizability, and specific examples include an ethenyl group (vinyl group), a 2-propenyl group (allyl group), a (meth)acryloyl group, a (meth)acrylamide group, and the like, , an acryloyl group is preferred.

Although the number average molecular weight of the epoxy resin (B1) is not particularly limited, the curability of the thermosetting first protective film-forming film and the strength and heat resistance of the cured product (eg, first protective film) of the thermosetting first protective film-forming film From this, it is preferably 300 to 30000, more preferably 400 to 10000, and particularly preferably 500 to 3000.

It is preferable that it is 100-1000 g/eq, and, as for the epoxy equivalent of an epoxy resin (B1), it is more preferable that it is 200-800 g/eq.

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

·Heat curing agent (B2)

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

Examples of the heat curing agent (B2) include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, and an anhydride acid group. It is more preferable that it is a hydroxyl group or an amino group.

Among the thermosetting agents (B2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenols, novolak-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins. can

Among the thermal curing agents (B2), examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as "DICY") and the like.

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

As the thermosetting agent (B2) having an unsaturated hydrocarbon group, for example, a compound having a structure in which a part of the hydroxyl group of a phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a compound having a structure in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring of the phenol resin. etc. can be mentioned.

The unsaturated hydrocarbon group in the heat curing agent (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.

Among the thermosetting agents (B2), for example, the number average molecular weight of resin components such as polyfunctional phenolic resins, novolak-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins is preferably 300 to 30000 , more preferably from 400 to 10000, and particularly preferably from 500 to 3000.

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

A heat curing agent (B2) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, these combination and ratio can be arbitrarily selected.

The content of the thermosetting agent (B2) in the thermosetting first protective film-forming film 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), For example, any one of 5-150 mass parts, 10-100 mass parts, and 15-75 mass parts may be sufficient. When the said content of a thermosetting agent (B2) is more than the said lower limit, hardening of a thermosetting 1st protective film formation film advances more easily. When the content of the thermosetting agent (B2) is equal to or less than the above upper limit, the moisture absorption rate of the thermosetting first protective film forming film is reduced, and, for example, the reliability of a package obtained by using the thermosetting first protective film forming film is further improved.

The content of the thermosetting component (B) in the thermosetting first protective film-forming film (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is based on 100 parts by mass of the polymer component (A). , It is preferable that it is 600-1000 mass parts. When the content of the thermosetting component (B) is within this range, when the thermosetting first protective film-forming film is affixed on the bump formation surface, the effect of suppressing the remaining of the thermosetting first protective film-forming film on the upper part of the bump is higher, , It is also possible to form a hard first protective film.

In addition, you may adjust content of the thermosetting component (B) suitably according to the kind of polymer component (A) from the point which such an effect is acquired more remarkably.

For example, when the polymer component (A) is the polyvinyl acetal, the content of the thermosetting component (B) in the thermosetting first protective film-forming film is 600 to 600 parts by mass with respect to 100 parts by mass of the polymer component (A). It is preferably 1000 parts by mass, more preferably 600 to 900 parts by mass, and still more preferably 600 to 800 parts by mass.

[Curing accelerator (C)]

The curing accelerator (C) is a component for adjusting the curing speed of the composition (III).

Preferred curing accelerators (C) include, for example, 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 (imidazoles in which one or more hydrogen atoms are substituted with groups other than hydrogen atoms); organic phosphines (phosphine in which one or more hydrogen atoms are substituted with organic groups) such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenyl boron salts such as tetraphenylphosphonium tetraphenyl borate and triphenylphosphine tetraphenyl borate; and the like.

The curing accelerator (C) contained in the composition (III) and the thermosetting first protective film-forming film may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

The content of the curing accelerator (C) in the thermosetting first protective film-forming film is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the thermosetting component (B). When the said content of a hardening accelerator (C) is more than the said lower limit, the effect by using a hardening accelerator (C) is acquired more remarkably. When the content of the curing accelerator (C) is equal to or less than the above upper limit, the highly polar curing accelerator (C) moves to the bonding interface side with the adherend in the thermosetting first protective film-forming film under high temperature and high humidity conditions and segregates, for example. The effect of suppressing this is enhanced, and the reliability of a package obtained by using, for example, a thermosetting first protective film forming film is further improved.

[Filling material (D)]

By adjusting the amount of the filler (D) in the composition (III) and the thermosetting first protective film-forming film, when the thermosetting first protective film-forming film is attached to the bump formation surface, the thermosetting first protective film-forming film at the top of the bump The effect of suppressing the residual can be controlled. In addition, the thermal expansion coefficient of the cured product (eg, the first protective film) of the thermosetting first protective film-forming film can be more easily adjusted. By optimizing, the reliability of the package obtained by using the thermosetting first protective film forming film is further improved. In addition, as will be described later, since the first protective film is formed not only on the bump formation surface of the semiconductor chip but also on the side surface, when filling the grooves formed on the bump formation surface of the semiconductor wafer with the first protective film formation film, the filling thereof You can adjust the degree of In addition, by using the thermosetting first protective film-forming film containing the filler (D), the moisture absorption rate of the cured product (eg, the first protective film) of the thermosetting first protective film-forming film can be reduced or heat dissipation can be improved.

The filler (D) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.

Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, bengala, silicon carbide, boron nitride and the like; Beads which spheroidized these inorganic fillers; 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.

Composition (III) and the filler (D) contained in the thermosetting first protective film-forming film may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

The ratio of the content of the filler (D) to the total mass of the thermosetting first protective film-forming film in the thermosetting first protective film-forming film is preferably 5 to 45% by mass, more preferably 5 to 40% by mass, , It is more preferable that it is 5-30 mass %. When the ratio is within this range, when the thermosetting first protective film forming film is attached to the bump formation surface, the effect of suppressing the remaining of the thermosetting first protective film forming film on the upper part of the bump is higher, and the above thermal expansion The coefficient can be more easily adjusted. Moreover, it can suppress that resin oozes out other than a wafer at the time of sticking.

[Additive (I)]

By adjusting the type or amount of the additive (I) in the composition (III) and the thermosetting first protective film-forming film, when the thermosetting first protective film-forming film is attached to the bump formation surface, a thermosetting first protective film is formed on the top of the bump The effect of suppressing the remaining of the film can be adjusted.

Among them, preferable additives (I) include, for example, a rheology modifier, a surfactant, and a silicone oil from the viewpoint of further enhancing the effect of suppressing the survival of the above-described thermosetting first protective film-forming film.

More specifically, examples of the rheology modifier include polyhydroxycarboxylic acid esters, polyhydric carboxylic acids, and polyamide resins.

As said surfactant, modified siloxane, an acrylic polymer, etc. are mentioned, for example.

Examples of the silicone oil include aralkyl-modified silicone oil and modified polydimethylsiloxane, and examples of the modifier include an aralkyl group; Polar groups, such as a hydroxyl group; and groups having unsaturated bonds such as a vinyl group and a phenyl group.

As additive (I), other various general purpose additives, such as a plasticizer, an antistatic agent, antioxidant, a gettering agent, a ultraviolet absorber, and a tackifier, are also mentioned as things other than the above, for example.

The additive (I) contained in the composition (III) and the thermosetting first protective film-forming film may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

The content of the additive (I) in the composition (III) and the thermosetting first protective film-forming film is not particularly limited and can be appropriately adjusted depending on the type or purpose.

For example, in the case where the purpose is to control the effect of suppressing the survival of the above-described thermosetting first protective film-forming film, the additive (I) relative to the total mass of the thermosetting first protective film-forming film in the thermosetting first protective film-forming film It is preferable that it is 0.5-10 mass %, as for the ratio of content, it is more preferable that it is 0.5-7 mass %, and it is still more preferable that it is 0.5-5 mass %.

[Coupling agent (E)]

Composition (III) and the thermosetting first protective film-forming film may contain a coupling agent (E). By using a coupling agent (E) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesiveness and adhesiveness of the thermosetting first protective film-forming film to the adherend can be improved. Further, by using the coupling agent (E), the cured product of the thermosetting first protective film-forming film (for example, the first protective film) has improved water resistance without impairing heat resistance.

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

Preferable examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 3-glycidyloxypropyltriethoxysilane. Cidyloxymethyldiethoxysilane, 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, methyltri Ethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, etc. are mentioned.

The coupling agent (E) contained in the composition (III) and the thermosetting first protective film-forming film may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

In the case of using a coupling agent (E), the content of the coupling agent (E) in the thermosetting first protective film forming film is, for example, relative to 100 parts by mass of the total content of the polymer component (A) and the thermosetting component (B). For example, 0.03 to 20 mass may be given. When the content of the coupling agent (E) is equal to or greater than the lower limit, the dispersibility of the filler (D) is improved, and the adhesion of the thermosetting first protective film forming film to the adherend is improved. The coupling agent (E) is used effect is obtained more remarkably. Generation|occurrence|production of outgas is suppressed more because the said content of a coupling agent (E) is below the said upper limit.

[Crosslinking agent (F)]

Composition (III) and a thermosetting first protective film-forming film when a polymer component (A) having a functional group such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxy group, or an isocyanate group capable of bonding with another compound is used You may contain the silver crosslinking agent (F). The crosslinking agent (F) is a component for crosslinking by binding the functional groups in the polymer component (A) to other compounds, and by crosslinking in this way, the initial adhesive force and cohesive force of the thermosetting first protective film-forming film can be adjusted.

Examples of the crosslinking agent (F) include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate crosslinking agent (a crosslinking agent having a metal chelate structure), and an aziridine crosslinking agent (a crosslinking agent having an aziridinyl group).

Examples of the organic polyvalent isocyanate compound include an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds may be collectively abbreviated as “aromatic polyvalent isocyanate compound, etc.”); Trimer, isocyanurate body, and adduct body, such as the said aromatic polyhydric isocyanate compound; Terminal isocyanate urethane prepolymers etc. which are a reaction product of the said aromatic polyhydric isocyanate compound etc. and a polyol compound are mentioned. The "adduct body" is an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, or an alicyclic polyvalent isocyanate compound, and a low molecular weight active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, or castor oil. means the reactant of Examples of the adducts include xylylene diisocyanate adducts of trimethylolpropane described later. In this specification, "terminal isocyanate urethane prepolymer" means a prepolymer having an isocyanate group at the terminal portion of the molecule while having a urethane bond.

As the organic polyhydric 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.

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

When using an organic polyhydric isocyanate compound as a crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as a 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 easily introduced into the thermosetting first protective film-forming film by the reaction between the crosslinking agent (F) and the polymer component (A). .

The composition (III) and the crosslinking agent (F) contained in the thermosetting first protective film-forming film may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

When using a crosslinking agent (F), the content of the crosslinking agent (F) in the composition (III) may be, for example, 0.01 to 20 parts by mass relative to 100 parts by mass of the polymer component (A). When the content of the cross-linking agent (F) is equal to or greater than the lower limit, the effect of using the cross-linking agent (F) is obtained more remarkably. Excessive use of a crosslinking agent (F) is suppressed because the said content of a crosslinking agent (F) is below the said upper limit.

[Other Ingredients]

Composition (III) and the thermosetting first protective film forming film are the polymer component (A), the thermosetting component (B), the curing accelerator (C), and the filler (D) within a range that does not impair the effects of the present invention. ), additive (I), coupling agent (E), and other components that do not correspond to any of the crosslinking agents (F) may be contained.

As said other component, energy-beam curable resin, a photoinitiator, etc. are mentioned, for example.

The other components contained in the composition (III) and the thermosetting first protective film-forming film may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

The content of the composition (III) and the above other components in the thermosetting first protective film-forming film is not particularly limited, and may be appropriately selected according to the purpose.

[menstruum]

Composition (III) preferably further contains a solvent. The solvent-containing composition (III) has good handleability.

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

The solvent contained in the composition (III) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

A more preferable solvent to be contained in the composition (III) is, for example, methyl ethyl ketone from the viewpoint of being able to more uniformly mix the components contained in the composition (III).

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

An example of a preferred thermosetting first protective film-forming film from the viewpoint of further enhancing the desired effect of the present invention (high-speed sticking of the sheet for forming a first protective film described later and penetrability of the first protective film-forming film) is a polymer component ( A), a thermosetting component (B), a curing accelerator (C), a filler (D), and an additive (I), the thermosetting first protective film-forming film in the thermosetting first protective film-forming film The ratio of the total content of the polymer component (A), the thermosetting component (B), the curing accelerator (C), the filler (D), and the additive (I) to the total mass is 85% by mass or more , Preferably it is 90 mass % or more, More preferably, it is 95 mass % or more.

In view of the above, as an example of a more preferable thermosetting first protective film-forming film, a polymer component (A), a thermosetting component (B), a curing accelerator (C), a filler (D), and an additive (I) wherein the polymer component (A) is polyvinyl acetal, the thermosetting component (B) is an epoxy resin (B1) and a thermosetting agent (B2), and the additive (I) is a rheology modifier, surfactant, and silicone It is one or two or more selected from the group consisting of oil, and the polymer component (A) and the thermosetting component (B) with respect to the total mass of the thermosetting first protective film-forming film in the thermosetting first protective film-forming film ), the curing accelerator (C), the filler (D), and the ratio of the total content of the additive (I) is 85% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more can hear

It is preferable that it is 2 to 7 times, and, as for the thickness of these thermosetting 1st protective film formation films, it is more preferable that it is 3 to 6 times the thickness of an intermediate release layer.

<Method for Producing Composition for Forming Thermosetting First Protective Film>

A composition for forming a thermosetting first protective film, such as composition (III), is obtained by blending the respective components to constitute it.

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

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

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.

○Energy ray curable first protective film forming film

Examples of the energy ray-curable first protective film-forming film include those containing the energy ray-curable component (a), a filler, and an additive.

Curing conditions for forming the first protective film by curing the energy ray-curable first protective film-forming film are not particularly limited, as long as the curing degree is such that the first protective film sufficiently exhibits its function, and the energy ray-curable first protective film What is necessary is just to select suitably according to the kind of formation film etc.

For example, it is preferable that the illuminance of the energy beam at the time of hardening of the energy beam curable first protective film forming film is 180 to 280 mW/cm 2 . And it is preferable that the light quantity of the energy ray at the time of the said hardening is 450-1000 mJ/cm<2>.

<Composition for Forming Energy Ray Curable First Protective Film>

As the composition for forming a first energy ray curable protective film, for example, the composition for forming an energy ray curable first protective film (IV) containing an energy ray curable component (a), a filler, and an additive (in this specification, simply Sometimes referred to as "composition (IV)"), etc. are mentioned.

[Energy ray curable component (a)]

The energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and is also a component for imparting film formability and flexibility to the energy ray-curable first protective film-forming film.

The energy ray-curable component (a) is preferably uncured, preferably has adhesive properties, and is more preferably uncured and has adhesive properties.

Examples of the energy ray curable component (a) include a polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80000 to 2000000 and a compound (a2) having an energy ray curable group and a molecular weight of 100 to 80000. . At least a part of the polymer (a1) may be crosslinked with a crosslinking agent or may not be crosslinked.

(Polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80000 to 2000000)

As the polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80000 to 2000000, for example, an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound, a group reacting with the functional group, and an energy ray curable double and an acrylic resin (a1-1) having a structure in which an energy ray-curable compound (a12) having an energy ray-curable group such as a bond is polymerized.

Examples of the functional groups capable of reacting with groups of other compounds include hydroxyl groups, carboxy groups, amino groups, substituted amino groups (groups having a structure in which one or two hydrogen atoms of an amino group are substituted with groups other than hydrogen atoms), epoxy groups, and the like. can However, in terms of preventing corrosion of circuits such as semiconductor wafers and semiconductor chips, the functional group is preferably a group other than a carboxyl group.

Among these, it is preferable that the said functional group is a hydroxyl group.

・Acrylic polymer (a11) having a functional group

Examples of the acrylic polymer (a11) having the functional group include those having a structure obtained by copolymerization of an acrylic monomer having the functional group and an acrylic monomer not having the functional group, and other than these monomers, further other than the acrylic monomer. It may have a structure in which a monomer (non-acrylic monomer) copolymerized.

The acrylic polymer (a11) may be a random copolymer or a block copolymer.

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

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

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having ethylenically unsaturated bonds) such as fumaric acid, itaconic acid, maleic acid and citraconic acid; anhydrides of the above ethylenically unsaturated dicarboxylic acids; (meth)acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate; and the like.

A hydroxyl group-containing monomer and a carboxyl group-containing monomer are preferable, and, as for the acrylic monomer which has the said functional group, a hydroxyl group-containing monomer is more preferable.

The acrylic monomers having the functional groups constituting the acrylic polymer (a11) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

Examples of the acrylic monomer having no functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (metha)acrylate. ) isobutyl acrylate, (meth) sec-butyl acrylate, (meth) tert-butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)acrylate ) Isooctyl acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (( lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate (palmityl ((meth)acrylate)) , (meth)acrylate heptadecyl, (meth)acrylate octadecyl (meth)acrylate (stearyl (meth)acrylate), etc., the alkyl group constituting the alkyl ester has a chain structure of 1 to 18 carbon atoms (meth)acrylate alkyl ester, etc. can be heard

Examples of the acrylic monomer having no functional group include alkoxyalkyl groups such as methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate ( meth) acrylic acid ester; (meth)acrylic acid esters having an aromatic group including (meth)acrylic acid aryl esters such as phenyl (meth)acrylate; non-crosslinkable (meth)acrylamide and its derivatives; (meth)acrylic acid esters having non-crosslinkable tertiary amino groups, such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate; and the like.

The acrylic monomer having no functional group constituting the acrylic polymer (a11) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; Styrene etc. are mentioned.

The non-acrylic monomer constituting the acrylic polymer (a11) may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

In the acrylic polymer (a11), the ratio (content) of the amount of the structural units derived from the acrylic monomer having the functional group to the total amount of the structural units constituting the acrylic polymer is preferably 0.1 to 50% by mass, and 1 It is more preferable that it is -40 mass %, and it is especially preferable that it is 3-30 mass %. When the ratio is within this range, the content of the energy ray curable group in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray curable compound (a12) is increased according to the energy ray curable agent. 1 It becomes possible to easily adjust the degree of hardening of the hardened|cured material (for example, 1st protective film) of a protective film formation film to a preferable range.

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

The ratio of the content of the acrylic resin (a1-1) to the total mass of the energy ray-curable first protective film-forming film in the energy ray-curable first protective film-forming film is preferably 1 to 40% by mass, and 2 to 30 It is more preferable that it is mass %, and it is especially preferable that it is 3-20 mass %.

・Energy ray curable compound (a12)

The energy ray-curable compound (a12) preferably has one or two or more groups selected from the group consisting of an isocyanate group, an epoxy group, and a carboxy group as a group capable of reacting with a functional group of the acrylic polymer (a11). It is more preferable to have an isocyanate group as a group. For example, when the energy ray-curable compound (a12) has an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

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

Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1- (bisacryloyloxymethyl)ethyl isocyanate;

Acryloyl monoisocyanate compound obtained by reaction of a diisocyanate compound or polyisocyanate compound, and hydroxyethyl (meth)acrylate;

The acryloyl monoisocyanate compound etc. which are obtained by reaction of a diisocyanate compound or a polyisocyanate compound, a polyol compound, and hydroxyethyl (meth)acrylate are mentioned.

Among these, it is preferable that the said energy ray-curable compound (a12) is 2-methacryloyloxyethyl isocyanate.

The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

In the acrylic resin (a1-1), the ratio of the content of the energy ray curable group derived from the energy ray curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is 20 to 120 It is preferably mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the ratio of the content is within this range, the adhesive force of the cured product (for example, the first protective film) of the energy ray-curable first protective film-forming film becomes larger. On the other hand, when the energy ray-curable compound (a12) is a monofunctional (having one of the groups in one molecule) compound, the upper limit of the ratio of the content is 100 mol%, but the energy ray-curable compound (a12) In the case of a polyfunctional (having two or more of the above groups in one molecule) compound, the upper limit of the ratio of the above content may exceed 100 mol%.

It is preferable that it is 100000-2000000, and, as for the weight average molecular weight (Mw) of the said polymer (a1), it is more preferable that it is 300000-1500000.

When the polymer (a1) is at least partially crosslinked by a crosslinking agent, the polymer (a1) does not correspond to any of the above-mentioned monomers described as constituting the acrylic polymer (a11), and also a crosslinking agent. A monomer having a group reactive with polymerizes, and may be crosslinked in a group reactive with the crosslinking agent, or may be crosslinked in a group reactive with the functional group derived from the energy ray curable compound (a12).

The polymer (a1) contained in the composition (IV) and the energy ray-curable first protective film-forming film may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

(Compound (a2) having an energy ray curable group and having a molecular weight of 100 to 80000)

Examples of the energy ray-curable group in the compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80000 include a group containing an energy ray-curable double bond, preferably a (meth)acryloyl group, a vinyl group, and the like. can be heard

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

Examples of the low molecular weight compound having an energy ray curable group among the compounds (a2) include polyfunctional monomers or oligomers, and an acrylate-based compound having a (meth)acryloyl group is preferable.

Examples of the acrylate-based compound include 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth) Acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxy Diethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloyloxypolypropoxy ) Phenyl] propane, tricyclodecane dimethanol di(meth)acrylate, 1,10-decanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,9-nonanedioldi (meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethylene glycol di (meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloxyethoxy)phenyl]propane, neopentyl glycol bifunctional (meth)acrylates such as di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, and 2-hydroxy-1,3-di(meth)acryloxypropane;

Tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone modified tris-(2-(meth)acryloxyethyl)isocyanurate, ethoxylated glycerin tri(meth)acrylate, pentaerythritol Tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipenta polyfunctional (meth)acrylates such as erythritol poly(meth)acrylate and dipentaerythritol hexa(meth)acrylate;

Polyfunctional (meth)acrylate oligomers, such as a urethane (meth)acrylate oligomer, etc. are mentioned.

Among the compounds (a2), as the epoxy resin having an energy ray curable group and the phenol resin having an energy ray curable group, those described in, for example, Paragraph 0043 of "Japanese Unexamined Patent Publication No. 2013-194102" can be used. Although such a resin also corresponds to a resin constituting a thermosetting component described later, in the present embodiment, it is handled as the compound (a2).

It is preferable that it is 100-30000, and, as for the weight average molecular weight of the said compound (a2), it is more preferable that it is 300-10000.

The compound (a2) contained in the composition (IV) and the energy ray curable first protective film-forming film may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

[Polymer (b) having no energy ray curable group]

When the composition (IV) and the energy ray-curable first protective film-forming film contain the compound (a2) as the energy ray-curable component (a), it is preferable to further contain a polymer (b) having no energy ray-curable group. do.

At least a part of the polymer (b) may be crosslinked with a crosslinking agent or may not be crosslinked.

Examples of the polymer (b) having no energy ray curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, and acrylic urethane resins.

Among these, it is preferable that the said polymer (b) is an acrylic polymer (it may abbreviate as "acrylic polymer (b-1)" hereafter).

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

Examples of the acrylic monomer constituting the acrylic polymer (b-1) include (meth)acrylic acid alkyl esters, (meth)acrylic acid esters having a cyclic backbone, glycidyl group-containing (meth)acrylic acid esters, and hydroxyl group-containing (meth)acrylic acid esters. meth)acrylic acid esters, substituted amino group-containing (meth)acrylic acid esters, and the like. Here, the "substituted amino group" is as described above.

As the (meth)acrylic acid alkyl ester, for example, an acrylic monomer having no functional group constituting the acrylic polymer (a11) described above (the alkyl group constituting the alkyl ester is a chain structure having 1 to 18 carbon atoms ( meta) acrylic acid alkyl ester etc.) and the same things are mentioned.

Examples of the (meth)acrylic acid ester having the cyclic skeleton include (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)acrylic acid cycloalkenyl esters such as (meth)acrylic acid dicyclopentenyl ester;

(meth)acrylic acid cycloalkenyloxyalkyl esters such as (meth)acrylic acid dicyclopentenyloxyethyl ester; and the like.

As said glycidyl group-containing (meth)acrylic acid ester, glycidyl (meth)acrylate etc. are mentioned, for example.

Examples of the hydroxyl group-containing (meth)acrylic acid ester include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxy (meth)acrylate. Propyl, (meth)acrylic acid 2-hydroxybutyl, (meth)acrylic acid 3-hydroxybutyl, (meth)acrylic acid 4-hydroxybutyl, etc. are mentioned.

Examples of the substituted amino group-containing (meth)acrylic acid ester include N-methylaminoethyl (meth)acrylic acid.

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

Examples of the polymer (b) having no energy ray curable groups at least partially crosslinked by a crosslinking agent include those in which the reactive functional groups in the polymer (b) reacted with the crosslinking agent.

The reactive functional group may be appropriately selected depending on the type of crosslinking agent and the like, and is not particularly limited. For example, when a crosslinking agent is a polyisocyanate compound, a hydroxyl group, a carboxy group, an amino group etc. are mentioned as said reactive functional group, Among these, a hydroxyl group highly reactive with an isocyanate group is preferable. In the case where the crosslinking agent is an epoxy-based compound, examples of the reactive functional group include a carboxy group, an amino group, an amide group, and the like, and among these, a carboxy group highly reactive with an epoxy group is preferable. However, in terms of preventing corrosion of circuits of semiconductor wafers or semiconductor chips, the reactive functional group is preferably a group other than a carboxy group.

Examples of the polymer (b) having the reactive functional group and not having an energy ray curable group include those obtained by polymerizing at least a monomer having the reactive functional group. In the case of the acrylic polymer (b-1), one or both of the acrylic monomer and the non-acrylic monomer mentioned as the monomers constituting this may be used which have the reactive functional group. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include one obtained by polymerizing a hydroxyl group-containing (meth)acrylic acid ester. In addition to this, in the aforementioned acrylic monomer or non-acrylic monomer, one or more and those obtained by polymerizing a monomer having a structure in which two or more hydrogen atoms are substituted with the above reactive functional groups.

In the polymer (b) having a reactive functional group, the ratio (content) of the amount of the constituent unit derived from the monomer having a reactive functional group to the total amount of the constituent unit constituting the polymer is preferably 1 to 20% by mass, , It is more preferable that it is 2-10 mass %. When the ratio is in this range, the degree of crosslinking in the polymer (b) is in a more preferable range.

The weight average molecular weight (Mw) of the polymer (b) not having an energy ray curable group is preferably from 10000 to 2000000, more preferably from 100000 to 1500000, from the viewpoint of improving the film formability of the composition (IV).

The composition (IV) and the polymer (b) having no energy ray curable group contained in the first energy ray-curable protective film-forming film may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof are can be selected arbitrarily.

Examples of the composition (IV) include those containing either or both of the polymer (a1) and the compound (a2). And, when composition (IV) contains the said compound (a2), it is preferable to also contain the polymer (b) which does not have an energy ray curable group further, and in this case, also containing the said polymer (a1) further desirable. In addition, the composition (IV) may contain both the polymer (a1) and the polymer (b) not having an energy ray curable group without containing the compound (a2).

When the composition (IV) contains the polymer (a1), the compound (a2), and the polymer (b) not having an energy ray curable group, the content of the compound (a2) in the composition (IV) is It is preferably 10 to 400 parts by mass, and more preferably 30 to 350 parts by mass with respect to 100 parts by mass of the total content of (a1) and the polymer (b) having no energy ray curable group.

The ratio of the total content of the energy ray-curable component (a) and the polymer (b) not having an energy ray-curable group to the total mass of the energy ray-curable first protective film-forming film in the energy ray-curable first protective film-forming film is , It is preferable that it is 5-90 mass %, it is more preferable that it is 10-80 mass %, and it is especially preferable that it is 20-70 mass %. When the ratio is within this range, the energy ray curability of the energy ray curable first protective film-forming film becomes better.

[filling]

By adjusting the amount of the filler in the composition (IV) and the energy ray curable first protective film forming film, when the energy ray curable first protective film forming film is attached to the bump formation surface, the energy ray curable first protective film on the upper part of the bump The effect of suppressing the remaining of the formed film can be controlled. In addition, the thermal expansion coefficient of the cured product (eg, the first protective film) of the energy ray-curable first protective film-forming film can be more easily adjusted. By optimizing for , the reliability of the package obtained by using the energy ray curable first protective film forming film is further improved. In addition, as will be described later, since the first protective film is formed not only on the bump formation surface of the semiconductor chip but also on the side surface, when filling the grooves formed on the bump formation surface of the semiconductor wafer with the first protective film formation film, the filling thereof You can adjust the degree of In addition, by using the energy ray-curable first protective film-forming film containing a filler, the moisture absorption rate of the cured product (eg, the first protective film) of the energy ray-curable first protective film-forming film can be reduced or heat dissipation can be improved. .

The filler contained in the composition (IV) and the energy ray-curable first protective film-forming film is the same as the filler (D) contained in the previously described composition (III) and the thermosetting first protective film-forming film.

The content of the filler in the composition (IV) and the first energy ray-curable protective film-forming film may be the same as the content of the filler (D) in the composition (III) and the thermosetting first protective film-forming film.

The filler contained in the composition (IV) and the energy ray-curable first protective film-forming film may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

The ratio of the content of the filler to the total mass of the energy ray-curable first protective film-forming film in the energy ray-curable first protective film-forming film may be, for example, 5 to 45% by mass. When the ratio is within this range, when the energy ray curable first protective film forming film is affixed to the bump formation surface, the effect of suppressing the remaining energy ray curable first protective film forming film on the upper part of the bump is higher, and , the above thermal expansion coefficient can be more easily adjusted. In addition, as will be described later, since the first protective film is formed not only on the bump formation surface of the semiconductor chip but also on the side surface, when filling the grooves formed on the bump formation surface of the semiconductor wafer with the non-curing first protective film formation film, enough to charge.

[additive]

By adjusting the type or amount of additives in the composition (IV) and the energy ray curable first protective film forming film, when the energy ray curable first protective film forming film is attached to the bump formation surface, the energy ray curable agent on the top of the bump 1 The effect of suppressing the survival of the protective film formation film can be adjusted.

The additives contained in the composition (IV) and the energy ray-curable first protective film-forming film are the same as the additives (I) contained in the above-described composition (III) and the thermosetting first protective film-forming film.

For example, preferable additives include a rheology modifier, a surfactant, and silicone oil from the viewpoint of being able to more easily control the effect of suppressing the survival of the above-described energy ray-curable first protective film-forming film.

The aspect of the composition (IV) and the first energy ray-curable protective film-forming film containing additives may be the same as the additive (I) contained in the composition (III) and the thermosetting first protective film-forming film.

The additives contained in the composition (IV) and the energy ray curable first protective film-forming film may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

The composition (IV) and the content of additives in the energy ray-curable first protective film-forming film are not particularly limited and can be appropriately adjusted depending on the type or purpose.

For example, in the case where the purpose is to control the effect of suppressing the survival of the above-described energy ray curable first protective film forming film, the total mass of the energy ray curable first protective film forming film in the energy ray curable first protective film forming film The ratio of the content of the additive to the additive may be, for example, 0.5 to 10% by mass.

[Other Ingredients]

The composition (IV) and the energy ray curable first protective film-forming film are the energy ray curable component (a), the filler, the additive, and a polymer having no energy ray curable group, within a range that does not impair the effects of the present invention. You may contain other components which do not correspond to any of (b).

As said other component, a thermosetting component, a photoinitiator, a coupling agent, a crosslinking agent, etc. are mentioned, for example. For example, by using the composition (IV) containing the energy ray curable component (a) and the thermosetting component, the energy ray curable first protective film-forming film is improved in adhesive strength to an adherend by heating, and this energy The strength of the cured product of the pre-curable first protective film-forming film (eg, the first protective film) is also improved.

The thermosetting component, photopolymerization initiator, coupling agent, and crosslinking agent in the composition (IV) are the thermosetting component (B), photopolymerization initiator, coupling agent (E), and crosslinking agent (F) in the composition (III), respectively. and the same can be mentioned.

The other components contained in the composition (IV) and the energy ray curable first protective film-forming film may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

The contents of the composition (IV) and the above-mentioned other components of the energy ray-curable first protective film-forming film are not particularly limited, and may be appropriately selected according to the purpose.

[menstruum]

Composition (IV) preferably further contains a solvent. The composition (IV) containing the solvent has good handleability.

The solvent contained in the composition (IV) includes, for example, the same solvent as the solvent contained in the above-described composition (III).

The solvent contained in the composition (IV) may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

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

An example of a preferred energy ray-curable first protective film-forming film from the viewpoint of further enhancing the desired effect of the present invention (the high-speed adhesion of the sheet for forming a first protective film described later and the penetrability of the first protective film-forming film) is energy The energy ray curable component (a) containing a radiation curable component (a), a filler, and an additive, with respect to the total mass of the energy ray curable first protective film forming film in the energy ray curable first protective film forming film (a) ), the filler, and the ratio of the total content of the additives is 85% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more.

In view of the above, an example of a more preferable energy ray-curable first protective film-forming film contains an energy ray-curable component (a), a polymer (b) having no energy ray-curable group, a filler, and an additive, The energy ray curable component (a) is either or both of a polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80000 to 2000000 and a compound (a2) having an energy ray curable group and having a molecular weight of 100 to 80000. The polymer (b) not having an energy ray curable group is one or two or more selected from the group consisting of acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, and acrylic urethane resins, and the additives are rheological It is one or two or more selected from the group consisting of a regulator, a surfactant, and a silicone oil, and the above energy ray curable first protective film forming film relative to the total mass of the energy ray curable first protective film forming film The ratio of the total content of the energy ray curable component (a), the polymer (b) having no energy ray curable group, the filler, and the additives is 85% by mass or more, preferably 90% by mass or more, more preferably is 95% by mass or more.

The thickness of these energy ray-curable first protective film-forming films is preferably 2 to 7 times, more preferably 3 to 6 times the thickness of the intermediate peeling layer.

<Method for Producing Composition for Forming Energy Ray Curable First Protective Film>

A composition for forming an energy ray-curable first protective film, such as composition (IV), is obtained by blending the respective components to constitute it.

The energy ray-curable composition for forming a first protective film may be prepared in the same manner as the above-described thermosetting composition for forming a first protective film, except that the types of ingredients are different.

○ Non-curing first protective film forming film

As a non-curing 1st protective film formation film, what contains a thermoplastic resin, a filler, and an additive is mentioned, for example.

<Composition (V) for forming a non-curable first protective film>

As the composition for forming a first non-curing protective film, for example, a composition for forming a first non-curing protective film (V) containing a thermoplastic resin, a filler, and an additive (in this specification, simply referred to as “composition (V)”) may be abbreviated).

[Thermoplastic resin]

The thermoplastic resin is not particularly limited.

As the thermoplastic resin, more specifically, for example, the curability of polyvinyl acetal, acrylic resin, urethane resin, phenoxy resin, silicone resin, saturated polyester resin, etc. The same thing as resin which is not is mentioned.

The thermoplastic resin contained in the composition (V) and the non-curing first protective film-forming film may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

It is preferable that the content ratio of the said thermoplastic resin with respect to the total mass of the non-curing 1st protective film-forming film in a non-curing 1st protective film-forming film is 25-75 mass %.

[filling]

The non-curable first protective film-forming film containing the filler exhibits the same effect as the thermosetting first protective film-forming film containing the filler (D).

Examples of the filler contained in the composition (V) and the non-curable first protective film-forming film include the same fillers (D) as those contained in the composition (III) and the thermosetting first protective film-forming film.

The filler contained in the composition (V) and the non-curing first protective film-forming film may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

The ratio of the content of the filler to the total mass of the non-curable first protective film-forming film in the non-curable first protective film-forming film is preferably 15 to 70% by mass. When the ratio is within this range, as in the case of using the composition (III), when the non-curable first protective film-forming film is attached to the bump formation surface, the remaining non-curable first protective film-forming film on the upper part of the bump While the effect of suppressing .

[additive]

By adjusting the type or amount of additives in the composition (V) and the non-curing first protective film-forming film, when the non-curing first protective film-forming film is attached to the bump formation surface, a non-curing first protective film is formed on the upper part of the bump The effect of suppressing the remaining of the film can be controlled.

The additive contained in the composition (V) and the non-curable first protective film-forming film is the same as the additive (I) contained in the above-described composition (III) and the thermosetting first protective film-forming film.

For example, preferable additives include a rheology modifier, a surfactant, and silicone oil from the viewpoint of being able to more easily control the effect of suppressing the survival of the above-described non-curable first protective film-forming film.

The composition (V) and the non-curable first protective film-forming film may contain the additive (I) in the composition (III) and the thermosetting first protective film-forming film.

The additives contained in the composition (V) and the non-curing first protective film-forming film may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

The content of the additives in the composition (V) and the non-curable first protective film-forming film is not particularly limited and can be appropriately adjusted depending on the type or purpose.

For example, in the case where the purpose is to control the effect of suppressing the survival of the above-described non-curable first protective film-forming film, the amount of additives relative to the total mass of the non-curable first protective film-forming film in the non-curable first protective film-forming film The ratio of the content may be, for example, 0.5 to 10% by mass.

[Other Ingredients]

Composition (V) and the non-curing first protective film-forming film may contain other components that do not correspond to any of the thermoplastic resin, the filler, and the additives within a range that does not impair the effects of the present invention.

The above other components are not particularly limited and may be arbitrarily selected according to the purpose.

The other components contained in the composition (V) and the non-curing first protective film-forming film may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

The content of the composition (V) and the above-mentioned other components of the non-curing first protective film-forming film is not particularly limited, and may be appropriately selected according to the purpose.

[menstruum]

Composition (V) preferably further contains a solvent. The composition (V) containing the solvent has good handleability.

Examples of the solvent contained in the composition (V) include the same solvent as the solvent contained in the above-described composition (III).

The solvent contained in the composition (V) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

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

One example of a preferred non-curable first protective film-forming film is a thermoplastic resin from the viewpoint of further enhancing the desired effect of the present invention (high-speed adhesion of the first protective film-forming sheet described later and penetrability of the first protective film-forming film) and a filler and an additive, and the ratio of the total content of the thermoplastic resin, the filler, and the additive to the total mass of the non-curable first protective film-forming film in the non-curable first protective film-forming film 85% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more.

In view of the above, an example of a more preferable non-curable first protective film-forming film contains a thermoplastic resin, a filler, and an additive, and the thermoplastic resin is polyvinyl acetal, acrylic resin, urethane resin, phenoxy resin, silicone resin, and one or two or more selected from the group consisting of a saturated polyester resin, and the additive is one or two or more selected from the group consisting of a rheology modifier, a surfactant, and a silicone oil, and the parenteral The ratio of the total content of the thermoplastic resin, the filler, and the additive to the total mass of the non-curable first protective film-forming film in the chemical conversion first protective film-forming film is 85% by mass or more, preferably 90% by mass or higher, more preferably 95% by mass or higher.

It is preferable that it is 2 to 7 times, and, as for the thickness of these non-curing 1st protective film formation film, it is more preferable that it is 3 to 6 times with respect to the thickness of an intermediate|middle peeling layer.

<Method for Producing Composition for Forming Non-curable First Protective Film>

A composition for forming a non-curable first protective film such as composition (V) is obtained by blending each component for constituting it.

The composition for forming a first non-curable protective film may be prepared in the same manner as the above-described composition for forming a thermosetting first protective film, except that the types of ingredients are different.

◎Intermediate release layer

When _the ratio (G _x '/GA ') of the shear storage modulus (G _x ') of the intermediate release layer to the shear storage modulus (GA _' ) of the buffer layer is less than 0.6, the bump formation surface of the semiconductor wafer is formed. When the sheet for forming the first protective film is attached to the surface, the embeddability of the bumps of the first protective film forming film is improved. This improves both the high-speed adhesion of the sheet for forming a first protective film to the bump formation surface of the semiconductor wafer and the penetrability of the bumps of the first protective film formation film.

The intermediate release layer preferably contains an ethylene-vinyl acetate copolymer (EVA). By containing EVA, the embeddability of the bump of the 1st protective film formation film is improved at the time of affixing the sheet|seat for 1st protective film formation with respect to the bump formation surface of a semiconductor wafer. Thereby, high-speed sticking of the sheet|seat for forming a 1st protective film to the bump formation surface of a semiconductor wafer is attained. In this specification, such a characteristic that enables high-speed sticking of the sheet for forming a first protective film is sometimes referred to as “high-speed sticking property”.

Further, since the intermediate peeling layer contains EVA, the first protective film forming film is strongly pressed by the buffer layer when the sheet for forming the first protective film is attached to the bump formation surface of the semiconductor wafer. This makes it possible to make the top of the bump protrude from the first protective film forming film and further suppress the remaining of the first protective film forming film on the top of the bump even when the sheet for forming the first protective film is attached at high speed. In this specification, in this way, the survival of the bumps at the top of the first protective film forming film in the first protective film forming sheet is suppressed, and the characteristic that the top of the bumps easily protrudes is sometimes referred to as "penetrability". .

Since EVA has a property of appropriately softening when heated, these effects, that is, the effect that the sheet for forming the first protective film has high-speed stickability and the first protective film-forming film has penetrability, particularly the first protective film When the sheet|seat for formation is attached while heating, it expresses remarkably.

Since the first sheet for forming a protective film of the present embodiment includes an intermediate peeling layer, the above-described excellent effect is exhibited regardless of the type of the first protective film forming film.

The intermediate release layer preferably contains an ethylene-vinyl acetate copolymer (EVA), and may contain only an ethylene-vinyl acetate copolymer (in other words, it may be a layer composed of an ethylene-vinyl acetate copolymer), or an ethylene-vinyl acetate copolymer. You may contain a vinyl acetate copolymer and other components other than that.

The intermediate release layer is in the form of a sheet or film.

The intermediate peeling layer may be only one layer (single layer) or may be a plurality of layers of two or more layers.

The thickness of the intermediate release layer is preferably 5 to 30 μm, more preferably 6 to 25 μm, and particularly preferably 7 to 20 μm.

Here, the "thickness of the intermediate peeling layer" means the thickness of the entire intermediate peeling layer. .

<<Composition for Forming Intermediate Release Layer>>

The intermediate release layer can be formed using a composition for forming an intermediate release layer containing the constituent materials thereof. For example, an intermediate release layer can be formed by coating a composition for forming an intermediate release layer on the surface to be formed of the intermediate release layer and drying it as necessary. A more specific method of forming the intermediate peeling layer will be described in detail later together with methods of forming the other layers. In the composition for forming an intermediate peeling layer, the ratio of the contents of components that do not vaporize at normal temperature is usually the same as the ratio of the contents of the above components in the intermediate peeling layer.

The composition of the intermediate peeling layer is not limited as long as it can be adjusted so that the ratio ( _Gx '/ _GA ') is less than 0.6. In the intermediate release layer, the ratio of the total content of one or two or more components described below to the total mass of the intermediate release layer does not exceed 100% by mass.

Similarly, in the composition for forming an intermediate release layer, the ratio of the total content of one or more of the following components in the composition for forming an intermediate release layer to the total mass of the composition for forming an intermediate release layer is 100% by mass. do not exceed

The composition for forming an intermediate peeling layer may be applied in the same manner as in the case of the composition for forming the first protective film described above.

Drying conditions for the composition for forming an intermediate release layer are not particularly limited. However, when the composition for forming an intermediate peeling layer contains a solvent described later, it is preferable to heat-dry the composition. Then, it is preferable to heat-dry the solvent-containing composition for forming an intermediate peeling layer under conditions of, for example, 70 to 130°C for 10 seconds to 5 minutes.

<Composition for Forming Intermediate Release Layer (VII)>

As the composition for forming an intermediate release layer, for example, the composition for forming an intermediate release layer (VII) containing an ethylene-vinyl acetate copolymer (EVA) (in this specification, it is simply referred to as “composition (VII)”). have), etc.

The composition (VII) may contain the ethylene-vinyl acetate copolymer and other components.

In the ethylene-vinyl acetate copolymer, the total amount of the constituent units (total amount of all constituent units constituting the ethylene-vinyl acetate copolymer. Hereinafter, the same.) (mass part) of the constituent units derived from vinyl acetate Ratio of the amount (parts by mass) ([amount of structural units derived from vinyl acetate constituting the ethylene-vinyl acetate copolymer (parts by mass)] / [total amount of all structural units constituting the ethylene-vinyl acetate copolymer) (Parts by mass)] × 100) is preferably 40% by mass or less, more preferably 37% by mass or less, still more preferably 34% by mass or less, for example, 30% by mass or less and 25% by mass or less. It can be any one. When the ratio is equal to or less than the upper limit, the handleability of the composition (VII) is further improved, the shear storage modulus (G _x ') of the intermediate peeling layer can be adjusted to be smaller, and the ratio (G _x '/ _GA ' ) can be adjusted smaller, and the high-speed sticking property of the sheet for forming a first protective film and the penetrability of the first protective film-forming film are higher.

In the present specification, the ratio of the amount (parts by mass) of structural units derived from vinyl acetate to the total amount (parts by mass) of the structural units in the ethylene-vinyl acetate copolymer is sometimes referred to as "VA content". .

In the ethylene-vinyl acetate copolymer, the ratio (VA content) of the amount (parts by mass) of the structural units derived from vinyl acetate to the total amount (parts by mass) of the structural units is preferably 40% by mass or less, and 37 It is more preferable that it is mass % or less, and it is more preferable that it is 34 mass % or less, and for example, either 30 mass % or less and 25 mass % or less may be sufficient. When the ratio is equal to or less than the above upper limit, the handleability of Composition (VII) is further improved, and the first protective film-forming film can be formed more easily.

In the ethylene-vinyl acetate copolymer, the ratio (VA content) of the amount (parts by mass) of the constituent units derived from vinyl acetate to the total amount (parts by mass) of the constituent units is the lower limit of any one of the above and the above Any one of the upper limit values can be arbitrarily combined and properly adjusted within the set range. For example, the ratio is preferably 16 to 40% by mass, more preferably 17.5 to 37% by mass, still more preferably 19 to 34% by mass, and, for example, 25 to 34% by mass and 30% by mass. Any one of -34 mass % may be sufficient, and any one of 19-30 mass % and 19-25 mass % may be sufficient. However, these are examples of the ratio.

The weight average molecular weight of the ethylene-vinyl acetate copolymer is preferably 200000 or less, more preferably 180000 or less, still more preferably 160000 or less, and may be, for example, 100000 or less and 60000 or less. When the weight average molecular weight is equal to or less than the upper limit, the high-speed sticking property of the sheet for forming a first protective film and the penetrability of the first protective film-forming film are further increased.

The lower limit of the weight average molecular weight of the ethylene-vinyl acetate copolymer is not particularly limited. For example, the weight average molecular weight may be 5000 or more in terms of improving the film-forming properties of Composition (VII).

The weight average molecular weight of the said ethylene-vinyl acetate copolymer may be any one of 5000-200000, 5000-180000, 5000-160000, 5000-100000, and 5000-60000, for example. However, these are examples of the above weight average molecular weight.

The ethylene-vinyl acetate copolymer is preferably the main component of the intermediate release layer. Thereby, the high-speed sticking property of the sheet|seat for forming a 1st protective film and the penetrability of a 1st protective film formation film become higher.

In particular, the ratio of the content of the ethylene-vinyl acetate copolymer to the total mass of the intermediate release layer in the intermediate release layer ([Content of ethylene-vinyl acetate copolymer in the intermediate release layer (parts by mass)] / [Intermediate release The total mass (parts by mass) of the layer] × 100) is preferably 80% by mass or more, more preferably 90% by mass or more, and for example, 95% by mass or more, 97% by mass or more, and 99% by mass or more. may be any one of When the ratio is equal to or greater than the lower limit, the high-speed adhesion of the sheet for forming a first protective film and the penetrability of the first protective film-forming film further increase.

The said ratio is 100 mass % or less.

[Other Ingredients]

The other components contained in Composition (VII) and the intermediate peeling layer are not particularly limited and can be appropriately selected according to the purpose.

The other components contained in Composition (VII) and the intermediate peeling layer may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

Examples of the other components contained in the composition (VII) and the intermediate release layer include non-polar resins such as ethylene polymers.

The ethylene-based polymer is a polymer having at least structural units derived from ethylene, and may be a homopolymer of ethylene or a copolymer of ethylene and another monomer.

Examples of the ethylene homopolymer (ie, polyethylene) include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), metallocene catalyst linear low density polyethylene (mLLDPE), medium density polyethylene (MDPE), and high density polyethylene. (HDPE) etc. are mentioned.

Oil components such as paraffin oil and paraffin wax may be sufficient as the non-polar resin, such as the said ethylenic polymer.

The other component contained in the composition (VII) includes a solvent. The solvent-containing composition (VII) is excellent in handling.

Examples of the solvent contained in the composition (VII) include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone; and the like.

The solvent contained in Composition (VII) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

The content of the other components in Composition (VII) and the intermediate peeling layer can be appropriately adjusted depending on the types of the other components.

When the other component is a component other than the solvent, the ratio of the content of the other component (component other than the solvent) to the total mass of the intermediate release layer in the intermediate release layer ([the other component other than the solvent in the intermediate release layer) The content (parts by mass)]/[total mass (parts by mass) of the intermediate peeling layer] × 100) is preferably 20% by mass or less, more preferably 10% by mass or less, for example, 5% by mass or less. , 3% by mass or less, and 1% by mass or less. When the ratio is equal to or less than the upper limit, the high-speed sticking property of the sheet for forming a first protective film and the penetrability of the first protective film-forming film are further enhanced.

When the said other component is a component other than a solvent, the said ratio is 0 mass % or more.

When the other component is a solvent, the ratio of the content of the other component (solvent) to the total mass of the composition (VII) in the composition (VII) ([content of the solvent in composition (VII) (parts by mass)]) /[total mass (parts by mass) of composition (VII)] × 100) is preferably 5 to 50% by mass, and may be, for example, 5 to 35% by mass or 5 to 20% by mass. When the ratio is equal to or greater than the lower limit, the handling properties of the composition (VII) are further improved. When the ratio is equal to or less than the upper limit, the first protective film-forming film can be formed more efficiently.

<Modification of Intermediate Peeling Layer>

So far, description has been given of the intermediate release layer formed using a composition for forming an intermediate release layer containing an ethylene-vinyl acetate copolymer (EVA), but in the present embodiment, the intermediate release layer is an ethylene-vinyl acetate copolymer Instead of (EVA), it may be formed using a composition for forming an intermediate release layer containing another resin component such as an acrylic resin. Examples of the acrylic resin include the acrylic resin described in the above-described composition for forming a thermosetting first protective film, the acrylic resin (a1-1) described in the above-described composition for forming an energy ray curable first protective film, and the like.

From the viewpoint of further enhancing the desired effect of the present invention (high-speed adhesion of the first protective film-forming sheet and penetrability of the first protective film-forming film), an example of a preferable intermediate release layer contains an ethylene-vinyl acetate copolymer and the ratio of the content of the ethylene-vinyl acetate copolymer to the total mass of the intermediate release layer in the intermediate release layer is 80% by mass or more, preferably 90% by mass or more, and the ethylene-vinyl acetate Among the copolymers, the ratio of the amount of structural units derived from vinyl acetate to the total amount of structural units is 16 to 40% by mass, and the weight average molecular weight of the ethylene-vinyl acetate copolymer is 200,000 or less. .

<<Method for Producing Composition for Forming Intermediate Release Layer>>

A composition for forming an intermediate peeling layer, such as Composition (VII), is obtained by blending the respective components to constitute it.

The composition for forming an intermediate release layer may be prepared by the same method as the above-described composition for forming a thermosetting first protective film, except that the types of ingredients are different.

◎Buffer layer

The buffer layer has a buffering action against a force applied to the buffer layer and the layers in its vicinity. Here, the "layer near the buffer layer" includes an intermediate peeling layer, a first protective film-forming film, and a first protective film.

The constituent material of the buffer layer is not particularly limited, but is preferably a resin.

Preferred examples of the buffer layer include those formed using a composition for forming a buffer layer containing urethane (meth)acrylate and the like.

The buffer layer may be only one layer (single layer) or may be a plurality of layers of two or more layers.

The thickness of the buffer layer is preferably 150 to 1000 μm, more preferably 150 to 800 μm, still more preferably 200 to 600 μm, and particularly preferably 250 to 500 μm.

Here, the "thickness of the buffer layer" means the thickness of the entire buffer layer, and, for example, the thickness of a buffer layer composed of a plurality of layers means the total thickness of all layers constituting the buffer layer.

<<Composition for Forming Buffer Layer>>

The buffer layer can be formed using a composition for forming a buffer layer containing a material for forming it. For example, the buffer layer can be formed by coating the composition for forming a buffer layer on the surface to be formed of the buffer layer and drying it as necessary. When the composition for forming a buffer layer has energy ray curability as described later, it is preferable to further cure the composition for forming a buffer layer after coating with energy ray. A more specific method of forming the buffer layer will be described in detail later along with methods of forming other layers.

In the composition for forming a buffer layer, the ratio of the total content of one or two or more of the components to be described later in the composition for forming a buffer layer to the total mass of the composition for forming a buffer layer does not exceed 100% by mass.

The composition for forming a buffer layer may be applied in the same manner as in the case of the above-described composition for forming a first protective film.

Drying conditions for the composition for forming a buffer layer are not particularly limited, and may be, for example, the same as those for the above-described composition for forming an intermediate peeling layer.

It is preferable that the illuminance of the energy beam at the time of energy-beam hardening of the composition for forming an energy-beam curable buffer layer is 100-350 mW/cm<2>, and it is preferable that the light quantity of an energy-beam is 200-1400 mJ/cm<2>. The energy-beam curing of the composition for forming an energy-beam-curable buffer layer may be performed once, or divided into two or more plural times (through semi-curing). In the case where the energy ray curing is performed by dividing into a plurality of times, it is preferable that the light amount of the energy ray is 200 to 1400 mJ/cm 2 in all times, and the total light amount of all times is preferably 200 to 1400 mJ/cm 2 .

<Composition for Forming Buffer Layer (VI)>

As the composition for forming a buffer layer, for example, a composition for forming a buffer layer (VI) containing urethane (meth)acrylate (X) (in this specification, it may be simply referred to as "composition (VI)"), etc. can be heard

[Urethane (meth)acrylate (X)]

The urethane (meth)acrylate (X) contained in the composition (VI) is a compound having at least a (meth)acryloyl group and a urethane bond, and has a property of polymerizing when irradiated with energy rays. That is, composition (VI) has energy ray curability. The number of (meth)acryloyl groups in the urethane (meth)acrylate (X) may be 1, 2, or 3 or more (ie, urethane (meth)acrylate (X) is monofunctional , bifunctional, and trifunctional or more than one may be used), but monofunctional urethane (meth)acrylate (X) is preferred. Since monofunctional urethane (meth)acrylate (X) does not participate in the formation of a three-dimensional network structure in the polymerization structure, it becomes difficult to form a three-dimensional network structure in the buffer layer, in which case the first sheet for forming a protective film is It becomes easy to follow the bump formation surface of a semiconductor wafer.

The urethane (meth)acrylate (X) contained in the composition (VI) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

Examples of the urethane (meth)acrylate (X) include a terminal isocyanate urethane prepolymer, which is a reaction product of a polyol compound (x1) and a polyisocyanate compound (x2), and a reaction product of a compound (x3) having a (meth)acryloyl group. can be heard Here, "terminal isocyanate urethane prepolymer" is as having previously demonstrated.

The polyol compound (x1) is not particularly limited as long as it is a compound having two or more hydroxyl groups in one molecule.

Examples of the polyol compound (x1) include alkylene diols, polyether polyols, polyester polyols, and polycarbonate polyols. Among these, it is preferable that the polyol compound (x1) is a polyether type polyol.

The polyol compound (x1) may be any of a bifunctional diol, a trifunctional triol, and a tetrafunctional or higher functional polyol, but from the viewpoints of availability, versatility, reactivity, etc., a bifunctional diol is preferred. It is more preferable that it is an ether type diol.

As said polyether type diol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol etc. are mentioned, for example.

The polyester type polyol is obtained by subjecting a polyol component and a polybasic acid component to a polycondensation reaction. Examples of the polyol component include various alkanediols such as ethylene glycol, diethylene glycol, and butanediol (preferably, alkanediol having 2 to 10 carbon atoms), various glycols, and the like.

As said polybasic acid component, well-known components are mentioned as a polybasic acid component of general polyester, for example. As the polybasic acid component, more specifically, for example, aliphatic dibasic acids having 4 to 20 carbon atoms, such as adipic acid and sebacic acid; aromatic dibasic acids such as terephthalic acid; aromatic polybasic acids such as trimellitic acid; anhydrides of these dibasic or polybasic acids; Derivatives of these dibasic acids or polybasic acids, dimer acids, hydrogenated dimer acids, and the like are exemplified.

The polycarbonate type polyol is not particularly limited. As said polycarbonate type polyol, the reaction material of glycols and alkylene carbonate, etc. are mentioned, for example.

Examples of the polyisocyanate compound (x2) include aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates.

Examples of the compound (x3) having a (meth)acryloyl group include (meth)acrylate having a hydroxyl group, which was previously mentioned as constituting the acrylic resin as the polymer component (A), which is a component of composition (III). The same thing as hydroxyl-containing (meth)acrylic acid ester is mentioned.

Especially, it is preferable that the (meth)acrylate which has the said hydroxyl group is a hydroxyalkyl (meth)acrylate.

The weight average molecular weight of the urethane (meth)acrylate (X) is preferably 1000 to 100000, more preferably 3000 to 80000, still more preferably 5000 to 65000. When the weight average molecular weight is 1000 or more, appropriate hardness is imparted to the buffer layer by a polymer of urethane (meth)acrylate (X) and a polymerizable monomer (Z) described later.

Ratio of the content of urethane (meth)acrylate (X) to the total content of components other than the solvent in composition (VI) ([content of urethane (meth)acrylate (X) in composition (VI) (part by mass) )]/[total content (parts by mass) of components other than the solvent of composition (VI)] × 100) is preferably 10 to 70% by mass, more preferably 20 to 70% by mass, and 25 to 60% by mass. It is more preferable that it is mass %, and it is especially preferable that it is 30-50 mass %. When the ratio is within this range, the effect obtained by providing the buffer layer in the first sheet for forming a protective film is higher without impairing other effects.

[Other Ingredients]

Composition (VI) may contain urethane (meth)acrylate (X) and other components not corresponding to urethane (meth)acrylate (X).

Examples of the other components in the composition (VI) include a thiol group-containing compound (Y) and a polymerizable monomer (Z).

The other components contained in the composition (VI) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

Composition (VI) may contain only either one of the thiol group-containing compound (Y) and the polymerizable monomer (Z), but preferably contains both the thiol group-containing compound (Y) and the polymerizable monomer (Z). .

(thiol group-containing compound (Y))

The thiol group-containing compound (Y) is not particularly limited as long as it is a compound having one or two or more thiol groups (-SH) in one molecule.

Examples of the thiol group-containing compound (Y) include nonylmercaptan, 1-dodecanethiol, 1,2-ethanedithiol, 1,3-propanedithiol, triazinethiol, triazinedithiol, and triazinetrithiol. , 1,2,3-propanetrithiol, tetraethylene glycol-bis(3-mercaptopropionate), trimethylolpropanetris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate) cionate), pentaerythritol tetrakithioglycolate, dipentaerythritol hexakis (3-mercaptopropionate), tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, 1,4 -bis(3-mercaptobutyryloxy)butane, pentaerythritoltetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine -2,4,6-(1H,3H,5H)-trion etc. are mentioned.

The thiol group-containing compound (Y) is preferably a polyfunctional thiol group-containing compound (a compound having two or more thiol groups in one molecule), and a tetrafunctional thiol group-containing compound (a compound having four thiol groups in one molecule). is more preferable.

The thiol group-containing compound (Y) contained in the composition (VI) may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

Content of thiol group-containing compound (Y) relative to 100 parts by mass of the total content of urethane (meth)acrylate (X) and polymerizable monomer (Z) in composition (VI) ([thiol group of composition (VI) Content (parts by mass) of containing compound (Y)]/[total content (parts by mass) of urethane (meth)acrylate (X) and polymerizable monomer (Z) in composition (VI)] × 100) is 1 to It is preferably 4.9 parts by mass, and more preferably 1.5 to 4.8 parts by mass.

(polymerizable monomer (Z))

Composition (VI) preferably contains a polymerizable monomer (Z) from the viewpoint of improving the film-forming properties of the buffer layer. The polymerizable monomer (Z) is a polymerizable compound other than the urethane (meth)acrylate (X), which can be polymerized by irradiation with energy rays. However, the resin component is not contained in the polymerizable monomer (Z). Here, the "resin component" means an oligomer or polymer having a repeating structure in its structure, and a compound having a weight average molecular weight of 1000 or more.

It is preferable that the said polymerizable monomer (Z) is a compound which has 1 or 2 or more (meth)acryloyl groups. Examples of such a polymerizable monomer (Z) include (meth)acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester has a chain structure of 1 to 18 carbon atoms; (meth)acrylic acid ester having a functional group such as a hydroxyl group, an amide group, an amino group, or an epoxy group; (meth)acrylic acid esters having alicyclic structures such as (meth)acrylic acid cycloalkyl esters; (meth)acrylic acid ester having an aromatic structure; (meth)acrylic acid ester having a heterocyclic structure; Vinyl compounds other than these, etc. are mentioned.

Among the (meth)acrylic acid esters having the functional group, the (meth)acrylic acid esters having the hydroxyl group include, for example, those containing the hydroxyl group mentioned above as constituting the acrylic resin as the polymer component (A) that is the component (III) contained in the composition (III). The same thing as (meth)acrylic acid ester is mentioned.

Examples of the (meth)acrylic acid ester having the alicyclic structure include isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyloxy. (meth)acrylate, cyclohexyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, etc. are mentioned.

Examples of (meth)acrylic acid esters having an aromatic structure include phenylhydroxypropyl (meth)acrylate, benzyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate. can be heard

As (meth)acrylic acid ester which has the said heterocyclic structure, tetrahydrofurfuryl (meth)acrylate, 2-morpholinoethyl (meth)acrylate, etc. are mentioned, for example.

The polymerizable monomer (Z) contained in the composition (VI) may be one type or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

Composition (VI) preferably contains at least a (meth)acrylic acid ester having an alicyclic structure as the polymerizable monomer (Z), and a (meth)acrylic acid ester having an alicyclic structure and a (meth)acrylic acid ester having a functional group. It is more preferable to contain together, and it is more preferable to contain isobornyl (meth)acrylate and hydroxyalkyl (meth)acrylate together.

Ratio of the content of the polymerizable monomer (Z) to the total content of components other than the solvent in the composition (VI) ([content of the polymerizable monomer (Z) in the composition (VI) (parts by mass)] / [composition The total content (parts by mass) of components other than the solvent of (VI)] × 100) is preferably 20 to 80% by mass, more preferably 30 to 80% by mass, and still more preferably 40 to 75% by mass. It is preferable, and it is especially preferable that it is 50-70 mass %. When the content is within this range, since the movement of the portion having the structure in which the polymerizable monomer (Z) is polymerized in the buffer layer is higher, the buffer layer tends to be more flexible, and the first sheet for forming a protective film is a semiconductor wafer. It becomes easy to track by the bump formation surface of .

The ratio of the content of (meth)acrylic acid ester having an alicyclic structure to the total content of polymerizable monomers (Z) in composition (VI) ([(meth)acrylic acid ester having an alicyclic structure of composition (VI) content (parts by mass)]/[total content (parts by mass) of polymerizable monomers (Z) of composition (VI)] × 100) is preferably 52 to 87 mass%, preferably 55 to 85 mass% It is more preferable, and it is still more preferable that it is 60-80 mass %. When the content is within this range, the first sheet for forming a protective film easily follows the bump formation surface of the semiconductor wafer.

The mass ratio of [content (parts by mass) of urethane (meth)acrylate (X) in composition (VI)]/[content (parts by mass) of polymerizable monomer (Z) in composition (VI)] is 20/80 to It is preferably 60/40, more preferably 30/70 to 50/50, and still more preferably 35/65 to 45/55. When the mass ratio is within this range, the first sheet for forming a protective film easily follows the bump formation surface of the semiconductor wafer.

(photopolymerization initiator)

Composition (VI) preferably further contains a photopolymerization initiator. Composition (VI) containing a photopolymerization initiator is more easily cured by irradiation with energy rays.

Examples of the photopolymerization initiator contained in the composition (VI) include acetophenone, 2,2-diethoxybenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, Michler's ketone, and benzoin. , benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldiphenylsulfide, tetramethylthiurammonosulfide, benzyldimethylketal, dibenzyl, diacetyl, 1-chloroanthraquinone , 2-chloroanthraquinone, 2-ethylanthraquinone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4- (methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-hydroxy-2- low molecular weight polymerization initiators such as methyl-1-phenyl-propan-1-one, diethylthioxanthone, isopropylthioxanthone, and 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide; and oligomerized polymerization initiators such as oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}.

The photopolymerization initiator contained in the composition (VI) may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

Content of photopolymerization initiator relative to 100 parts by mass of the total content of urethane (meth)acrylate (X) and polymerizable monomer (Z) in composition (VI) ([Content of photopolymerization initiator in composition (VI) (part by mass )]/[total content (parts by mass) of urethane (meth)acrylate (X) and polymerizable monomer (Z) in composition (VI) × 100) is preferably 0.05 to 15 parts by mass, and preferably 0.1 to 10 It is more preferable that it is a mass part, and it is still more preferable that it is 0.3-5 mass parts.

(other additives)

Composition (VI) may contain other additives that do not correspond to the components described above, within a range that does not impair the effects of the present invention.

Examples of the other additives include crosslinking agents, antioxidants, softeners (plasticizers), fillers, rust preventives, pigments, and dyes.

When the composition (VI) contains the above other additives, the above other additives relative to 100 parts by mass of the total content of the urethane (meth)acrylate (X) and the polymerizable monomer (Z) in the composition (VI) Content of additives ([content of other additives in composition (VI) (parts by mass)] / [total content of urethane (meth)acrylate (X) and polymerizable monomer (Z) in composition (VI) (parts by mass)) ]×100) is preferably 0.01 to 6 parts by mass, and more preferably 0.1 to 3 parts by mass.

(Other resin components)

Composition (VI) may contain other resin components that do not correspond to urethane (meth)acrylate (X) within a range that does not impair the effects of the present invention.

<Modification of buffer layer>

Up until now, it has been described that the buffer layer is formed using a composition for forming a buffer layer containing urethane (meth)acrylate (X) as the buffer layer, but in this embodiment, the buffer layer is urethane (meth)acrylate (X) instead of olefin It may be formed using a composition for forming a buffer layer containing another resin component such as a system resin.

From the point where the desired effect of the present invention (high-speed adhesion of the first protective film-forming sheet and penetrability of the first protective film-forming film) is higher, examples of preferred buffer layers include urethane (meth)acrylate (X) and , A buffer layer obtained by using a composition for forming a buffer layer (composition (VI)) containing a thiol group-containing compound (Y), a polymerizable monomer (Z), a photopolymerization initiator, and a crosslinking agent, in the composition for forming a buffer layer Sum of the urethane (meth)acrylate (X), the thiol group-containing compound (Y), the polymerizable monomer (Z), the photopolymerization initiator, and the crosslinking agent relative to the total content of components other than the solvent of The ratio of content is 85 mass % or more, Preferably it is 90 mass % or more, More preferably, it is 95 mass % or more.

In view of the above, an example of a more preferred buffer layer is a buffer layer containing urethane (meth)acrylate (X), a thiol group-containing compound (Y), a polymerizable monomer (Z), a photopolymerization initiator, and a crosslinking agent A buffer layer obtained using the composition for formation (composition (VI)), wherein the urethane (meth)acrylate (X) is a terminal isocyanate urethane prepolymer that is a reaction product of a polyol compound (x1) and a polyisocyanate compound (x2), (meth ) A reactant of a compound (x3) having an acryloyl group, wherein the thiol group-containing compound (Y) is a polyfunctional thiol group-containing compound having two or more thiol groups in one molecule, and the polymerizable monomer (Z) (meth)acrylic acid ester having an alicyclic structure and (meth)acrylic acid ester having a functional group, and the urethane (meth)acrylate (X) with respect to the total content of components other than the solvent in the composition for forming a buffer layer The ratio of the total content of the thiol group-containing compound (Y), the polymerizable monomer (Z), the photopolymerization initiator, and the crosslinking agent is 85% by mass or more, preferably 90% by mass or more, more preferably Those of 95% by mass or more are exemplified.

These buffer layers are preferably obtained by energy ray curing of the composition for forming a buffer layer.

The thickness of these buffer layers is preferably 10 to 70 times the thickness of the intermediate release layer, and more preferably 30 to 50 times.

<<Method for Producing Composition for Forming Buffer Layer>>

A composition for forming a buffer layer, such as composition (VI), is obtained by blending each component to constitute it.

The composition for forming a buffer layer may be prepared in the same manner as the above-described composition for forming a first thermosetting protective film, except that the types of ingredients are different.

◎First equipment

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

Examples of the resin include polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); polyolefins other than polyethylene, such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin; Ethylene-based copolymers such as ethylene-vinyl acetate copolymers, ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylic acid ester copolymers, and ethylene-norbornene copolymers (copolymers obtained by using ethylene as a monomer) ; vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymers (resin obtained by using vinyl chloride as a monomer); polystyrene; polycycloolefins; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, and fully aromatic polyesters in which all constituent units have aromatic cyclic groups; copolymers 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.

Examples of the resin include polymer alloys such as mixtures of the polyester and other resins. In the polymer alloy of the polyester and other resins, it is preferable that the amount of the resin other than the polyester is relatively small.

Examples of the resin include a crosslinked resin in which one or two or more of the resins exemplified so far are crosslinked; Modified resins such as ionomers using one or two or more of the above resins exemplified so far are also included.

The resin constituting the first substrate may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

The first base material may be only one layer (single layer) or may be a plurality of layers of two or more layers.

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, and, for example, the thickness of the first substrate composed of a plurality of layers means the total thickness of all the layers constituting the first substrate. .

It is preferable that the first substrate has a high thickness precision, that is, one in which variation in thickness is suppressed regardless of the site. Among the constituent materials described above, examples of materials usable for constructing the first base material having such high accuracy in thickness include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymers.

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

The first substrate may be transparent or opaque, may be colored depending on the purpose, or may have other layers deposited thereon.

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

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

The first sheet for forming a protective film of the present embodiment has the following side surfaces.

"1" A first sheet for forming a first protective film for forming a first protective film on at least a surface having bumps of a semiconductor wafer,

The first sheet for forming a protective film is formed by laminating a first substrate, a buffer layer, an intermediate peeling layer, and a first protective film forming film in this order in their thickness direction,

the intermediate release layer contains an ethylene-vinyl acetate copolymer, and the ratio of the content of the ethylene-vinyl acetate copolymer to the total mass of the intermediate release layer in the intermediate release layer is 80% by mass or more;

The sheet for forming a first protective film, wherein the ratio (G _x '/ _GA ') of the shear storage modulus ( _{G x} ') of the intermediate release layer to the shear storage modulus (GA ') of the buffer layer is less than 0.6.

[2] In the above-mentioned ethylene-vinyl acetate copolymer, the ratio of the amount of structural units derived from vinyl acetate to the total amount of structural units is 16 to 40% by mass, preferably 17.5 to 37% by mass, The first sheet for forming a protective film described in "1", more preferably 19 to 34% by mass, still more preferably 25 to 34% by mass.

"3" The weight average molecular weight of the ethylene-vinyl acetate copolymer is 200000 or less, preferably 180000 or less, more preferably 160000 or less, still more preferably 100000 or less, according to "1" or "2". A sheet for forming a first protective film.

"4" The first sheet for forming a protective film according to any one of "1" to "3", wherein the intermediate peeling layer has a shear storage modulus ( _Gx ') of 10000 Pa or less.

"5" Any one of "1" to "4", wherein the buffer layer has a shear storage modulus ( _GA ') of 10000 to 400000 Pa, preferably 50000 to 300000 Pa, and more preferably 100000 to 200000 Pa. A sheet for forming a first protective film.

[6] The first protective film-forming film is a thermosetting first protective film-forming film containing a polymer component (A), a thermosetting component (B), a curing accelerator (C), a filler (D), and an additive (I). Phosphorus, the sheet for forming a first protective film according to any one of "1" to "5".

"7" The polymer component (A) is polyvinyl acetal, the thermosetting component (B) is an epoxy resin (B1) and a thermosetting agent (B2), and the additive (I) is a rheology modifier, surfactant, and silicone It is one or two or more selected from the group consisting of oil, and the polymer component (A) with respect to the total mass of the thermosetting first protective film-forming film in the thermosetting first protective film-forming film, and the thermosetting component (B ), the curing accelerator (C), the filler (D), and the ratio of the total content of the additive (I) is 85 mass% or more, preferably 90 mass% or more, more preferably 95 mass% The above, the first sheet for forming a protective film according to “6”.

"8" The buffer layer obtained by using a composition for forming a buffer layer containing urethane (meth)acrylate (X), a thiol group-containing compound (Y), a polymerizable monomer (Z), a photopolymerization initiator, and a crosslinking agent As a buffer layer, the urethane (meth) acrylate (X), the thiol group-containing compound (Y), and the polymerizable monomer (Z) relative to the total content of components other than the solvent in the buffer layer forming composition In any one of "1" to "7", wherein the ratio of the total content of the photopolymerization initiator and the crosslinking agent is 85% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass or more. The sheet for forming the first protective film described above.

"9" The buffer layer obtained by using a composition for forming a buffer layer containing urethane (meth)acrylate (X), a thiol group-containing compound (Y), a polymerizable monomer (Z), a photopolymerization initiator, and a crosslinking agent As a buffer layer, the urethane (meth) acrylate (X) is a terminal isocyanate urethane prepolymer, which is a reaction product of a polyol compound (x1) and a polyisocyanate compound (x2), and a compound (x3) having a (meth) acryloyl group. , The thiol group-containing compound (Y) is a polyfunctional thiol group-containing compound having two or more thiol groups in one molecule, and the polymerizable monomer (Z) is a (meth)acrylic acid ester having an alicyclic structure, and a functional group The first sheet for forming a protective film according to any one of "1" to "8", which is a (meth)acrylic acid ester having.

"10" For forming the first protective film according to any one of "1" to "9", wherein the thickness of the first protective film-forming film is 2 to 7 times, more preferably 3 to 6 times the thickness of the intermediate peeling layer. Sheet.

◇Manufacturing method of sheet for forming first protective film

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

For example, the sheet|seat for forming a 1st protective film can be manufactured by the method shown below.

That is, a buffer layer is formed on the first substrate by coating a composition for forming a buffer layer (for example, the above composition (VI)) on one side of the first substrate and drying as necessary. When the composition for forming a buffer layer has energy ray curability, the composition for forming a buffer layer after coating is further cured with energy rays. As a result, a first laminated sheet formed by laminating the first substrate and the buffer layer is obtained. A peeling film may be further formed on the exposed surface (surface on the opposite side to the first substrate side) of the buffer layer in the first laminated sheet as needed.

Separately, an intermediate release layer is formed on the release film by coating a composition for forming an intermediate release layer (for example, the above composition (VII)) on the release film and drying as necessary. At this time, it is preferable to apply the composition for forming the intermediate peeling layer to the peeling-treated surface of the peeling film.

Separately, a composition for forming a first protective film (for example, the above composition (III), composition (IV), or composition (V)) is coated on a release film and dried as necessary to form a first protective film on the release film. A protective film forming film is formed. At this time, it is preferable to apply the composition for forming the first protective film to the release-treated surface of the release film.

Next, the exposed surface of the buffer layer (surface opposite to the first substrate side) and the exposed surface of the intermediate release layer (surface opposite to the release film side) of the first laminated sheet are bonded together. As a result, a second laminate sheet configured by laminating the first substrate, the buffer layer, the intermediate release layer, and the release film in this order in the thickness direction is obtained.

Next, in the second laminated sheet, the release film is removed, and the resulting exposed surface of the intermediate release layer (surface opposite to the buffer layer side) and the exposed surface of the first protective film forming film (opposite to the release film side) side) is attached. As a result, a first sheet for forming a protective film formed by laminating the first base material, the buffer layer, the intermediate peeling layer, the first protective film forming film, and the peeling film in this order in the thickness direction is obtained. What is necessary is just to remove the peeling film formed on the 1st protective film formation film in the 1st protective film formation sheet|seat at any stage from after manufacture of a 1st protective film formation sheet to after use.

In the manufacturing method described above, the first sheet for forming a protective film having layers other than the above-mentioned layers is either one of the step of forming the other layer and the step of lamination so that the lamination position of the other layer is at an appropriate position. Or it can manufacture by adding both suitably.

◇Method of manufacturing semiconductor device (method of using sheet for forming first protective film)

As described above, using the first sheet for forming a protective film of the present embodiment, the first protective film forming film therein is adhered to the bump formation surface of the semiconductor wafer, and then, if necessary, the first protective film forming film is cured. , A semiconductor wafer having a first protective film having a semiconductor wafer and a first protective film formed on a bump formation surface of the semiconductor wafer can be manufactured. At this time, the first sheet for forming a protective film of the present embodiment can be applied at high speed to the bump formation surface of the semiconductor wafer. In addition, even when the sheet for forming the first protective film is attached at high speed, it is possible to make the top of the bump protrude from the first protective film forming film and suppress the remaining of the first protective film forming film on the top of the bump. Subsequently, by dividing the semiconductor wafer with the first protective film, a semiconductor chip with a first protective film comprising a semiconductor chip and a first protective film formed on a bump formation surface of the semiconductor chip can be manufactured. At this time, since the survival of the first protective film forming film on the upper part of the bump of the semiconductor wafer on which the first protective film was formed was suppressed, adhesion of the first protective film to the upper part of the bump of the obtained semiconductor chip on which the first protective film was formed was also suppressed. are suppressed In addition, a semiconductor device can be manufactured by flip-chip-connecting the semiconductor chip on which the first protective film is formed to the substrate at the bump therein. At this time, since the adhesion of the first protective film on the top of the bump of the semiconductor chip on which the first protective film is formed is suppressed, the electrical connection between the semiconductor chip and the substrate is not hindered. That is, the first sheet for forming a protective film of the present embodiment is suitable for manufacturing a semiconductor device.

Hereinafter, the manufacturing method of the semiconductor device in the case of using the said 1st sheet|seat for forming a protective film is demonstrated.

A method for manufacturing a semiconductor device according to an embodiment of the present invention is a method for manufacturing a semiconductor device using the sheet for forming a first protective film according to an embodiment of the present invention described above, the manufacturing method comprising: For forming the first protective film on the semiconductor wafer by attaching the first protective film forming film in the sheet to the bump-bearing surface (bump formation surface) of the semiconductor wafer and protruding the top of the bump from the first protective film forming film An attaching step of forming a sheet, and after the attaching step, layers other than the first protective film forming film of the first protective film forming sheet are removed from the first protective film forming film, and the first protective film forming film is When the first protective film-forming film is curable, the first protective film-forming film is formed by curing the first protective film-forming film, and when the first protective film-forming film is non-curable, the first protective film is formed after removing layers other than the first protective film-forming film. A first protective film forming step of forming the first protective film on the surface having the bumps (bump formation surface) by treating the film as a first protective film, and dividing the semiconductor wafer after the first protective film forming step to divide the semiconductor chip. A division step of producing a semiconductor chip, and a cutting step of cutting the first protective film after the first protective film forming step, and the semiconductor chip obtained after the division process and the cutting process, and the bump-bearing surface of the semiconductor chip A semiconductor chip having the formed first protective film and having a first protective film protruding from the top of the bump is flip-chip connected to a substrate at the top of the bump.

Among the semiconductor device manufacturing methods of the present embodiment, the manufacturing method when the first protective film forming film is curable (in this specification, sometimes referred to as "manufacturing method (1)") is for forming the first protective film For forming the first protective film on the semiconductor wafer by attaching the first protective film forming film in the sheet to the bump-bearing surface (bump formation surface) of the semiconductor wafer and protruding the top of the bump from the first protective film forming film An attaching step of forming a sheet, and after the attaching step, layers other than the first protective film forming film are removed from the first protective film forming film in the sheet for forming the first protective film, and further, the first protective film forming film a first protective film forming step of forming the first protective film on the surface having the bumps (bump formation surface) by curing to form a first protective film; and dividing the semiconductor wafer after the first protective film forming step. A division step of fabricating a chip; a cutting step of cutting the first protective film after the first protective film forming step; the semiconductor chip obtained after the division process and the cutting process; and the surface of the semiconductor chip having the bumps. and a mounting step of flip-chip connecting a semiconductor chip having a first protective film formed thereon, and having a top portion of the bump protruding from the first protective film, to a substrate at the top portion of the bump. .

Among the semiconductor device manufacturing methods of the present embodiment, the manufacturing method in the case where the first protective film-forming film is non-curing (in this specification, it may be referred to as “manufacturing method (2)”) is for forming the first protective film For forming the first protective film on the semiconductor wafer by attaching the first protective film forming film in the sheet to the bump-bearing surface (bump formation surface) of the semiconductor wafer and protruding the top of the bump from the first protective film forming film An attaching step of forming a sheet, and after the attaching step, layers other than the first protective film forming film are removed from the first protective film forming film in the sheet for forming a first protective film, and other than the first protective film forming film A first protective film forming step of forming the first protective film on the surface having the bumps (bump formation surface) by treating the first protective film-forming film after removing the layer of the first protective film as a first protective film, and the first protective film forming step. Then, a division step of manufacturing a semiconductor chip by dividing the semiconductor wafer, a cutting step of cutting the first protective film after the first protective film forming step, and the semiconductor chip obtained after the dividing step and the cutting step, A semiconductor chip having the first protective film formed on a surface of the semiconductor chip having the bump and having a first protective film formed on the top of the bump protruding from the first protective film, at the top of the bump, a substrate It has a mounting process to connect the flip chip to.

<<Manufacturing method (1)>>

The manufacturing method (1) will be described below.

3A to 3E are cross-sectional views for schematically explaining an example of a manufacturing method (1) in the case of using the first sheet for forming a protective film 1 shown in FIG. 2 .

Meanwhile, in the drawings after FIG. 3A , the same reference numerals as those in the previously described drawings are assigned the same reference numerals, and detailed descriptions thereof are omitted.

<Applying process>

In the affixing step of the manufacturing method (1), as shown in Figs. For forming a first protective film on the semiconductor wafer 9 by attaching it to the surface (bump formation surface) 9a having a Sheet 1 is formed.

In the sticking step, first, as shown in FIG. 3A, for example, the first protective film forming film 14 of the sheet 1 for forming a first protective film is formed on the bump formation surface 9a of the semiconductor wafer 9 ) is placed opposite to

The height of the bump 91 is not particularly limited, but is preferably 120 to 300 μm, more preferably 150 to 270 μm, and particularly preferably 180 to 240 μm. When the height of the bump 91 is equal to or greater than the lower limit, the function of the bump 91 can be further improved. When the height of the bump 91 is equal to or less than the above upper limit, the effect of suppressing the remaining of the first protective film forming film 14 on the upper portion 910 of the bump 91 is further enhanced.

In this specification, the "height of a bump" means the height of a part of a bump that exists at the highest position from the bump formation surface.

The width of the bump 91 is not particularly limited, but is preferably 170 to 350 μm, more preferably 200 to 320 μm, and particularly preferably 230 to 290 μm. When the width of the bump 91 is greater than or equal to the lower limit, the function of the bump 91 can be further improved. When the width of the bump 91 is equal to or less than the above upper limit, the effect of suppressing the remaining of the first protective film-forming film 14 on the upper portion 910 of the bump 91 is further enhanced.

In this specification, the "width of a bump" means the maximum value of the length of a line segment obtained by connecting two different points on the bump surface with a straight line when looking down at the bump from a direction perpendicular to the bump formation surface and seeing it in a plane view. do.

The distance between adjacent bumps 91 is not particularly limited, but is preferably 250 to 800 μm, more preferably 300 to 600 μm, and particularly preferably 350 to 500 μm. When the distance is greater than or equal to the lower limit, the function of the bump 91 can be further improved. When the distance is equal to or less than the upper limit value, the effect of suppressing the remaining of the first protective film forming film 14 on the upper portion 910 of the bump 91 is further increased.

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

Next, in the sticking step, the first protective film forming film 14 is brought into contact with the bumps 91 on the semiconductor wafer 9 to bring the first protective film forming sheet 1 into close contact with the semiconductor wafer 9 . In this way, the first surface 14a of the first protective film forming film 14 is sequentially pressed against the surface 91a of the bump 91 and the bump formation surface 9a of the semiconductor wafer 9 . At this time, by heating the first protective film forming film 14, the first protective film forming film 14 is softened and diffused between the bumps 91 so as to cover the bumps 91, and on the bump formation surface 9a. While adhering, the surface 91a of the bump 91, especially the surface 91a of the vicinity of the bump formation surface 9a, is covered, and the base of the bump 91 is buried.

By the above, as shown in FIG. 3B, the 1st protective film formation film 14 in the sheet|seat 1 for 1st protective film formation is affixed on the bump formation surface 9a of the semiconductor wafer 9.

As described above, as a method of pressing (in other words, attaching) the first sheet for forming a protective film 1 to the semiconductor wafer 9, a known method of pressing and attaching various sheets to an object can be applied. , For example, the method of using a roller type laminator, etc. are mentioned.

The heating temperature of the first protective film-forming sheet 1 (first protective film-forming film 14) at the time of pressure bonding (affixing) to the semiconductor wafer 9 is such that the curing of the thermosetting first protective film-forming film 14 It may be a temperature that does not progress at all or excessively, and may be, for example, 80 to 100°C.

However, it is more preferable that the said heating temperature is 85-95 degreeC from the point which the effect of suppressing the survival|survival of the 1st protective film formation film 14 in the upper part 910 of the bump 91 becomes higher.

The pressure at which the sheet 1 for forming the first protective film (first protective film forming film 14) is pressed (attached) to the semiconductor wafer 9 is not particularly limited, and is, for example, 0.1 to 1.5 MPa. may be continued

However, it is more preferable that the said pressure is 0.3-1 MPa in the point which the effect of suppressing the survival|survival of the 1st protective film formation film 14 in the upper part 910 of the bump 91 becomes higher.

The speed (adhesion speed) at the time of sticking the sheet|seat 1 (1st protective film formation film 14) for 1st protective film formation to the semiconductor wafer 9 may be 3 mm/s or more, for example, but 4 It is preferable that it is mm/s or more. That is, in the said sticking process, it is preferable to stick the 1st protective film formation film 14 to the bump formation surface 9a of the semiconductor wafer 9 at the sticking speed of 4 mm/s or more. By attaching the first protective film-forming film 14 at a high speed of 4 mm/s or more, the effect of suppressing the remaining of the first protective film-forming film 14 on the upper part 910 of the bump 91 described above is more markedly expressed. On the other hand, when the attaching speed is 20 mm/s or less, the above-described effect of suppressing the remaining of the first protective film-forming film 14 on the upper portion 910 of the bump 91 is more stably expressed.

As described above, when the first sheet 1 for forming a protective film is compressed (applied) to the semiconductor wafer 9, the first protective film forming film 14 and the intermediate peeling layer in the sheet 1 for forming a first protective film ( 13), pressure is applied from the bumps 91 by press-fitting through the buffer layer 12, and initially, the first surface 14a of the first protective film forming film 14 and the intermediate peeling layer 13 The first surface 13a of is deformed into a concave shape. And as it is, in the 1st protective film formation film 14 to which pressure was applied from the bump 91, a fracture arises. Finally, in the step where the first surface 14a of the first protective film forming film 14 is pressed against the bump formation surface 9a of the semiconductor wafer 9, the top portion 9101 of the bump 91 is formed. The upper portion 910 protrudes through the first protective film forming film 14 . On the other hand, when the intermediate peeling layer 13 contains an olefinic thermoplastic resin such as EVA, in this final step, the upper part 910 of the bump 91 does not penetrate the intermediate peeling layer 13.

As shown in FIG. 3B, at the stage where the attaching process is completed, the first protective film forming film 14 does not remain at all or almost on the upper part 910 including the top part 9101 of the bump 91, In the upper portion 910 of the bump 91, the remaining of the first protective film forming film 14 is suppressed. On the other hand, in this specification, "the first protective film forming film hardly remains on the upper part of the bump" unless otherwise specified, although the first protective film forming film remains slightly on the upper part of the bump, the remaining amount is this bump It means that it is an amount that does not interfere with the electrical connection between the semiconductor chip and the substrate when flip-chip connecting the semiconductor chip provided with the substrate.

After the attaching step of the manufacturing method (1), if necessary, the surface (rear surface) 9b of the semiconductor wafer 9 opposite to the bump formation surface 9a is further ground, then this back surface 9b ), a sheet for forming a second protective film (not shown) is attached.

<First protective film formation step>

After the sticking step of the manufacturing method (1), in the first protective film forming step, first, as shown in FIG. 3C, among the first protective film forming sheets 1, other than the first protective film forming film 14 The layer is removed from the first protective film forming film 14 . In this specification, this step in the first protective film forming step may be referred to as a “removal step”. The layers to be removed here are, more specifically, the first substrate 11, the buffer layer 12, and the intermediate peeling layer 13. As a result, a semiconductor wafer 914 having a first protective film forming film comprising the semiconductor wafer 9 and the first protective film forming film 14 formed on the bump formation surface 9a of the semiconductor wafer 9 is obtained. lose

Layers other than the first protective film-forming film 14 can be removed from the first protective film-forming film 14 by a known method.

In the first protective film formation step of the manufacturing method (1), as shown in Fig. 3D, the first protective film forming film 14 is further cured to form the first protective film 14', thereby forming bumps. A first protective film 14' is formed on the surface 9a. In this specification, this step in the first protective film forming step may be referred to as a “curing step”. Thus, a semiconductor wafer 914' with a first protective film comprising the semiconductor wafer 9 and the first protective film 14' formed on the bump formation surface 9a of the semiconductor wafer 9 is obtained.

The first protective film-forming film 14 is curable, and in this step (the curing step), when the first protective film-forming film 14 is thermosetting, the first protective film-forming film 14 is cured by heating. , In the case where the first protective film-forming film 14 is energy ray-curable, the first protective film-forming film 14 is cured by irradiation with energy rays. Heating conditions and energy ray irradiation conditions at this time are as described above.

<Division process, cutting process>

After the first protective film forming step of the manufacturing method (1), in the dividing step, the semiconductor chip 90 is manufactured by dividing the semiconductor wafer 9, and in the cutting step, the first protective film 14' is formed. Cut it. Here, a new reference numeral 140' is assigned to the first protective film 14' after cutting.

By performing the division process and the cutting process, as shown in FIG. 3E , the first protective film ( In this specification, a semiconductor chip 9140' with a first protective film formed by including (sometimes simply referred to as a "first protective film") 140' is obtained.

The said division process and cutting process can be performed by a well-known method.

Although the order in which the division process and the cutting process are performed is not particularly limited, it is preferable to perform the division process and the cutting process simultaneously or to perform the division process and the cutting process in this order. In the case where the division step and the cutting step are performed in this order, the division step may be performed by known dicing, for example, and then the cutting step may be performed continuously and immediately thereafter. Dicing can be performed by forming a dicing sheet (not shown) on the back surface (which may be the back surface after grinding) 9b of the semiconductor wafer 9 .

In the cutting step, the first protective film 14' is cut along the portion where the semiconductor wafer 9 is to be divided or the portion where it is divided (ie, the outer periphery of the semiconductor chip 90).

In the semiconductor chip 9140' on which the first passivation film is formed, the top portion 9101 of the bump 91 protrudes from the first passivation film 140', and includes the top portion 9101 of the bump 91. The first passivation layer is not or almost not attached to the upper portion 910 , and adhesion of the first passivation layer to the upper portion 910 of the bump 91 is suppressed. On the other hand, in this specification, "the first protective film is hardly adhered to the upper part of the bump", unless otherwise specified, although the first protective film is slightly adhered to the upper part of the bump, the amount of the first protective film is provided with this bump. It means that it is an amount that does not interfere with the electrical connection between the semiconductor chip and the substrate when the semiconductor chip is flip-chip connected to the substrate.

＜Mounting process＞

In the mounting step of the manufacturing method (1), the top portion 9101 of the bump 91 obtained after the dividing step and the cutting step protrudes from the first protective film 140'. The semiconductor chip with the first protective film ( 9140') is flip-chip connected to the substrate at the top portion 9101 of the bump 91 (not shown). At this time, the semiconductor chip 9140' on which the first protective film is formed is connected to the circuit formation surface of the substrate.

Since the adhesion of the first protective film 140' to the upper part 910 of the bump 91 in the semiconductor chip 9140' on which the first protective film is formed is suppressed, in this step, the semiconductor chip 90 and the substrate has a high degree of electrical connection.

When the second sheet for forming a protective film is used, the semiconductor chip 9140' on which the first protective film is formed is separated from the dicing sheet (not shown) in the second sheet for forming a protective film and picked up prior to the flip chip connection. .

The semiconductor chip 9140' on which the first passivation film is formed can be picked up by a known method.

When the sheet for forming the second protective film is used, the semiconductor chip 90 in the semiconductor chip 9140' on which the first protective film is formed has a second protective film after cutting on its back surface 90b (not shown).

In the case where the second protective film-forming film in the sheet for forming a second protective film is curable, the second protective film-forming film is cured at an appropriate timing according to its type to form a second protective film. Then, the second protective film is cut at an appropriate timing according to its type.

The second protective film-forming film may be cured in the same way as the first protective film-forming film 14, and may be cured simultaneously with the first protective film-forming film 14, or separately from the first protective film-forming film 14. It may be hardened.

The second passivation layer may be cut in the same way as the first passivation layer.

Although the order of the division process and the cutting of the second protective film is not particularly limited, it is preferable to perform the division process and the cutting of the second protective film simultaneously or to cut the second protective film after the division process. In the case where the dividing step and the cutting of the second protective film are performed in this order, the dividing step may be performed by known dicing, for example, and then the second protective film may be cut immediately in succession.

The second protective film is cut along the portion to be divided or the divided portion of the semiconductor wafer 9 (ie, the outer periphery of the semiconductor chip 90).

After that, a semiconductor package is manufactured according to a known method using the circuit board on which the semiconductor chip 90 obtained in this way is mounted, and the target semiconductor device can be manufactured by using the semiconductor package. (Cities omitted).

<<Manufacturing method (2)>>

Next, the manufacturing method (2) will be described.

4A to 4D are cross-sectional views for schematically explaining an example of a manufacturing method (2) in the case of using the first sheet for forming a protective film 1 shown in FIG. 2 .

In the affixing step of the manufacturing method (2), as shown in Figs. For forming a first protective film on the semiconductor wafer 9 by attaching it to the surface (bump formation surface) 9a having a Sheet 1 is formed.

The sticking step of the manufacturing method (2) is the same as the sticking step of the manufacturing method (1) except that the first protective film-forming film 14 in the first sheet for forming a protective film 1 is non-curable and not curable. , It can be performed similarly to the said sticking process of manufacturing method (1). Therefore, the detailed description above about the sticking process of the manufacturing method (2) is abbreviate|omitted.

Also in the manufacturing method (2), even if the first protective film forming film 14 is affixed to the bump formation surface 9a of the semiconductor wafer 9 at high speed, as shown in FIG. , The first protective film forming film 14 does not or hardly remain on the upper part 910 including the top part 9101 of the bump 91, and in the upper part 910 of the bump 91, the first protective film Survival of the formed film 14 is suppressed.

After the attaching step of the manufacturing method (2), the surface (rear surface) 9b of the semiconductor wafer 9 on the opposite side to the bump formation surface 9a is further ground as needed, and then this back surface 9b ), a sheet for forming a second protective film (not shown) is attached.

<First protective film formation step>

After the sticking step of the manufacturing method (2), in the first protective film forming step, layers other than the first protective film forming film 14 among the first protective film forming sheets 1 are applied to the first protective film forming film 14 ) is removed from In this specification, as in the case of the manufacturing method (1), this step in the first protective film forming step may be referred to as a “removal step”. This step (the above-mentioned removal step) is the above-mentioned removal step in the above-mentioned manufacturing method (1) except that the first protective film-forming film 14 in the first sheet for forming a protective film 1 is not curable but non-curable. It is the same as, and can be performed in the same manner as the removal step in the manufacturing method (1). Therefore, the above detailed description of the removal step in the manufacturing method (2) is omitted.

In the first protective film formation step of the manufacturing method (2), the non-curable first protective film forming film 14 after removing layers other than the first protective film forming film 14 is treated as the first protective film. As a result, as shown in Fig. 4C, the first protective film 14' is formed on the bump formation surface 9a.

The non-curing first protective film-forming film 14 also functions as a protective film in its state. Accordingly, in this embodiment, the non-curable first protective film-forming film 14 is regarded as the first protective film 14' after the intermediate peeling layer 13 is removed during its use.

Thus, the semiconductor wafer 914' on which the first protective film is formed is obtained similarly to the case after the curing step in the manufacturing method (1).

Also in the manufacturing method (2), in the semiconductor chip 9140' on which the first protective film is formed, the top portion 9101 of the bump 91 protrudes from the first protective film 140', and the The first passivation layer is not or almost not attached to the upper portion 910 including the top portion 9101 , and adhesion of the first passivation layer to the upper portion 910 of the bump 91 is suppressed.

<Division process, cutting process>

After the first protective film forming step of the manufacturing method (1), in the dividing step, the semiconductor chip 90 is manufactured by dividing the semiconductor wafer 9, and in the cutting step, the first protective film 14' cut the

By performing the division process and the cutting process, a semiconductor chip 9140' with a first protective film is obtained as shown in Fig. 4D.

The division process and the cutting process of the manufacturing method (2) are the above division process and the cutting process of the manufacturing method (1), except that the first protective film 14' is not a cured product of the first protective film-forming film 14. It is the same as the process, and can be performed in the same manner as the above-mentioned division process and cutting process of the manufacturing method (1). Therefore, the detailed description above about the division process and the cutting process of the manufacturing method (2) is abbreviate|omitted.

＜Mounting process＞

In the mounting step of the manufacturing method (2), the top portion 9101 of the bump 91 obtained after the dividing step and the cutting step protrudes from the first protective film 140'. The semiconductor chip with the first protective film ( 9140') is flip-chip connected to the substrate at the top portion 9101 of the bump 91 (not shown). At this time, the semiconductor chip 9140' on which the first protective film is formed is connected to the circuit formation surface of the substrate.

Since the adhesion of the first protective film 140' to the upper part 910 of the bump 91 in the semiconductor chip 9140' on which the first protective film is formed is suppressed, in this step, the semiconductor chip 90 and the substrate has a high degree of electrical connection.

The mounting process of the manufacturing method (2) is the same as the above mounting process of the manufacturing method (1) except that the first protective film 140' is not a cured product of the first protective film forming film 14, and the manufacturing method It can be carried out in the same way as the mounting step of (1). Therefore, the above detailed description of the mounting process of the manufacturing method (2) is omitted.

Also in the manufacturing method (2), from now on, a semiconductor package is fabricated using the circuit board on which the semiconductor chip 90 is mounted in the same way as in the case of the manufacturing method (1), and this semiconductor package is used for the purpose. A semiconductor device can be manufactured (not shown).

In either of the manufacturing method (1) and the manufacturing method (2), the case where the first sheet for forming a protective film 1 shown in FIG. 2 was used was described here, but the first sheet for forming a protective film of another embodiment was Even when used, this first sheet for forming a protective film exhibits the same effect as in the case of using the sheet 1 for forming a first protective film.

<<Modified Example of Method for Manufacturing Semiconductor Device (Method of Using Sheet for Forming First Protective Film)>>

In the semiconductor device manufacturing method of the present embodiment, as the semiconductor wafer, one having grooves formed on the bump formation surface to be divided into semiconductor chips when the semiconductor wafer is divided into semiconductor chips can be used. By using such a semiconductor wafer, it is possible to manufacture a semiconductor chip in which the first protective film is formed not only on the bump formation surface but also on the side surface. Here, the side surface means the outer periphery of the semiconductor chip continuing to the bump formation surface, and a semiconductor chip having a rectangular planar shape has four side surfaces. In the semiconductor chip having a rectangular planar shape, a first protective film is formed on the bump formation surface and four side surfaces of the semiconductor chip. Regardless of the planar shape of the semiconductor chip, the semiconductor chip whose side surface is also protected in this way can obtain a higher protective effect by the first protective film.

In this case, the semiconductor device manufacturing method of the present embodiment is, for example, a semiconductor device manufacturing method using the first protective film forming sheet according to one embodiment of the present invention described above. , The first protective film forming film in the first sheet for forming a protective film is formed on the surface having the bumps (bump formation surface) in addition to grooves that serve as divisions of the semiconductor wafer. by attaching it to the bump-bearing surface (bump formation surface), protruding the top of the bump from the first protective film forming film, and filling the groove with the first protective film forming film, An attaching step of forming a first protective film forming sheet, and after the attaching step, removing layers other than the first protective film forming film from the first protective film forming film among the first protective film forming sheets, 1 If the protective film-forming film is curable, the first protective film-forming film is cured to form a first protective film, and if the first protective film-forming film is non-curable, after removing layers other than the first protective film-forming film A first protective film forming step of forming the first protective film on a surface having bumps (bump formation surface) by treating the first protective film forming film as a first protective film, and after the first protective film forming step, the semiconductor wafer The surface (back surface) opposite to the surface having bumps (bump formation surface) of the semiconductor is ground, and the grinding surface is brought to a groove filled with a protective film (the groove appears on the opposite surface). A division step of fabricating a group of semiconductor chips united by a first protective film filled in grooves by dividing the wafer; a cutting step of cutting the first protective film after the division step; a semiconductor chip including the semiconductor chip and the first protective film formed on surfaces and side surfaces of the semiconductor chip having the bumps, wherein tops of the bumps protrude from the first protective film; A manufacturing method of a semiconductor device having a mounting step of flip chip connection to a substrate at the top of the bump is exemplified.

Among the modifications of the semiconductor device manufacturing method of the present embodiment, the manufacturing method in the case where the first protective film forming film is curable (in this specification, it may be referred to as “manufacturing method (3)”) is a semiconductor wafer , The first protective film forming film in the first sheet for forming a protective film is formed on the surface having the bumps (bump formation surface) in addition to grooves that serve as divisions of the semiconductor wafer. by attaching it to the bump-bearing surface (bump formation surface), protruding the top of the bump from the first protective film forming film, and filling the groove with the first protective film forming film, An attaching step of forming a first protective film forming sheet, and after the attaching step, removing layers other than the first protective film forming film from the first protective film forming film among the first protective film forming sheets, A first protective film forming step of forming a first protective film on a surface having bumps (bump formation surface) by curing a first protective film forming film to form a first protective film; and, after the first protective film forming step, the semiconductor The surface (back surface) opposite to the surface having the bumps (bump formation surface) of the wafer is ground, and the grinding surface is brought to the groove filled with the first protective film (the groove appears on the opposite surface) ), a division step of manufacturing a group of semiconductor chips united by a first protective film filled in grooves by dividing the semiconductor wafer, a cutting step of cutting the first protective film after the division step, the division step, and A semiconductor with a first protective film having the semiconductor chip obtained after the cutting process, and the first protective film formed on the bump-bearing surface and side surface of the semiconductor chip, wherein tops of the bumps protrude from the first protective film. A mounting process of flip-chip connecting the chip to the board at the top of the bump is provided.

Among the modifications of the semiconductor device manufacturing method of the present embodiment, the manufacturing method in the case where the first protective film forming film is non-curing (in this specification, it may be referred to as "manufacturing method (4)") is a semiconductor wafer , The first protective film forming film in the first sheet for forming a protective film is formed on the surface having the bumps (bump formation surface) in addition to grooves that serve as divisions of the semiconductor wafer. by attaching it to the bump-bearing surface (bump formation surface), protruding the top of the bump from the first protective film forming film, and filling the groove with the first protective film forming film, An attaching step of forming a first protective film forming sheet, and after the attaching step, removing layers other than the first protective film forming film from the first protective film forming film among the first protective film forming sheets, A first protective film forming step of forming the first protective film on the surface having the bumps (bump formation surface) by treating the first protective film forming film after removing layers other than the protective film forming film as a first protective film, and 1 After the protective film forming step, the surface (rear surface) opposite to the bump-bearing surface (bump formation surface) of the semiconductor wafer is ground, and the grinding surface is brought to the groove filled with the first protective film (the opposite side a division step of fabricating a group of semiconductor chips integrated by a first protective film filled in the grooves by dividing the semiconductor wafer by making the grooves appear on the surface), and cutting the first protective film after the division step. a cutting process, the semiconductor chip obtained after the dividing process and the cutting process, and the first protective film formed on surfaces and side surfaces of the semiconductor chip having the bumps, wherein tops of the bumps protrude from the first protective film and a mounting step of flip-chip connecting the semiconductor chip on which the first protective film is formed to the substrate at the top of the bump.

The above-described bonding step of the above-described modifications (manufacturing method (3) and manufacturing method (4)) is the same as described above, except that a semiconductor wafer having the groove formed in addition to the bump formation surface thereof is used. It can be carried out in the same manner as the above-mentioned affixing step of the manufacturing method (manufacturing method (1) and manufacturing method (2)) using a semiconductor wafer in which a single groove is not formed.

The first protective film forming step of the above-described modification (production method (3) and manufacturing method (4)) is a manufacturing method (production method (1) and manufacturing method using a semiconductor wafer in which the above-described groove is not formed). (2)) may be performed in the same manner as the first protective film forming step.

The above-mentioned division step of the above-mentioned modification (manufacturing method (3) and manufacturing method (4)) is the above-described groove except that the division method of the semiconductor wafer is limited to a specific method of grinding the back surface of the semiconductor wafer. It can be carried out in the same manner as the above division step of the manufacturing method (manufacturing method (1) and manufacturing method (2)) using the unformed semiconductor wafer.

The cutting step of the above-described modifications (manufacturing method (3) and manufacturing method (4)) is performed on, for example, the surface (rear surface) opposite to the surface (bump formation surface) of all semiconductor chips having the bumps. It can be carried out by attaching a dicing sheet and then cutting the first protective film filled in the groove along the side surface of the semiconductor chip at a site near the center of the groove in the width direction. By doing in this way, by cutting the 1st protective film between the side surfaces of adjacent semiconductor chips, the semiconductor chip in the state in which the 1st protective film was formed on these side surfaces is obtained. The cutting of the first protective film at this time can be performed by a known method.

The mounting step of the above-described modification (manufacturing method (3) and manufacturing method (4)) is a manufacturing method (manufacturing method (1) and manufacturing method (2)) using a semiconductor wafer in which the above-mentioned groove is not formed. ) can be performed in the same manner as the above mounting step.

The use of the sheet of this embodiment has the following aspects.

"101" Use of a sheet for forming a first protective film on at least the bumped surface of a semiconductor wafer,

Use of a sheet wherein the sheet is the sheet for forming a first protective film according to any one of [1] to [5] or any one of "1" to "10".

Example

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not at all limited to the examples shown below.

<Ingredients for producing the composition for forming the first protective film>

The raw material used for manufacture of the 1st composition for forming a protective film is shown below.

[Polymer component (A)]

(A)-1: Polyvinyl butyral having structural units represented by the following formulas (i)-1, (i)-2, and (i)-3 (manufactured by Sekisui Chemical Co., Ltd. "S-REC BL-10 ", weight average molecular weight 25000, glass transition temperature 59 ° C.)

(In the formula, l ₁ is about 28, m ₁ is 1 to 3, and n ₁ is an integer of 68 to 74.)

[Epoxy Resin (B1)]

(B1)-1: Liquid modified bisphenol A type epoxy resin ("Epiclon EXA-4850-150" manufactured by DIC, molecular weight 900, epoxy equivalent 450 g/eq)

(B1)-2: dicyclopentadiene type epoxy resin (“Epiclon HP-7200HH” manufactured by DIC, epoxy equivalent 254 to 264 g/eq)

[Heat curing agent (B2)]

(B2)-1: O-cresol type novolac resin (“Phenolite KA-1160” manufactured by DIC)

[Curing accelerator (C)]

(C)-1: 2-phenyl-4,5-dihydroxymethylimidazole ("Cuazole 2PHZ-PW" manufactured by Shikoku Kasei Kogyo)

[Filling material (D)]

(D)-1: Spherical silica modified with an epoxy group (“Admanano YA050C-MKK” manufactured by Admatechs, average particle size: 50 nm)

[Additive (I)]

(I)-1: Surfactant (acrylic polymer, “BYK-361N” manufactured by BYK)

(I)-2: Silicone oil (Aralkyl modified silicone oil, manufactured by Momentive Performance Material Japan "XF42-334")

[Example 1]

<<Manufacture of sheet for forming first protective film>>

<Preparation of composition for forming thermosetting first protective film>

Polymer component (A)-1 (100 parts by mass), epoxy resin (B1)-1 (290 parts by mass), epoxy resin (B1)-2 (220 parts by mass), (B2)-1 (160 parts by mass), Curing accelerator (C)-1 (2 parts by mass), filler (D)-1 (200 parts by mass), additive (I)-1 (25 parts by mass), and additive (I)-2 (3 parts by mass) It was dissolved or dispersed in methyl ethyl ketone and stirred at 23°C to obtain a composition (III) having a total concentration of 45% by mass of all components other than the solvent as a first thermosetting composition for forming a protective film. On the other hand, all of the compounding amounts of components other than the solvent shown here are the compounding amounts of the target material without solvent.

<Manufacture of the first protective film-forming film>

Using a release film ("SP-PET381031" manufactured by Lintec, 38 µm thick) in which one side of the polyethylene terephthalate film has been subjected to a release treatment by silicone treatment, the composition (III) obtained above is coated on the release treatment surface. And, by heat-drying at 120 degreeC for 2 minutes, the 45 micrometer-thick 1st protective film formation film was formed.

<Preparation of composition for forming buffer layer>

Monofunctional urethane acrylate (40 parts by mass), isobornyl acrylate (45 parts by mass), 2-hydroxypropyl acrylate (15 parts by mass), pentaerythritol tetrakis (3-mercaptobutyrate) (Showa Den "Karenz MT (registered trademark) PE1" manufactured by KOSA, a secondary tetrafunctional thiol group-containing compound, a solid content concentration of 100% by mass) (3.5 parts by mass), a crosslinking agent (1.8 parts by mass), and a photopolymerization initiator (2-hydroxy -2-methyl-1-phenyl-propan-1-one and "Darocur (registered trademark) 1173" manufactured by BASF, solid content concentration: 100% by mass) (1.0 parts by mass) were blended to prepare composition (VI). .

<Formation of buffer layer>

Using a PET-based film (“Cosmo Shine (registered trademark) A4300” manufactured by Toyobo Co., Ltd., thickness: 75 μm) as a first substrate, the composition (VI) obtained above was coated on one side of the first substrate, and a coating film was formed. formed The coating film was irradiated with ultraviolet rays from the outside on the exposed surface side (opposite side to the PET-based film side) to form a semi-cured product of the coating film. At this time, a belt conveyor type ultraviolet irradiation device ("ECS-401GGX" manufactured by Eye Graphics) is used as the ultraviolet irradiation device, and a high-pressure mercury lamp ("H04-L41" manufactured by Eye Graphics) is used as the ultraviolet source, and the wavelength A 365 nm ultraviolet ray was irradiated under conditions of an illuminance of 120 mW/cm 2 and a light quantity of 200 mJ/cm 2 . These irradiation conditions were specified using an ultraviolet integrated illuminance meter (“UVPF-A1” manufactured by Eye Graphics).

Next, to the exposed surface of the obtained semi-cured product, the release treated surface of the release film (“SP-PET381031” manufactured by Lintec, 38 μm) was bonded to prepare a laminate, and to this laminate, the release film side Ultraviolet rays were irradiated from the outside to completely cure the semi-cured material, thereby forming a buffer layer having a thickness of 400 µm. At this time, ultraviolet rays with a wavelength of 365 nm were irradiated under conditions of an illuminance of 330 mW/cm 2 and a light quantity of 1200 mJ/cm 2 using the same ultraviolet irradiation device and ultraviolet source as described above. These irradiation conditions were specified using the same ultraviolet ray integrating illuminometer as described above.

Thus, a laminated sheet (corresponding to the first laminated sheet) configured by laminating the first substrate, the buffer layer, and the release film in this order in the thickness direction was obtained.

<Preparation of composition for forming intermediate release layer>

An ethylene-vinyl acetate copolymer (EVA, weight average molecular weight: 55000, VA content: 20% by mass) was dissolved in toluene at room temperature to prepare a toluene solution having a solid content concentration of 12% by mass, which was used as Composition (VII).

<Formation of Intermediate Peeling Layer>

Composition (VII) obtained above was coated on the release-treated surface of the release film ("SP-PET381031" manufactured by Lintec, Inc., thickness 38 µm) and heated and dried at 100°C for 2 minutes to form an intermediate release layer having a thickness of 10 µm. formed

<Manufacture of sheet for forming first protective film>

In the laminated sheet with a buffer layer obtained above (first laminated sheet), the release film is removed, and the exposed surface of the resulting buffer layer is bonded to the exposed surface of the intermediate release layer obtained above, thereby adding an intermediate release layer A laminated sheet (corresponding to the second laminated sheet) was obtained. Next, the peeling film was removed from the intermediate peeling layer after bonding (in the second laminated sheet), and the exposed surface of the first protective film forming film obtained above was bonded to the exposed surface of the resulting intermediate peeling layer.

As a result of the above, the first substrate (thickness 75 μm), buffer layer (thickness 400 μm), intermediate peeling layer (thickness 10 μm), and first protective film forming film (thickness 45 μm) were formed in this order in their thickness direction. Thus, a first sheet for forming a protective film formed by being laminated was obtained.

<<Evaluation of sheet for forming first protective film>>

<Measurement of Shear Storage Modulus (G _x ') of Intermediate Peeling Layer)>

The first sheet for forming a protective film was obtained by pressing the exposed surface of the first protective film forming film (surface opposite to the intermediate peeling layer side) of the first sheet for forming a protective film obtained above to the mirror surface of a semiconductor mirror wafer having a diameter of 8 inches. It was affixed to the mirror surface of the semiconductor mirror wafer. At this time, the first sheet for forming a protective film was attached using an attaching device (roller type laminator, manufactured by Lintec, “RAD-3510 F/12”) at a table temperature of 90° C., an attaching speed of 5 mm/s, and an attaching pressure of 0.5 It carried out while heating the 1st sheet|seat for forming a protective film on conditions of MPa and roller sticking height -400 micrometers.

Next, the first protective film formation film was left on the semiconductor mirror wafer, and the first substrate, buffer layer, and intermediate peeling layer were peeled off to obtain Structure 2 in which the first substrate, buffer layer, and intermediate peeling layer were laminated.

Thereafter, the intermediate peeling layer of Structure 2 was affixed to the adhesive layer of an adhesive sheet (Adwill (registered trademark) D-210 manufactured by Lintec) formed by laminating the adhesive layer and the base material.

Then, the structure 3 formed by laminating the first base material and the buffer layer was peeled off to obtain the structure 4 formed by laminating the intermediate release layer, the pressure-sensitive adhesive layer, and the base material.

Further, the pressure-sensitive adhesive layer and base material of structure 4 are peeled off, and only the intermediate peeling layer is laminated to have a thickness of 400 μm. A test piece of the release layer was obtained.

The installation location of the test piece of the shear viscosity measuring device (manufactured by Antonfa Co., Ltd.: MCR301) is insulated in advance at 90 ° C., the test piece of the intermediate peeling layer obtained above is placed on the installation location, and the measuring jig is closely adhered to the upper surface of the test piece. , the test piece was fixed to the above installation location and installed.

Next, the shear strain generated under the conditions of a temperature of 90°C and a measurement frequency of 1 Hz was raised stepwise to 0.01% to 10%, and the shear storage modulus ( _Gx ') of the test piece of the intermediate release layer at a shear strain of 1% was ) [Pa] was measured.

<Measurement of shear storage modulus ( _GA ') of buffer layer)>

The buffer layer of Structure 3 was cut into a circular shape with a diameter of 25 mm and peeled off from the first substrate to obtain a test piece of a disk-shaped buffer layer with a diameter of 25 mm and a thickness of 400 μm.

The installation location of the test piece of the shear viscosity measuring device (manufactured by Antonfa Co., Ltd.: MCR301) is insulated in advance at 90 ° C., the test piece of the buffer layer obtained above is placed on the installation location, and the test piece is brought into close contact with the upper surface of the test piece. was installed by fixing to the above installation location.

Subsequently, the shear strain generated under the conditions of a temperature of 90 ° C. and a measurement frequency of 1 Hz was raised stepwise from 0.01% to 1000%, and the shear storage modulus of the test piece of the buffer layer at a shear strain of 1% ( _GA ') [ Pa] was measured.

<Calculation of the ratio of the shear storage modulus (G _x ') of the intermediate release layer to the shear storage modulus ( _GA ') of the buffer layer (G _x '/GA _' )>

By dividing the value of the shear storage modulus (G _x ') [Pa] of the test piece of the intermediate release layer by the value of the shear storage modulus ( _GA ') [Pa] of the test piece of the buffer layer, the shear storage modulus (G The ratio (G _x '/ _GA ') of the shear storage modulus (G _x ') of the intermediate release layer to _A ') was obtained.

<Evaluation of bump penetrability of the first protective film-forming film (confirmation of thickness of deposits of the first protective film on top of bumps)>

The exposed surface (surface opposite to the intermediate release layer side) of the first protective film forming film in the first sheet for forming a protective film obtained above is pressed against the bump formation surface of a semiconductor wafer having bumps and having a diameter of 8 inches, so that the first protective film is formed. The formation sheet was affixed to the bump formation surface of the semiconductor wafer. At this time, as the semiconductor wafer, a bump having a height of 210 μm, a bump width of 250 μm, and a distance between bumps of 400 μm was used. In addition, the affixing of the 1st sheet|seat for forming a protective film was carried out using the affixing apparatus (roller-type laminator, "RAD-3510 F/12" by Lintec), table temperature 90 degreeC, affixing speed 5 mm/s, and affixing pressure 0.5 MPa , It was performed while heating the sheet|seat for forming a 1st protective film on the conditions of roller sticking height -400 micrometer.

Next, the back surface of the semiconductor wafer was ground using a grinding machine ("DFG8760" manufactured by Disco), and the thickness of the semiconductor wafer was set to 250 µm.

Then, using a multi-wafer mounter ("RAD-2700 F/12" manufactured by Lintec), the first substrate, the buffer layer, and the intermediate release layer were removed from the first protective film-forming film to expose the first protective film-forming film. . And the 1st protective film was formed by heating the 1st protective film formation film at 130 degreeC for 4 hours.

Next, a dicing sheet (dicing tape “Adwill D-686H” manufactured by Lintec) is attached to the back surface (grinding surface) of the semiconductor wafer, and a blade dicer (“DFD6362” manufactured by Disco) and a dicing blade (Disco) Manufacturing "ZH05-SD2000-N1-90CC"), the rotation speed of the blade is 30000 rpm, the feed speed of the blade is 30 mm/s, and the semiconductor wafer is cut into semiconductor chips with a size of 6 mm x 6 mm. It was divided, and at the same time, the first protective film was cut into the same size.

As a result of the above, a semiconductor chip having a semiconductor chip and a first protective film formed on a bump formation surface of the semiconductor chip, and a semiconductor chip having a plurality (plural) first protective films are arranged and held on a dicing sheet to form a first protective film. A group of formed semiconductor chips was obtained.

Among the group of semiconductor chips with the first protective film obtained above, one location in the central portion and four locations at equal intervals from each other in the vicinity of the outer periphery are selected, but at this time, two locations in the vicinity of the outer periphery and one location in the central portion are selected. The connecting direction coincided with the sticking direction of the sheet for forming the first protective film, and from these five locations, a total of five semiconductor chips were taken out, one at a time.

Next, using a scanning electron microscope (SEM, “VE-9700” manufactured by Keyence Corporation), from a direction perpendicular to the bump formation surface of the semiconductor chip on which the first protective film was formed and a direction forming an angle of 60°, these The surface of the bump of the semiconductor chip on which the first protective film was formed was observed, and the presence or absence of adhesion of the first protective film on the upper part of the bump was confirmed. On the other hand, the semiconductor chip on which these five first protective films are formed includes a total of 8 bumps, that is, the surfaces of 40 bumps in total are observed. In addition, the reason why the surface of the bump of the semiconductor chip on which the first protective film was formed was observed from the above-mentioned direction forming an angle of 60° is that the first protective film remaining on the upper part of the bump is most easily identified by doing this. am.

Next, each of these five semiconductor chips with the first protective film was sealed with an epoxy resin, and the sealed material was polished using a polishing sheet until the cross section of the bump central portion was visible. The cross section was observed using a field emission scanning electron microscope (FE-SEM, manufactured by Hitachi High-Technologies Co., Ltd. "S-4700"), the thickness of the deposit of the first protective film on the upper part of the bump was measured, and the maximum The value was adopted as the thickness of the deposit. Since the amount (thickness) of the adhered substance of the first protective film on the upper part of the bump reflects the amount of the remaining substance of the first protective film forming film on the upper part of the bump, the penetrability of the bump of the first protective film forming film is It serves as an indicator for evaluation. The results are shown in Table 1.

<<Manufacture and evaluation of sheet for forming first protective film>>

[Example 2]

When preparing the composition for forming an intermediate release layer (composition (VII)), ethylene-vinyl acetate copolymer (EVA, weight average A first sheet for forming a protective film was prepared and evaluated in the same manner as in Example 1, except that a molecular weight of 65000 and a VA content of 28% by mass) was used. The results are shown in Table 1.

[Example 3]

When preparing the composition for forming an intermediate release layer (composition (VII)), ethylene-vinyl acetate copolymer (EVA, weight average A first sheet for forming a protective film was prepared and evaluated in the same manner as in Example 1, except that a molecular weight of 150000 and a VA content of 32% by mass) was used. The results are shown in Table 1.

<<Manufacture and evaluation of sheet for forming first protective film>>

[Example 4]

<Preparation of composition for forming intermediate release layer>

An acrylic copolymer formed by copolymerization of n-butyl acrylate (52 parts by mass), methyl methacrylate (20 parts by mass), and 4-hydroxybutyl acrylate (28 parts by mass) is used, and the acrylic copolymer 2-isocyanate ethyl methacrylate (manufactured by Showa Denko Co., Ltd. “Karenz MOI (registered trademark)”) to obtain an energy ray-curable acrylic polymer (weight average molecular weight: 750000).

Methyl ethyl ketone was added to the acrylic polymer to prepare a liquid having an acrylic polymer concentration of 20% by mass, and the liquid was stirred for 30 minutes to prepare a solution composition (VII).

<Formation of Intermediate Peeling Layer>

Using the release film (“SP-PET381031” manufactured by Lintec, 38 μm in thickness), the composition (VII) obtained above was coated on the release treatment surface, followed by heating and drying at 100° C. for 2 minutes to obtain a thickness of 10 μm. An intermediate peeling layer was formed.

<Manufacture of sheet for forming first protective film>

A sheet for forming a first protective film was manufactured in the same manner as in Example 1, except that the intermediate peeling layer was used.

<<Manufacture of sheet for forming first protective film>>

[Comparative Example 1]

<Manufacture of adhesive composition>

An acrylic copolymer formed by copolymerization of 2-ethylhexyl acrylate (82 parts by mass) and 2-hydroxyethyl acrylate (18 parts by mass) is used, and the composition derived from 2-hydroxyethyl acrylate in the acrylic copolymer is used. The acrylic A polymer (weight average molecular weight 800000) was obtained.

With respect to this acrylic polymer (100 parts by mass), 1-hydroxycyclohexylphenyl ketone (photopolymerization initiator, “Irgacure (registered trademark) 184” manufactured by BASF) (3 parts by mass) and trimethylolpropane adduct tolylene diisocyanate (Crosslinking agent, "Coronate (registered trademark) L" manufactured by Tosoh Corporation) (1.0 parts by mass) was added, a liquid was prepared using methyl ethyl ketone, and the liquid was stirred for 30 minutes to obtain a solid content concentration of 20 A solution-like pressure-sensitive adhesive composition in mass % was prepared.

Using the release film (“SP-PET381031” manufactured by Lintec, 38 μm in thickness), coating the adhesive composition obtained above on the release treatment surface and heating and drying it at 120° C. for 2 minutes to obtain a pressure-sensitive adhesive having a thickness of 10 μm. layer was formed.

A sheet for forming a first protective film was manufactured in the same manner as in Example 1, except that the pressure-sensitive adhesive layer obtained above was used instead of the intermediate release layer.

[Comparative Example 2]

<Manufacture of adhesive composition>

An acrylic copolymer formed by copolymerization of 2-ethylhexyl acrylate (80 parts by mass) and 2-hydroxyethyl acrylate (20 parts by mass) is used, and the composition derived from 2-hydroxyethyl acrylate in the acrylic copolymer is used. Acrylic A polymer (weight average molecular weight 800000) was obtained.

With respect to this acrylic polymer (100 parts by mass), 1-hydroxycyclohexylphenyl ketone (photopolymerization initiator, “Irgacure (registered trademark) 184” manufactured by BASF) (3 parts by mass) and trimethylolpropane adduct tolylene diisocyanate (Crosslinking agent, “Coronate (registered trademark) L” manufactured by Tosoh Corporation) (1.5 parts by mass) was added, a liquid was prepared using methyl ethyl ketone, and the liquid was stirred for 30 minutes to obtain a solid content concentration of 20 A solution-like pressure-sensitive adhesive composition in mass % was prepared.

Using the release film (“SP-PET381031” manufactured by Lintec, 38 μm in thickness), coating the adhesive composition obtained above on the release treatment surface and heating and drying it at 100° C. for 2 minutes to obtain a pressure-sensitive adhesive having a thickness of 10 μm. layer was formed.

A sheet for forming a first protective film was manufactured in the same manner as in Example 1, except that the pressure-sensitive adhesive layer obtained above was used instead of the intermediate release layer.

<<Evaluation of sheet for forming first protective film>>

The first protective film-forming sheets of Comparative Examples 1 and 2 obtained above were evaluated in the same manner as in Example 1. The results are shown in Table 1.

As is clear from the above results, in Examples 1 to 4, the first sheet for forming a protective film was normally adhered to the bump formation surface of the semiconductor wafer with the first protective film forming film therein at a sticking speed of 5 mm/s. and the first sheet for forming a protective film had high-speed adhesion. And, even if it was applied at high speed in this way, the adhesion of the first protective film on the top of the bump was 0.7 μm or less (0.1 to 0.7 μm), and the adhesion of the first protective film on the top of the bump could be suppressed. That is, in Examples 1 to 4, even if the first sheet for forming a protective film is affixed to the bump formation surface of the semiconductor wafer at high speed, the top of the bump can protrude from the protective film formation film, and the first Residual|survival of the protective film formation film was able to be suppressed. Thus, in Examples 1 to 4, both the high-speed sticking property of the sheet for forming the first protective film and the penetrability of the bumps of the first protective film-forming film were both high.

The first sheets for forming a protective film of Examples 1 to 3 had an intermediate release layer containing an ethylene-vinyl acetate copolymer. The first sheet for forming a protective film of Examples 1 to 3 has a smaller ratio (G _x '/ _GA ') than the first sheet for forming a protective film of Example 4 containing an acrylic polymer, and the first sheet for forming a protective film at the top of the bump The thickness of the attachment of the protective film is thin. The first sheet for forming a protective film of Examples 1 to 3 had higher penetrability of the bumps of the first protective film forming film than the first sheet for forming a protective film of Example 4 containing an acrylic polymer.

From the results of Examples 1 to 3, as the VA content of the ethylene-vinyl acetate copolymer decreased and the weight average molecular weight of the ethylene-vinyl acetate copolymer decreased, the bump penetration of the first protective film forming film An increasing trend was observed.

On the other hand, when the sheet for forming the first protective film of Comparative Example 1 or 2 was affixed with the first protective film forming film therein at an attaching speed of 5 mm/s, the thickness of the deposit of the first protective film on the upper part of the bump was 1.5 μm or 1.3 μm, and adhesion of the first protective film on the top of the bump could not be suppressed. That is, in Comparative Examples 1 and 2, when the sheet for forming the first protective film was attached to the bump formation surface of the semiconductor wafer at a sticking speed of 5 mm/s, the remaining of the first protective film forming film on the upper part of the bump Couldn't contain it. Thus, in Comparative Examples 1 and 2, the sheet for forming the first protective film did not have high-speed adhesion, and the penetrability of the bumps of the first protective film-forming film was also low.

The first sheets for forming a protective film of Comparative Examples 1 and 2 had an adhesive layer containing an acrylic polymer instead of an intermediate release layer containing an ethylene-vinyl acetate copolymer.

INDUSTRIAL APPLICABILITY The present invention is a semiconductor chip for use in a flip chip connection method, and can be used for manufacturing a semiconductor chip or the like having bumps and having a protective film on the bump formation surface.

One… Sheet for forming the first protective film, 11 . . . 1st substrate, 12... buffer layer, 13 . . . middle exfoliation layer, 14 . . . 1st protective film formation film, 14'... First protective film, 140'... 1st protective film after cutting, 9... semiconductor wafer, 9a... bump formation surface of semiconductor wafer (surface having bumps of semiconductor wafer), 90 . . . semiconductor chip, 90a... bump formation surface of semiconductor chip (surface having bumps of semiconductor chip), 91 . . . Bump, 9101... Top of bump, 9140'... Semiconductor chip on which the first protective film is formed

Claims (8)

A first protective film forming sheet for forming a first protective film on at least a surface having bumps of a semiconductor wafer,
The first sheet for forming a protective film is formed by laminating a first substrate, a buffer layer, an intermediate peeling layer, and a first protective film forming film in this order in their thickness direction,
The sheet for forming a first protective film, wherein the ratio (G _x '/ _GA ') of the shear storage modulus ( _{G x} ') of the intermediate release layer to the shear storage modulus (GA ') of the buffer layer is less than 0.6. According to claim 1,
The first sheet for forming a protective film, wherein the intermediate release layer contains an ethylene-vinyl acetate copolymer. According to claim 2,
In the above ethylene-vinyl acetate copolymer, the ratio of the amount of structural units derived from vinyl acetate to the total amount of structural units is 16 to 40% by mass, The first sheet for forming a protective film. According to claim 2 or 3,
The first sheet for forming a protective film, wherein the ethylene-vinyl acetate copolymer has a weight average molecular weight of 200,000 or less. According to any one of claims 1 to 4,
The sheet for forming a first protective film, wherein the shear storage modulus (G _x ') of the intermediate release layer is 10000 Pa or less. A method for manufacturing a semiconductor device using the sheet for forming a first protective film according to any one of claims 1 to 5,
In the manufacturing method, the first protective film forming film in the first protective film forming sheet is adhered to a surface of a semiconductor wafer having bumps, and the tops of the bumps protrude from the first protective film forming film, An attaching step of forming a sheet for forming a first protective film;
After the sticking step, in the first sheet for forming a protective film, layers other than the first protective film forming film are removed from the first protective film forming film, and when the first protective film forming film is curable, the first 1 Curing the protective film-forming film to form a first protective film, and when the first protective film-forming film is non-curable, the first protective film-forming film after removing layers other than the first protective film-forming film is treated as the first protective film. A first protective film forming step of forming the first protective film on the surface having the bumps by doing so;
a division step of fabricating a semiconductor chip by dividing the semiconductor wafer after the first protective film formation step;
A cutting step of cutting the first protective film after the first protective film forming step;
A first protective film comprising the semiconductor chip obtained after the dividing process and the cutting process, and the first protective film formed on a surface having the bumps of the semiconductor chip, wherein tops of the bumps protrude from the first protective film A semiconductor device manufacturing method comprising a mounting step of flip-chip connecting the formed semiconductor chip to a substrate at the top of the bump. According to claim 6,
In the sticking step, the first protective film forming film is attached to the bump-bearing surface of the semiconductor wafer at a sticking speed of 4 mm/s or higher. As use of a sheet for forming a first protective film on at least a surface having bumps of a semiconductor wafer,
The sheet is formed by laminating a first substrate, a buffer layer, an intermediate release layer, and a first protective film forming film in this order in their thickness direction,
The use of the sheet, wherein _the ratio (G _x '/GA ') of the shear storage modulus (G _x ') of the intermediate release layer to the shear storage modulus (GA _' ) of the buffer layer is less than 0.6.

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