JP7439575B2 - Manufacturing method of semiconductor device and resin sheet - Google Patents

Description

The present invention relates to a method for manufacturing a semiconductor device and a resin sheet that can be used in the method.

In recent years, demand for small, high-performance mobile terminals such as smartphones and tablet PCs has been increasing. There is a demand for further improvements in functionality and miniaturization of semiconductor devices used in such small, highly functional mobile terminals. In order to meet these demands, for example, multi-chip packages that are sealed to contain two or more semiconductor chips, and package-on-packages that are constructed by bonding multiple multi-chip packages together. (PoP) is attracting attention. Such a package-on-package configuration includes, for example, a configuration in which another package is mounted on a predetermined package and electrically connected to each other.

In manufacturing the above-described package, several methods have been proposed for mounting a semiconductor chip on a mounting board. For example, wire bonding mounting is proposed, in which the electrodes of the semiconductor chip are mounted on the mounting board in a so-called face-up state with the electrodes facing away from the mounting board, and the electrodes of the semiconductor chip and the electrodes of the mounting board are connected using bonding wires. has been done. Further, for example, flip-chip mounting is known in which the semiconductor chip is mounted in a so-called face-down state with the electrodes facing the mounting board and the electrodes of the semiconductor chip and the electrodes of the mounting board are directly connected. In the case of flip-chip mounting, a protruding electrode called a bump is usually formed on the electrode on the semiconductor chip side, and the bump and the electrode on the mounting board are bonded.

Usually, a package is obtained by forming a sealing layer on a mounting board on which a semiconductor chip is mounted. The sealing layer can be formed by a method such as a transfer molding method using a resin composition such as an epoxy molding compound as a sealing material, or a vacuum heat pressing method in which a sealing film formed of a sealing material is bonded. It can be formed as a cured body layer containing a cured body of the resin composition. A sealing process using a vacuum hot press method using a sealing film is disclosed in Patent Document 1. Further, a technique as described in Patent Document 2 has also been proposed.

Japanese Patent Application Publication No. 2014-29958 JP2019-207955A

The cured body layer may be formed, for example, by a compression molding method. In the compression molding method, a cured body layer is generally formed using a mold. However, when using solid resin compositions such as granules and powders, dust may be generated and adhere to the equipment and manufacturing environment. Furthermore, especially when sealing a large-area mounting board, it takes time to supply the resin composition to the mold, which tends to reduce yield. Furthermore, when a solid resin composition is used, the thickness of the cured layer may be poorly balanced in the in-plane direction. "In-plane direction" refers to a direction perpendicular to the thickness direction, unless otherwise specified.

Furthermore, when a liquid resin composition is used in the compression molding method, flow marks are likely to occur in the cured layer that is formed. Furthermore, liquid resin compositions usually have poor storage stability. Furthermore, depending on the shape of the mounting board, the filling properties of the resin composition may be poor. For example, when compression molding is performed using a liquid resin composition on a rectangular mounting board, the filling properties may be poor.

On the other hand, the compression molding method using a film-like resin composition can make the thickness of the cured body layer uniform in the in-plane direction, and is less likely to cause flow marks. Therefore, the present inventor investigated a compression molding method using a film-like resin composition. Specifically, we attempted to form a cured body layer on a mounting board by compression molding using a resin sheet comprising a support film and a resin composition layer provided on the entire one side of the support film. .

However, it has been found that when the above resin sheet is used, the following problems may occur.
For example, if a resin sheet smaller than the mold cavity is used, the support film may dig into the cured layer obtained after compression molding, resulting in unevenness on the surface of the cured layer. Since a product containing a cured layer having such irregularities is not suitable for shipping, the irregularities may cause a decrease in yield. Moreover, if the support film digs into the cured body layer, it becomes difficult to peel off the support film.

For example, when a resin sheet larger than the mold cavity is used, it is possible to suppress the support film from digging into the cured material layer. However, a part of the resin composition layer may flow out of the mold or adhere to the mold, contaminating the apparatus.

For example, even when a resin sheet having the same size as the mold cavity is used, the equipment may become contaminated due to the resin composition flowing out. Furthermore, even if the mold is not stained, the support film will usually dig into the cured layer, so that unevenness may be formed on the surface of the cured layer.

The above-mentioned problem may also occur in manufacturing methods using substrates other than mounting substrates.

The present invention was devised in view of the above-mentioned problems, and includes a cured body layer formed of a cured body of a resin composition by a compression molding method using a resin sheet including a support film and a resin composition layer. A manufacturing method for manufacturing a semiconductor device comprising: a manufacturing method capable of suppressing the formation of irregularities in a cured body layer and suppressing staining of a mold due to outflow of a resin composition; and a resin that can be used in the manufacturing method. The purpose is to provide a sheet;

The inventors of the present invention have made extensive studies to solve the above problems. As a result, the present inventors have discovered that the above problem can be solved by providing a supporting film with a margin portion that can protrude from the cavity when the resin composition layer is not formed and the mold is closed. The present invention has been completed.
That is, the present invention includes the following.

[1] Compression molding comprising a first mold capable of supporting a substrate and a second mold provided opposite to the first mold, with a cavity formed in at least one of the first mold and the second mold. A method for manufacturing a semiconductor device, the method comprising manufacturing a semiconductor device using an apparatus, the method comprising:
The manufacturing method includes:
preparing the substrate;
a step of preparing a resin sheet comprising a support film and a resin composition layer formed of a thermosetting resin composition on the support film;
a step of placing the resin composition layer in the cavity and pressurizing the substrate and the resin sheet between the first mold and the second mold,
The support film includes a support portion on which the resin composition layer is formed and a margin portion on which the resin composition layer is not formed,
A method for manufacturing a semiconductor device, wherein the margin portion is located around the entire circumference of the support portion when viewed from the thickness direction.
[2] The method for manufacturing a semiconductor device according to [1], wherein in the step of pressurizing the substrate and the resin sheet, the margin portion of the support film protrudes from the cavity around the entire circumference of the cavity.
[3] The method for manufacturing a semiconductor device according to [1] or [2], wherein the elastic modulus E ₀ of the support film at 120° C. is 6.0 GPa or less.
[4] [1] to [3], wherein the resin composition layer has a capacity that can fill the inside of the cavity when the resin composition layer is pressurized in the step of pressurizing the substrate and the resin sheet. A method for manufacturing a semiconductor device according to any one of the above.
[5] The method for manufacturing a semiconductor device according to any one of [1] to [4], wherein the resin composition has a melt viscosity η ₀ of 300 poise or more and 20,000 poise or less at 120° C.
[6] The method for manufacturing a semiconductor device according to any one of [1] to [5], wherein the resin composition layer has a thickness of 10 μm or more and 500 μm or less.
[7] A support film, and a resin composition layer formed of a thermosetting resin composition on the support film,
The support film includes a support portion on which the resin composition layer is formed and a margin portion on which the resin composition layer is not formed,
When viewed from the thickness direction, the margin portion is located around the entire circumference of the support portion,
A resin sheet, wherein the support film has an elastic modulus E ₀ of 6.0 GPa or less at 120°C.
[8] The resin sheet according to [7], wherein the resin composition has a melt viscosity η ₀ of 300 poise or more and 20000 poise or less at 120°C.
[9] The product (η ₀ ×E ₀ ) of the melt viscosity _η 0 of the resin composition at 120°C and the elastic modulus E ₀ of the support film is 20.0 × 10 ³ [Poise·GPa] or less The resin sheet according to [7] or [8], which is
[10] The product of [7] to [9], wherein the product (t×E ₀ ) of the thickness t of the support film and the elastic modulus E ₀ of the support film is 300 [μm·GPa] or less. The resin sheet according to any one of the items.
[11] The product (η ₀ ×t×E ₀ ) of the melt viscosity η ₀ of the resin composition at 120° C., the thickness t of the support film, and the elastic modulus E ₀ of the support film is 10 .0×10 ⁵ [μm・Poise・GPa] or less, the resin sheet according to any one of [7] to [10].

According to the present invention, a method for manufacturing a semiconductor device using a compression molding method that can suppress the formation of irregularities in a cured body layer and also suppress staining of a mold due to outflow of a resin composition; A usable resin sheet can be provided.

FIG. 1 is a cross-sectional view schematically showing a compression molding apparatus used in a method for manufacturing a semiconductor device according to a first embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing how a substrate is installed in a compression molding apparatus used in the method for manufacturing a semiconductor device according to the first embodiment of the present invention. FIG. 3 is a plan view schematically showing a resin sheet prepared in the method for manufacturing a semiconductor device according to the first embodiment of the present invention, as viewed from the thickness direction. FIG. 4 is a cross-sectional view schematically showing a cross section of a resin sheet prepared by the method for manufacturing a semiconductor device according to the first embodiment of the present invention, taken along a plane parallel to the thickness direction. FIG. 5 is a perspective view schematically showing an example of a long resin sheet manufacturing apparatus. FIG. 6 is a cross-sectional view schematically showing a resin sheet installed in a compression molding apparatus used in the method for manufacturing a semiconductor device according to the first embodiment of the present invention. FIG. 7 is a cross-sectional view schematically showing compression molding performed using a compression molding apparatus used in the method for manufacturing a semiconductor device according to the first embodiment of the present invention. FIG. 8 is a cross-sectional view schematically showing a multilayer body that can be manufactured by the manufacturing method according to the first embodiment of the present invention. FIG. 9 is a cross-sectional view schematically showing a compression molding apparatus when compression molding is performed using a resin sheet with no blank space and a support film smaller than the cavity. FIG. 10 is a cross-sectional view schematically showing a state in which a substrate and a resin sheet are installed in a compression molding apparatus used in a method for manufacturing a semiconductor device according to a second embodiment of the present invention. FIG. 11 is a cross-sectional view schematically showing compression molding performed using a compression molding apparatus used in the method for manufacturing a semiconductor device according to the second embodiment of the present invention. FIG. 12 is a cross-sectional view schematically showing a state in which a substrate and a resin sheet are installed in a compression molding apparatus used in a method for manufacturing a semiconductor device according to a third embodiment of the present invention. FIG. 13 is a cross-sectional view schematically showing compression molding performed using a compression molding apparatus used in a method for manufacturing a semiconductor device according to a third embodiment of the present invention.

Hereinafter, the present invention will be described in detail by showing embodiments and examples. However, the present invention is not limited to the embodiments and examples listed below, and may be implemented with arbitrary changes within the scope of the claims of the present invention and equivalents thereof.

[1. First embodiment]
FIG. 1 is a cross-sectional view schematically showing a compression molding apparatus 100 used in a method for manufacturing a semiconductor device according to a first embodiment of the present invention.
As shown in FIG. 1, a compression molding apparatus 100 used in the manufacturing method according to the first embodiment of the present invention includes a first mold 110 and a second mold 120. These first mold 110 and second mold 120 are provided so that the mold is closed when they approach each other, and the mold is opened when they are separated from each other. In this embodiment, an example will be described in which the first mold 110 is provided above and the second mold 120 is provided below so that the thickness directions of the first mold 110 and the second mold are parallel to the vertical direction.

The first mold 110 is provided so as to be able to support the substrate 200. The first mold 110 may include a fixing mechanism (not shown) that can fix the substrate 200. Examples of the fixing mechanism include a suction section that can attract and fix the substrate 200, a locking section that can hook and fix the substrate 200, and the like. However, since the substrate 200 may be fixed to the first mold 110 using a fixing member (not shown) such as an adhesive tape, the first mold 110 does not need to have a fixing mechanism.

The second mold 120 is provided opposite the first mold 110. A cavity 130 serving as a molding recess is formed in at least one of the first mold 110 and the second mold 120. Usually, as shown in FIG. 1, a cavity 130 is formed on the side of the second mold 120 that faces the first mold 110. This cavity 130 is formed so that a space for compression molding can be formed when the mold is closed. In the example shown in this embodiment, a space corresponding to the cavity 130 is formed between the surface 200D of the substrate 200 supported by the first mold 110 and the second mold 120, and within this space. It is formed so that a resin composition layer of a resin sheet (not shown in FIG. 1) can be compression molded.

The first mold 110 and the second mold 120 are provided so that the inside of the cavity 130 can be pressurized. In this embodiment, in order to realize the above-mentioned pressurization, an example is shown in which the second mold 120 includes a bottom block 121 and a side block 122 provided annularly so as to surround the bottom block 121. I will explain. Bottom block 121 forms the bottom of cavity 130. Additionally, the side block 122 forms a side wall of the cavity 130. The bottom block 121 is provided movably relative to the side blocks 122. Therefore, in this example, the second mold 120 is provided so that the inside of the cavity 130 can be pressurized by pressing the bottom block 121 upward in the figure. However, the method of pressurizing the inside of the cavity 130 is not limited to the example shown here.

Furthermore, the first mold 110 and the second mold 120 may be provided with a release film (not shown) in order to suppress sticking of the substrate 200 and the resin sheet. Further, the first mold 110 and the second mold 120 may be equipped with a temperature adjustment device such as a heater (not shown) in order to heat the inside of the cavity 130. Further, the first mold 110 and the second mold 120 may be formed with an air vent passage (not shown) through which gas can flow, communicating with the cavity 130, and this air vent passage may be provided with a pressure reducing device (not shown). ) may be connected.

In the manufacturing method according to the first embodiment of the present invention, a semiconductor device is manufactured using the compression molding apparatus 100 described above. This manufacturing method is
Step (I) of preparing the substrate 200;
Step (II) of preparing a resin sheet (not shown in FIG. 1) comprising a support film and a resin composition layer formed of a thermosetting resin composition on the support film;
The method includes a step (III) of placing the resin composition layer in the cavity 130 and pressurizing the substrate 200 and the resin sheet between the first mold 110 and the second mold 120.

[1.1. Step (I) of preparing a substrate]
The manufacturing method according to the first embodiment of the present invention includes a step (I) of preparing a substrate. Examples of substrates include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold rolled steel plate (SPCC); glass epoxy substrates such as FR-4 substrates; polyester substrates; polyimide substrates; BT Examples include a resin substrate; a thermosetting polyphenylene ether substrate; and the like. Further, the substrate may include a temporary fixing film that can temporarily fix the semiconductor chip in a removable manner. Furthermore, the temporary fixing film itself may be used as the substrate. Commercially available temporary fixing films include, for example, "Riva Alpha" manufactured by Nitto Denko Corporation. Further, the substrate may have a metal layer such as copper foil on the surface as a part of the substrate. For example, a substrate having a releasable first metal layer and a second metal layer on both surfaces may be used. When using such a substrate, a conductor layer as a wiring layer that can function as circuit wiring is usually formed on the surface of the second metal layer opposite to the first metal layer. An example of a substrate having such a metal layer is "Micro Thin", an ultra-thin copper foil with carrier copper foil manufactured by Mitsui Mining & Mining Co., Ltd.

Further, the substrate may include a conductor layer formed on one or both surfaces thereof. The conductor material included in the conductor layer is, for example, one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Examples include materials containing the above metals. As the conductor material, a single metal or an alloy may be used. Examples of the alloy include alloys of two or more metals selected from the above group (eg, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among these, from the viewpoint of versatility in forming conductor layers, cost, and ease of patterning, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as single metals; and nickel-chromium alloys as alloys , copper/nickel alloy, copper/titanium alloy; are preferred. Among these, single metals such as chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and nickel-chromium alloys are more preferred, and single metals such as copper are particularly preferred. Further, the conductor layer may be patterned, for example, in order to function as a wiring layer.

Additionally, the substrate may include electronic components mounted on one or both sides. Examples of electronic components include passive components such as capacitors, inductors, and resistors; and active components such as semiconductor chips.

The in-plane dimension of the substrate may be smaller than, larger than, or the same as the in-plane dimension of the cavity. Thus, the width of the substrate can typically be smaller, larger, or the same as the width of the cavity. Further, the area of the substrate may be smaller than, larger than, or the same as the opening area of the cavity. Unless otherwise specified, the area of the substrate refers to the area when the substrate is viewed from the thickness direction. Further, unless otherwise specified, the opening area of the cavity refers to the area of the opening (portion indicated by reference numeral 130U in FIG. 1) when the cavity is viewed from the thickness direction. For example, a substrate smaller than the cavity can fit within the cavity so that the substrate itself can be embedded in the cured material layer. Further, for example, if the substrate is larger than the cavity, the cured layer can be formed on the substrate because the substrate can cover the cavity.

FIG. 2 is a cross-sectional view schematically showing a substrate 200 installed in a compression molding apparatus 100 used in the method for manufacturing a semiconductor device according to the first embodiment of the present invention. As shown in FIG. 2, the prepared substrate 200 is placed in the first mold 110. In this embodiment, as shown in FIG. 2, an example will be described in which a substrate 200 large enough to cover the cavity 130 is used.

[1.2. Step (II) of preparing a resin sheet]
FIG. 3 is a plan view schematically showing a resin sheet 300 prepared in the method for manufacturing a semiconductor device according to the first embodiment of the present invention, viewed from the thickness direction. Further, FIG. 4 is a cross-sectional view schematically showing a cross section of the resin sheet 300 prepared by the method for manufacturing a semiconductor device according to the first embodiment of the present invention, taken along a plane parallel to the thickness direction.

The manufacturing method according to the first embodiment of the present invention includes a step (II) of preparing a resin sheet 300 shown in FIGS. 3 and 4. The resin sheet 300 includes a support film 310 and a resin composition layer 320 formed of a thermosetting resin composition on the support film 310.

The resin composition layer 320 is partially formed on one side 310U of the support film 310. The portion of the support film 310 on which the resin composition layer 320 is formed may be referred to as a “support portion” 311. Further, a portion of the support film 310 on which the resin composition layer 320 is not formed may be referred to as a “margin portion” 312. Therefore, the support film 310 includes a support portion 311 and a margin portion 312. The support film 310 has a margin portion 312 around the entire circumference of the support portion 311 when viewed from the thickness direction. Therefore, the entire circumference of the support portion 311 is surrounded by the margin portion 312.

The resin composition layer 320 is formed small so that the entire resin composition layer 320 can be accommodated within the cavity 130. Therefore, the support portion 311 of the support film 310 on which the resin composition layer 320 is formed is also formed small so that the entire support portion 311 can be accommodated within the cavity 130. By being able to accommodate the resin composition layer 320 within the cavity 130, it is possible to suppress the resin composition from flowing out of the cavity 130 when the mold is closed. Therefore, staining of the first mold 110 and the second mold 120 due to the resin composition can be suppressed.

On the other hand, the margin portion 312 of the support film 310 is formed to be large so that at least a portion of the margin portion 312 can protrude from the cavity 130. Preferably, the margin portion 312 is formed such that the margin portion 312 can protrude around the entire circumference of the cavity 130 when the mold is closed. The entire circumference of the cavity 130 refers to the entire circumference viewed from the thickness direction. By allowing the margin portion 312 of the support film 310 to protrude from the cavity 130, it is possible to prevent the end portion 310E of the support film 310 from digging into the resin composition layer 320. Therefore, the formation of irregularities in the cured body layer (not shown in FIGS. 3 and 4) can be suppressed.

The dimensions of the resin composition layer 320 will be explained below. Unless otherwise specified, the dimensions of the resin composition layer 320 described below represent the dimensions of the resin composition layer 320 before pressurization in step (III). The in-plane dimension of the resin composition layer 320 is set to be smaller than the in-plane dimension of the cavity 130 from the viewpoint of being able to accommodate the entire resin composition layer 320 within the cavity 130. It is formed. Therefore, the width W ₃₂₀ of the resin composition layer 320 is usually smaller than the width W ₁₃₀ of the cavity 130 (see FIG. 1).

The ratio (W ₃₂₀ /W ₁₃₀ ) of the width W ₃₂₀ of the resin composition layer 320 to the width W ₁₃₀ of the cavity 130 is preferably 0.99 or less, more preferably 0.98 or less, particularly preferably 0.97 or less. be. When the ratio (W ₃₂₀ /W ₁₃₀ ) is within the above range, outflow of the resin composition to the outside of the cavity 130 can be effectively suppressed. The lower limit of the ratio (W ₃₂₀ /W ₁₃₀ ) is not particularly limited, but from the viewpoint of effectively filling every corner of the cavity 130 with the resin composition, it is preferably 0.80 or more, more preferably 0.85. It is particularly preferably 0.90 or more.

Further, the difference (W ₁₃₀ - W ₃₂₀ ) between the width W ₃₂₀ of the resin composition layer 320 and the width W ₁₃₀ of the cavity 130 is preferably 1 mm or more, more preferably 2 mm or more, and particularly preferably 5 mm or more. When the difference (W ₁₃₀ −W ₃₂₀ ) is within the above range, outflow of the resin composition to the outside of the cavity 130 can be effectively suppressed. The upper limit of the difference (W ₁₃₀ - W ₃₂₀ ) is not particularly limited, but from the viewpoint of effectively filling every corner of the cavity 130 with the resin composition, it is preferably 50 mm or less, more preferably 30 mm or less, and even more preferably is 20 mm or less.

Furthermore, the area of the resin composition layer 320 is formed to be smaller than the opening area of the cavity 130 from the viewpoint of allowing the entire resin composition layer 320 to be accommodated within the cavity 130. Unless otherwise specified, the area of the resin composition layer 320 represents the area when the resin composition layer 320 is viewed from the thickness direction. The area of the resin composition layer 320 with respect to 100% of the opening area of the cavity 130 is preferably 99% or less, more preferably 98% or less, particularly preferably 96% or less. When the area of the resin composition layer 320 is within the above range, outflow of the resin composition to the outside of the cavity 130 can be effectively suppressed. The lower limit of the area of the resin composition layer 320 is not particularly limited, but from the viewpoint of effectively filling every corner of the cavity 130 with the resin composition, it is preferably 50% or more, more preferably 70% or more, Particularly preferred is 80% or more.

As described above, since the resin composition layer 320 is formed on the support portion 311 of the support film 310 surrounded by the margin portion 312 on the entire periphery, the in-plane dimension of the resin composition layer 320 is as follows. It is smaller than the dimension of the support film 310 in the in-plane direction. Therefore, the width W ₃₂₀ of the resin composition layer 320 is usually smaller than the width W ₃₁₀ of the support film 310.

The ratio of the width W ₃₂₀ of the resin composition layer 320 to the width W ₃₁₀ of the support film 310 (W ₃₂₀ /W ₃₁₀ ) is preferably 0.99 or less, more preferably 0.95 or less, particularly preferably 0.90 or less. It is. When the ratio (W ₃₂₀ /W ₃₁₀ ) is within the above range, the support film 310 can usually have a sufficiently large margin portion 312, so that formation of irregularities in the cured material layer can be effectively suppressed. There is no particular restriction on the lower limit of the ratio (W ₃₂₀ /W ₃₁₀ ), but from the viewpoint of suppressing cost by suppressing the margin portion 312 of the support film 310 from becoming excessively wide, it is preferably 0.30 or more, or more. It is preferably 0.40 or more, particularly preferably 0.50 or more.

Further, the difference between the width W ₃₁₀ of the support film 310 and the width W ₃₂₀ of the resin composition layer 320 (W ₃₁₀ - W ₃₂₀ ) is preferably 10 mm or more, more preferably 20 mm or more, particularly preferably 30 mm or more. When the difference (W ₃₁₀ −W ₃₂₀ ) is within the above range, the support film 310 can usually have a sufficiently large margin portion 312, so that the formation of irregularities in the cured material layer can be effectively suppressed. The upper limit of the difference (W ₃₁₀ - W ₃₂₀ ) is not particularly limited, but from the viewpoint of suppressing costs by suppressing the margin portion 312 of the support film 310 from becoming excessively wide, it is preferably 500 mm or less, more preferably 500 mm or less. It is 300 mm or less, particularly preferably 200 mm or less.

Furthermore, since the resin composition layer 320 is partially formed on the support film 310, the area of the resin composition layer 320 is smaller than the area of the support film 310. The area of the support film 310 refers to the area when the support film 310 is viewed from the thickness direction, unless otherwise specified. The area of the resin composition layer 320 with respect to 100% of the area of the support film 310 is preferably 95% or less, more preferably 90% or less, particularly preferably 80% or less. When the area of the resin composition layer 320 is within the above range, the support film 310 can usually have a sufficiently large margin portion 312, so that formation of irregularities in the cured body layer can be effectively suppressed. There is no particular restriction on the lower limit of the area of the resin composition layer 320, but from the viewpoint of suppressing costs by suppressing the margin portion 312 of the support film 310 from becoming excessively wide, the area is preferably 20% or more, more preferably It is 30% or more, particularly preferably 40% or more.

The in-plane dimension of the resin composition layer 320 may be smaller, larger, or the same as the in-plane dimension of the substrate 200. Therefore, the width W ₃₂₀ of the resin composition layer 320 may be generally smaller than, larger than, or the same as the width W ₂₀₀ of the substrate 200 (see FIG. 2). In the compression molding method, the resin composition layer 320 is often expanded by pressure to form a cured layer on the surface 200D of the substrate 200, so the width of the resin composition layer 320 before being pressurized is W ₃₂₀ is typically smaller than the width W ₂₀₀ of substrate 200. In this case, from the viewpoint of improving the yield by forming a cured body layer with a large area, the ratio of the width W ₃₂₀ of the resin composition layer 320 to the width W ₂₀₀ of the substrate 200 (W ₃₂₀ /W ₂₀₀ ) is preferably 0. It is .50 or more, more preferably 0.70 or more, particularly preferably 0.80 or more. Further, from the same viewpoint, the difference (W ₂₀₀ - W ₃₂₀ ) between the width W ₂₀₀ of the substrate 200 and the width W ₃₂₀ of the resin composition layer 320 is preferably 100 mm or less, more preferably 80 mm or less, and particularly preferably 50 mm. It is as follows.

Furthermore, the area of the resin composition layer 320 may be smaller than, larger than, or the same as the area of the substrate 200. In the compression molding method, the resin composition layer 320 is often expanded by pressure to form a cured layer on the surface 200D of the substrate 200, so the area of the resin composition layer 320 before being pressurized is is typically smaller than the area of substrate 200. In this case, from the viewpoint of improving yield by forming a cured body layer with a large area, the area of the resin composition layer 320 with respect to 100% of the area of the substrate 200 is preferably 50% or more, more preferably 60% or more, especially Preferably it is 70% or more.

The resin composition layer 320 preferably has a capacity that can fill the inside of the cavity 130 when the resin composition layer 320 is pressurized in step (III). Therefore, when pressurized in step (III), the inside of the cavity 130 can be filled without any gaps by the part of the support film 310 housed in the cavity 130 and the entire resin composition layer 320. It is preferable that the capacity of the resin composition layer 320 is set to . The resin composition layer 320 having such a capacity can fill the inside of the cavity 130 without any gaps. For example, when the cavity 130 forms a space for compression molding between the substrate 200 supported by the first mold 110 and the second mold 120 as in this embodiment, the pressure is applied in step (III). A part of the supporting film 310 and the entire resin composition layer 320 can fill the space formed by the cavity 130 without any gaps. Therefore, in the cured body layer formed by curing the resin composition layer 320, the occurrence of unfilled portions and voids can be suppressed.

The thickness of the resin composition layer 320 can be appropriately set depending on the semiconductor device to be manufactured. For example, when the resin composition layer 320 is thin, a thin cured body layer can be easily formed, so that the semiconductor device can be easily made thinner. Further, for example, when the resin composition layer 320 is thick, a thick cured body layer can be easily formed, so that the cured body layer can easily seal a thick component that the substrate 200 may include. However, from the viewpoint of effectively obtaining the advantages of suppressing the formation of irregularities in the cured body layer and suppressing the staining of the first mold 110 and the second mold 120 due to the resin composition flowing out, the thickness of the resin composition layer 320 is The diameter is preferably 10 μm or more, more preferably 20 μm or more, particularly preferably 30 μm or more, and preferably 500 μm or less, more preferably 450 μm or less, particularly preferably 400 μm or less.

Further, the thickness of the resin composition layer 320 is preferably uniform. When the resin composition layer 320 has a uniform thickness, pressure can be applied to the entire cavity 130 in a well-balanced manner, so that sufficient pressure can be applied to the support film 310 at the end of the cavity 130. Therefore, since the support film 310 can smoothly follow the inner surface of the cavity 130, the generation of wrinkles in the support film 310 after pressurization can be suppressed. The uniformity of thickness can be expressed as the difference between the maximum and minimum thickness values. To give a specific range, the difference between the maximum and minimum thicknesses of the resin composition layer 320 is preferably 10 μm or less, more preferably 7 μm or less, particularly preferably 5 μm or less.

The resin composition contained in the resin composition layer 320 preferably has a melt viscosity η _C within a specific range under the temperature conditions during compression molding in step (III). Specifically, the melt viscosity η _C is preferably 300 poise or more, more preferably 500 poise or more, particularly preferably 1000 poise or more, and preferably 20000 poise or less, more preferably 10000 poise or less, particularly preferably is less than 5000 poise. When the melt viscosity η _C of the resin composition is equal to or higher than the lower limit of the above range, it is possible to prevent the fluidity of the resin composition from becoming excessively high. Therefore, outflow of the resin composition from the cavity 130 can be effectively suppressed. Furthermore, when the melt viscosity η _C of the resin composition is less than or equal to the upper limit of the above range, the resin composition can efficiently transmit the applied pressure to every corner of the cavity 130 . Therefore, sufficient pressure is applied to the support film 310 at the end of the cavity 130, so that the support film 310 can smoothly follow the inner surface of the cavity 130. Therefore, generation of wrinkles in the support film 310 after pressurization can be suppressed.

The melt viscosity of the resin composition can be measured by a dynamic viscoelasticity method. As specific measurement conditions, the conditions described in Examples can be adopted.

The resin composition included in the resin composition layer 320 preferably has a melt viscosity η ₀ within a specific range at 120°C. Specifically, the melt viscosity η ₀ is preferably in the same range as the melt viscosity η _C of the resin composition. Generally, the temperature conditions during compression molding in step (III) can be set to 120° C. or a temperature close to it. Therefore, a resin composition whose melt viscosity η ₀ at 120° C. is within the specific range can usually exhibit an appropriate melt viscosity η _C during compression molding in step (III). Therefore, when the resin composition has a melt viscosity η ₀ in the same range as the above melt viscosity η _C at 120° C., the same advantages as described as the advantages of the preferable range of the melt viscosity η _C can be obtained. I can do it.

The dimension in the in-plane direction of the support film 310 is set to be larger than the dimension in the in-plane direction of the cavity 130 from the viewpoint of allowing at least a part of the margin portion 312 of the support film 310 to protrude from the cavity 130. It is formed. Thus, the width W ₃₁₀ of the support film 310 is typically larger than the width W ₁₃₀ of the cavity 130 (see FIG. 1).

The ratio of the width W ₃₁₀ of the support film 310 to the width W ₁₃₀ of the cavity 130 (W ₃₁₀ /W ₁₃₀ ) is preferably 1.02 or more, more preferably 1.05 or more, particularly preferably 1.10 or more. When the ratio (W ₃₁₀ /W ₁₃₀ ) is within the above range, the compression molding in step (III) is usually performed while stably maintaining the state in which the end 310E of the support film 310 is outside the cavity 130. It can be carried out. Therefore, formation of unevenness in the cured body layer can be effectively suppressed. There is no particular restriction on the upper limit of the ratio (W ₃₁₀ /W ₁₃₀ ), but from the viewpoint of suppressing costs by suppressing the margin portion 312 of the support film 310 from becoming excessively wide, it is preferably 2.00 or less, and more preferably 2.00 or less. It is preferably 1.80 or less, particularly preferably 1.50 or less.

Further, the difference (W ₃₁₀ - W ₁₃₀ ) between the width W ₃₁₀ of the support film 310 and the width W 130 of the cavity ₁₃₀ is preferably 5 mm or more, more preferably 10 mm or more, and particularly preferably 20 mm or more. When the difference (W ₃₁₀ - W ₁₃₀ ) is within the above range, the compression molding in step (III) is usually performed while stably maintaining the state in which the end 310E of the support film 310 is outside the cavity 130. It can be carried out. Therefore, formation of unevenness in the cured body layer can be effectively suppressed. The upper limit of the difference (W ₃₁₀ - W ₁₃₀ ) is not particularly limited, but from the viewpoint of suppressing cost by suppressing the margin portion 312 of the support film 310 from becoming excessively wide, it is preferably 300 mm or less, more preferably 300 mm or less. It is 200 mm or less, particularly preferably 150 mm or less.

Furthermore, the area of the support film 310 is formed to be larger than the opening area of the cavity 130 from the viewpoint of allowing at least a portion of the margin portion 312 of the support film 310 to protrude from the cavity 130. The area of the support film 310 relative to 100% of the opening area of the cavity 130 is preferably 105% or more, more preferably 110% or more, particularly preferably 115% or more. When the area of the support film 310 is within the above range, it is usually possible to effectively suppress the formation of irregularities in the cured material layer. The upper limit of the area of the support film 310 is not particularly limited, but from the viewpoint of suppressing costs by suppressing the margin portion 312 of the support film 310 from becoming excessively wide, the upper limit of the area of the support film 310 is preferably 300% or less, more preferably 250%. It is particularly preferably 200% or less.

The in-plane dimension of the support film 310 is larger than the in-plane dimension of the substrate 200 when the substrate 200 is small enough to be accommodated in the cavity 130 . Further, the in-plane dimension of the support film 310 is smaller than the in-plane dimension of the substrate 200 when the substrate 200 is large enough to cover the cavity 130 as in the example shown in this embodiment. It can be large, it can be the same, it can be the same. Thus, the width W ₃₁₀ of the support film 310 may typically be smaller, larger, or the same as the width W ₂₀₀ of the substrate 200.

Among these, from the viewpoint of facilitating peeling of the support film 310, the width W ₃₁₀ of the support film 310 is preferably larger than the width W ₂₀₀ of the substrate 200. In this case, the ratio of the width W ₃₁₀ of the support film to the width W ₂₀₀ of the substrate 200 (W ₃₁₀ /W ₂₀₀ ) is preferably 1.01 or more, more preferably 1.03 or more, particularly preferably 1.05 or more. be. The upper limit is not particularly limited and may be, for example, 1.50 or less. Further, the difference (W ₃₁₀ - W ₂₀₀ ) between the width W ₃₁₀ of the support film 310 and the width W ₂₀₀ of the substrate 200 is preferably 2 mm or more, more preferably 5 mm or more, and particularly preferably 10 mm or more. The upper limit is not limited and may be, for example, 200 mm or less.

Further, when the substrate 200 is large enough to cover the cavity 130, the area of the support film 310 is preferably larger than the area of the substrate 200. In this case, the area of the support film 310 relative to 100% of the area of the substrate 200 is preferably 101% or more, more preferably 103% or more, particularly preferably 105% or more. There is no upper limit, and it can be, for example, 200% or less.

Since the support portion 311 of the support film 310 is a portion on which the resin composition layer 320 is formed, the dimensions and area in the in-plane direction of the support portion 311 may be the same as those of the resin composition layer 320 described above.

It is preferable that the dimension of the margin portion 312 of the support film 310 in the in-plane direction be large so that at least a portion of the margin portion 312 can protrude from the cavity 130 .

In particular, the width W ₃₁₂ of the margin portion 312 is preferably 60% or more with respect to 100% of the difference (W ₁₃₀ - _{W 320 )} between the width W ₁₃₀ of the cavity 130 and the width W 320 of the resin composition layer 320, It is more preferably 100% or more, still more preferably 200% or more, particularly preferably 300% or more. When the width W ₃₁₂ of the margin portion 312 is within the above range, the margin portion 312 of the support film 310 can protrude sufficiently from the cavity 130, so that the end portion 310E of the support film 310 extends outside the cavity 130. Compression molding in step (III) can be performed while maintaining a certain state stably. Therefore, formation of unevenness in the cured body layer can be effectively suppressed. The upper limit of the width W ₃₁₂ of the margin portion 312 is not particularly limited, but from the perspective of suppressing the margin portion 312 from becoming excessively wide and reducing costs, it is preferably 1000% or less, more preferably 900% or less, Particularly preferably, it is 800% or less.

Further, the width W ₃₁₂ of the margin portion 312 is preferably 10 mm or more, more preferably 15 mm or more, and particularly preferably 20 mm or more. When the width W ₃₁₂ of the margin portion 312 is within the above range, formation of irregularities in the cured material layer can be effectively suppressed. The upper limit of the width W ₃₁₂ of the margin portion 312 is not particularly limited, and may be, for example, 200 mm or less, 150 mm or less, or 100 mm or less.

Furthermore, the ratio (W ₃₂₀ /W ₃₁₂ ) between the width W ₃₁₂ of the margin portion 312 and the width W ₃₂₀ of the resin composition layer 320 is preferably 2.0 or more, more preferably 3.0 or more, particularly preferably 4 .0 or more. When the ratio (W ₃₂₀ /W ₃₁₂ ) is within the above range, the resin sheet 300 can be easily handled. The upper limit of the ratio (W ₃₂₀ /W ₃₁₂ ) is not particularly limited, but may be, for example, 50.0 or less.

The thickness t of the support film 310 is preferably 5 μm or more, more preferably 10 μm or more, particularly preferably 20 μm or more, and preferably 100 μm or less, more preferably 80 μm or less, particularly preferably 60 μm or less. Moreover, it is preferable that the thickness of the support film is uniform.

The support film 310 preferably has an elastic modulus E _C within a specific range under the temperature conditions during compression molding in step (III). Specifically, the elastic modulus E _C is preferably 6.0 GPa or less, more preferably 5.0 GPa or less, still more preferably 4.0 GPa or less, particularly preferably 1.0 GPa or less. When the support film 310 has an elastic modulus E _C within the above range, the support film 310 can smoothly follow the inner surface of the cavity 130 during compression molding, and thus the generation of wrinkles in the support film 310 after pressurization can be suppressed. The lower limit of the elastic modulus E _C of the support film 310 is not particularly limited, and may be, for example, 0.1 GPa or more.

Preferably, the support film 310 has an elastic modulus E ₀ in a certain range at 120°C. Specifically, the elastic modulus E ₀ is preferably in the same range as the elastic modulus E _C of the support film 310. Generally, the temperature conditions during compression molding in step (III) can be set to 120° C. or a temperature close to it. Therefore, the support film 310 whose elastic modulus E ₀ at 120° C. is within the specific range can usually exhibit an appropriate elastic modulus E _C during compression molding in step (III). Therefore, if the supporting film 310 has an elastic modulus E ₀ in the same range as the elastic modulus E _C at 120° C., the same advantages as described as the advantages of the preferred range of the elastic modulus E _C can be obtained. I can do it.

The elastic modulus of the support film 310 can be measured as a storage modulus by dynamic mechanical analysis (DMA).

The product (t×E _C ) of the thickness t of the support film 310 and the elastic modulus E _C of the support film 310 is preferably 300 [μm·GPa] or less, more preferably 200 [μm·GPa] or less, Particularly preferably, it is 100 [μm·GPa] or less. When the product (t×E _C ) is within the range, the support film 310 can smoothly follow the inner surface of the cavity 130 during compression molding, and thus the generation of wrinkles in the support film 310 after pressurization can be suppressed. The lower limit of the product (t×E _C ) is not particularly limited, and may be, for example, 10 [μm·GPa] or more.

The product (t×E ₀ ) of the thickness t of the support film 310 and the elastic modulus E ₀ of the support film 310 is the same as the product (t×E _C ) of the thickness t and the elastic modulus E _C Preferably within this range. In this case, advantages similar to those described above as advantages of the preferred range of the product (t×E _C ) can be obtained.

The product (η _C ×E _C ) of the melt viscosity η _C of the resin composition included in the resin composition layer 320 and the elastic modulus E _C of the support film 310 is preferably 20.0×10 ³ [ poise/GPa] or less, more preferably 15.0×10 ³ [poise/GPa] or less, particularly preferably 10.0×10 ³ [poise/GPa] or less. When the product (η _C ×E _C ) is within the range, the support film 310 can smoothly follow the inner surface of the cavity 130 during compression molding, so that wrinkles can be suppressed in the support film 310 after pressurization. The lower limit of the product (η _C ×E _C ) is not particularly limited, and may be, for example, 0.1×10 ³ [poise·GPa] or more.

The product (η ₀ ×E ₀ ) of the melt viscosity η ₀ of the resin composition included in the resin composition layer 320 and the elastic modulus E ₀ of the support film 310 is the melt viscosity η _C and the elastic modulus E _C It is preferable that it is in the same range as the product (η _C ×E _C ). In this case, advantages similar to those described above as advantages of the preferred range of the product (η _C ×E _C ) can be obtained.

The product (η _C ×t×E _C ) of the melt viscosity η _C of the resin composition included in the resin composition layer 320, the thickness t of the support film 310, and the elastic modulus E _C of the support film 310 is , preferably 10.0×10 ⁵ [μm・poise・GPa] or less, more preferably 7.0×10 ⁵ [μm・poise・GPa] or less, particularly preferably 5.0×10 ⁵ [μm・poise・GPa] or less GPa] or less. When the product (η _C ×t×E _C ) is within the range, the support film 310 can smoothly follow the inner surface of the cavity 130 during compression molding, thereby suppressing the occurrence of wrinkles in the support film 310 after pressurization. can. The lower limit of the product (η _C ×t×E _C ) is not particularly limited, and may be, for example, 0.1×10 ⁵ [μm·poise·GPa] or more.

The product (η ₀ ×t×E ₀ ) of the melt viscosity η ₀ of the resin composition included in the resin composition layer 320, the thickness t of the support film 310, and the elastic modulus E ₀ of the support film 310 is: It is preferably within the same range as the product of the melt viscosity η _C , the thickness t, and the elastic modulus E _C (η _C ×t×E _C ). In this case, advantages similar to those described above as advantages of the preferred range of the product (η _C ×t×E _C ) can be obtained.

The method for manufacturing the resin sheet 300 described above is not particularly limited. For example, the resin sheet 300 can be manufactured by a method that includes applying a resin composition onto the support film 310. Further, for example, the resin sheet 300 may be manufactured by a method including applying a resin varnish containing a resin composition and a solvent onto the support film 310. When a resin varnish is used, the resin composition layer 320 is usually formed by drying the resin varnish after application. Furthermore, from the viewpoint of improving manufacturing efficiency, the resin sheet 300 is preferably manufactured using a long support film. A "long" film refers to a film that is usually 10 times or more longer than its width, preferably a film that is long enough to be wound into a roll. Hereinafter, a method for manufacturing this preferable resin sheet 300 will be explained.

The method for manufacturing the resin sheet 300 exemplified here includes the steps of preparing a long support film, intermittently applying resin varnish on the support film, and drying the applied resin varnish to form a long support film. and a step of cutting the long resin sheet to obtain the resin sheet 300 described above.

FIG. 5 is a perspective view schematically showing a manufacturing apparatus 410 for a long resin sheet 400 according to an example. As shown in FIG. 5, the method for manufacturing a long resin sheet 400 according to the example shown here includes a step of preparing a long support film 420. Usually, the long support film 420 is prepared in the form of a roll.

The prepared long support film 420 is conveyed in the longitudinal direction and supplied to the coating device 430. The coating device 430 intermittently coats the resin varnish 440 onto the support film 420. As the coating device 430, a device capable of selectively coating the support portion 421 of the support film 420 can be used. For example, a rod coater, lip coater, comma coater, die coater, gravure coater, roll coater, etc. can be used.

Examples of solvents that the resin varnish 440 may contain in combination with the resin composition include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Solvents; organic solvents such as carbitol solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone; . One type of solvent may be used alone, or two or more types may be used in combination in any ratio.

After being coated with the resin varnish 440, the support film 420 is conveyed further downstream and supplied to a drying device 450. The drying device 450 dries the resin varnish 440 to remove volatile components such as solvents. Drying can be performed by heating, blowing hot air, or the like. The drying is preferably performed such that the content of the solvent in the resin composition layer 320 is usually 10% by mass or less, preferably 5% by mass or less. Although it may vary depending on the boiling point of the solvent contained in the resin varnish, for example, when using resin varnish 440 containing 30% by mass to 60% by mass of an organic solvent, the drying temperature is 50°C to 150°C, and the drying time is 3 minutes to 10 minutes. You can also use it as

By the drying, a long resin sheet 400 including a long support film 420 and a resin composition layer 320 formed on the support film 420 is obtained. In this resin sheet 400, the resin composition layer 320 is formed on the support portion 421 of the support film 420, but the resin composition layer 320 is not formed on the other margin portion 422. Therefore, by cutting this long resin sheet 400, the resin sheet 300 described above can be obtained.

The method for manufacturing resin sheet 300 may further include any steps. For example, the method for manufacturing the resin sheet 300 may include a step of providing a protective film (not shown) that protects the resin composition layer 320. The resin sheet 300 including a protective film may include a support film 310, a resin composition layer 320, and a protective film in this order in the thickness direction. According to the protective film, adhesion of dust and scratches to the resin composition layer 320 can be suppressed. The resin sheet 300 provided with a protective film can usually be used by peeling off the protective film.

FIG. 6 is a cross-sectional view schematically showing the resin sheet 300 installed in the compression molding apparatus 100 used in the method for manufacturing a semiconductor device according to the first embodiment of the present invention. As shown in FIG. 6, the prepared resin sheet 300 is placed in the second mold 120 so that the resin composition layer 320 fits into the cavity 130. At this time, the resin sheet 300 is installed so that the resin composition layer 320 and the support film 310 are lined up in this order from the substrate 200 side in the thickness direction. In this embodiment, as shown in FIG. 6, an example was shown in which the resin sheet 300 was installed in the second mold 120 after the substrate 200 was installed in the first mold 110, but the substrate 200 was installed in the first mold 110. The resin sheet 300 may be installed on the second mold 120 before installation.

[1.3. Compression molding process (III)]
FIG. 7 is a cross-sectional view schematically showing compression molding using the compression molding apparatus 100 used in the method for manufacturing a semiconductor device according to the first embodiment of the present invention.
In the manufacturing method according to the first embodiment of the present invention, after the above-described step (I) and step (II), as shown in FIG. A step (III) of pressurizing the substrate 200 and the resin sheet 300 between the mold 110 and the second mold 120 is included. Through this step (III), the resin composition layer 320 is compression molded to obtain a cured body layer 330 formed of a cured body of the resin composition.

Specifically, in step (III), the first mold 110 and the second mold 120 are closed. By closing the mold, the substrate 200 and the resin sheet 300 are placed between the first mold 110 and the second mold 120. At this time, a part or all of the margin portion 312 of the support film 310 included in the resin sheet 300 protrudes from the cavity 130 around the entire circumference of the cavity 130. Furthermore, a closed space surrounded by the substrate 200 and the support film 310 is formed within the cavity 130 . The entire resin composition layer 320 is contained within the closed space. With the resin composition layer 320 contained in the closed space within the cavity 130 in this manner, the bottom block 121 of the second mold 120 is pushed in to pressurize the substrate 200 and the resin sheet 300. By applying pressure, the resin composition layer 320 is bonded to the substrate 200, and the resin composition layer 320 is compression molded.

By applying the pressure, the entire closed space is filled with the resin composition layer 320. At this time, the margin portion 312 of the support film 310 is in close contact with the second mold 120 and the substrate 200. Therefore, since the gap 140 between the second mold 120 and the substrate 200 is closed by the margin portion 312 of the support film 310, the resin composition contained in the resin composition layer 320 does not flow out of the closed space. Therefore, staining of the first mold 110 and the second mold 120 due to the resin composition can be suppressed.

Usually, heating is performed with the resin composition layer 320 filled in the closed space as described above. By heating, the resin composition layer 320 is cured, and a cured body layer 330 containing a cured body of the resin composition is formed. In a pressurized state, the support film 310 can be tightly attached to the inner surface of the cavity 130, so that the closed space can have a similar shape to the cavity 130. Therefore, it is possible to form a cured material layer 330 that copies the shape of the cavity 130 with high precision.

At this time, since the margin portion 312 of the support film 310 protrudes from the cavity 130, it is possible to prevent the end portion 310E of the support film 310 from digging into the resin composition layer 320. Therefore, formation of irregularities in the cured body layer 330 can be suppressed.

The compression molding conditions described above vary depending on the composition of the resin composition, and appropriate conditions can be adopted so that a good cured body layer 330 can be obtained.
For example, the temperature of the mold during molding is preferably a temperature at which the resin composition can exhibit excellent compression moldability, preferably 80°C or higher, more preferably 100°C or higher, particularly preferably 120°C or higher, and preferably The temperature is 200°C or lower, more preferably 170°C or lower, particularly preferably 150°C or lower.
Further, for example, the pressure applied during molding is preferably 1 MPa or more, more preferably 3 MPa or more, particularly preferably 5 MPa or more, and preferably 50 MPa or less, more preferably 30 MPa or less, particularly preferably 20 MPa or less.
Further, for example, the cure time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 5 minutes or more, and preferably 60 minutes or less, more preferably 30 minutes or less, particularly preferably 20 minutes or less. be.

[1.4. [Optional process]
The manufacturing method according to the first embodiment of the present invention may include any steps in combination with the above-described steps (I), (II), and (III).
Usually, the manufacturing method according to this embodiment includes a step of opening the mold after step (III). By opening the mold in this manner, the substrate 200, the cured material layer 330, and the support film 310 can be removed from the compression molding apparatus 100. By removing the molded body in this manner, a molded body including the substrate 200, the cured body layer 330, and the support film 310 in this order in the thickness direction can be obtained.

Although the molded body described above may be used as a semiconductor device, the support film 310 is usually not necessary for the semiconductor device to be manufactured. Therefore, the manufacturing method according to the present embodiment may include a step of peeling off the support film 310. In the manufacturing method according to the present embodiment, it is possible to prevent the end portion 310E of the support film 310 from digging into the resin composition layer 320 during compression molding. Therefore, since the cured body layer 330 and the support film 310 can be easily separated, the support film 310 can be easily peeled off.

FIG. 8 is a cross-sectional view schematically showing a multilayer body 340 that can be manufactured by the manufacturing method according to the first embodiment of the present invention. As shown in FIG. 8, according to the manufacturing method according to the first embodiment, a multilayer body 340 including a substrate 200 and a cured body layer 330 formed on the substrate 200 by a cured body of a resin composition is manufactured. Obtainable. Such a multilayer body 340 may be obtained as a semiconductor device. For example, when a mounted board including a semiconductor chip (not shown) on the side of the cured body layer 330 is used as the board 200, the board 200 as the mounted board and a seal that seals the semiconductor chip included in the board 200 are used. The multilayer body 340 including the cured body layer 330 as a stopping layer can be obtained as a semiconductor chip package as a semiconductor device.

Further, the multilayer body 340 described above may further be provided with arbitrary elements such as a wiring layer, an insulating layer, a solder resist layer, and a semiconductor chip. Therefore, the manufacturing method according to this embodiment may include the step of providing these arbitrary elements.

Furthermore, the manufacturing method according to this embodiment may include a step of peeling the substrate 200 from the multilayer body 340. In this case, a semiconductor device including the cured body layer 330 but not including the substrate 200 can be obtained. For example, when a temporary fixing film that can temporarily fix a semiconductor chip in a removable manner is used as the substrate 200, a semiconductor device that does not include the substrate 200 can be obtained.

Furthermore, the manufacturing method according to the present embodiment may include a dicing step of dividing the multilayer body 340 or the cured body layer 330, which may include any element, into pieces.

Further, the manufacturing method according to the present embodiment may include a step of further thermally curing the obtained cured body layer 330 after opening the mold. Specifically, after opening the mold, a step of further heating the cured body layer 330 may be performed.

In the manufacturing method described above, the order in which each step is performed is not limited as long as a desired semiconductor device can be obtained. Moreover, a plurality of steps may be performed simultaneously.

[1.5. Main advantages of the manufacturing method according to the present embodiment]
According to the manufacturing method according to the first embodiment, formation of irregularities in the cured body layer 330 can be suppressed. Further, the support film 310 is usually easily peeled from the cured layer 330 obtained in this manner. These advantages will be explained below in comparison with other manufacturing methods.

FIG. 9 is a cross-sectional view schematically showing a compression molding apparatus 930 when compression molding is performed using a resin sheet 920 having a support film 910 that has no blank space and is smaller than the cavity 130. In FIG. 9, the same parts as described in the first embodiment described above are given the same reference numerals as in FIGS. 1 to 8.

As shown in FIG. 9, it is assumed that compression molding is performed using a resin sheet 920 that has no blank space and has a support film 910 that is smaller than the cavity 130. In this case, the entire support film 910 is contained within the cavity 130. Therefore, the end portion 910E of the support film 910 bites into the resin composition layer 320. Then, in the portion 940 of the resin composition layer 320 into which the end portion 910E of the support film 910 bites, unevenness is formed due to the digging. Further, when the end portion 910E is incorporated in this way, it becomes difficult to peel off the support film 910. Such a problem may similarly occur even in a method using a support film (not shown) having no blank space and having the same size as the cavity 130.

On the other hand, in the manufacturing method according to the first embodiment, as shown in FIG. is suppressed. Therefore, as shown in FIG. 8, formation of irregularities in the cured body layer 330 can be suppressed. Further, since the end portion 310E of the support film 310 is prevented from digging into the resin composition layer 320 in this way, the support film 310 can normally be easily peeled off.

Furthermore, according to the manufacturing method according to the first embodiment, staining of the first mold 110 and the second mold 120 due to outflow of the resin composition can be suppressed. This advantage will be explained below in comparison with other manufacturing methods.

Assume that compression molding is performed using a resin sheet with no blank space and a supporting film larger than the cavity. In this case, a portion of the resin composition layer protrudes outside the cavity. Therefore, when the protruding resin composition layer comes into contact with the first mold and the second mold, the resin composition adheres to the first mold and the second mold, causing stains. Such a problem may similarly occur even in a method using a support film (not shown) that has no blank space and has the same size as the cavity.

In contrast, in the manufacturing method according to the first embodiment, as shown in FIG. 7, the resin composition layer 320 is not provided in the blank area 312 of the support film 310 outside the cavity 130. Therefore, since the resin composition layer 320 does not come into contact with the first mold 110 and the second mold 120, staining due to adhesion of the resin composition can be suppressed.

Further, when appropriate conditions are adopted in the manufacturing method according to the first embodiment, the support film 310 can smoothly follow the inner surface of the cavity 130. Therefore, the occurrence of wrinkles in the support film 310 can be suppressed. Therefore, it is possible to prevent the wrinkles from being transferred to the cured body layer 330 and forming unintended deformed portions in the cured body layer 330.

[2. Second embodiment]
In the first embodiment, the method for manufacturing a semiconductor device was described using an example in which compression molding was performed after the substrate 200 was installed in the first mold 110 and the resin sheet 300 was installed in the second mold 120. However, the manner in which the substrate 200 and resin sheet 300 are installed is not limited to the first embodiment. For example, compression molding may be performed by placing both the substrate 200 and the resin sheet 300 in one of the first mold 110 and the second mold 120. The method will be described below by showing a second embodiment.

FIG. 10 is a cross-sectional view schematically showing a state in which a substrate 200 and a resin sheet 300 are installed in a compression molding apparatus 500 used in a method for manufacturing a semiconductor device according to the second embodiment of the present invention. In the second embodiment, the same parts as those described in the first embodiment are given the same reference numerals as in the first embodiment.

As shown in FIG. 10, a compression molding apparatus 500 used in the manufacturing method according to the second embodiment of the present invention has the following features: a first mold 110 is provided below and a second mold 120 is provided above. It is provided in the same manner as the compression molding apparatus 100 described in the embodiment. Therefore, the compression molding apparatus 500 has a first mold 110 that can support the substrate 200 and a second mold 120 provided opposite to the first mold 110 in the thickness direction of the first mold 110 and the second mold 120. be parallel to the vertical direction.

In the manufacturing method according to the second embodiment of the present invention, a semiconductor device is manufactured using the compression molding apparatus 500 described above. This manufacturing method is similar to the first embodiment,
Step (I) of preparing the substrate 200;
Step (II) of preparing a resin sheet 300;
The method includes a step (III) of placing the resin composition layer 320 in the cavity 130 and pressurizing the substrate 200 and the resin sheet 300 between the first mold 110 and the second mold 120.

The substrate 200 prepared in step (I) is the same as that described in the first embodiment. In the second embodiment, a prepared substrate 200 is placed in a first mold 110 as shown in FIG.

The resin sheet 300 prepared in step (II) is the same as that described in the first embodiment. In the second embodiment, as shown in FIG. 10, a prepared resin sheet 300 is placed on a substrate 200 so that the resin composition layer 320 fits into the cavity 130 when the mold is closed. At this time, the resin sheet 300 is installed so that the resin composition layer 320 and the support film 310 are lined up in this order from the substrate 200 side in the thickness direction. The resin sheet 300 may be placed on the substrate 200 after the substrate 200 is placed on the first mold 110, or may be placed on the substrate 200 before the substrate 200 is placed on the first mold 110.

FIG. 11 is a cross-sectional view schematically showing how compression molding is performed using a compression molding apparatus 500 used in the method for manufacturing a semiconductor device according to the second embodiment of the present invention.
In the manufacturing method according to the second embodiment of the present invention, after the above-mentioned step (I) and step (II), as shown in FIG. A step (III) of pressurizing the substrate 200 and the resin sheet 300 between the mold 110 and the second mold 120 is included. This step (III) can be performed in the same manner as in the first embodiment. Therefore, specifically, in step (III), the first mold 110 and the second mold 120 are closed, and the entire resin composition layer 320 is surrounded by the substrate 200 and the support film 310 of the resin sheet 300. It is housed in a closed space within the cavity 130. In this state, the substrate 200 and the resin sheet 300 are pressurized to bond the resin composition layer 320 to the substrate 200, and the resin composition layer 320 is compression-molded. Therefore, the cured body layer 330 can be obtained by curing the resin composition layer 320 by heating as necessary.

Thereafter, the mold is usually opened and the substrate 200, cured material layer 330, and support film 310 are removed from the compression molding apparatus 500. Then, the support film 310 is peeled off as needed, and a multilayer body 340 including the substrate 200 and the cured body layer 330 can be obtained as in the first embodiment.

According to the manufacturing method according to the second embodiment described above, the same advantages as the manufacturing method according to the first embodiment can be obtained.

The manufacturing method according to the second embodiment may include any steps as in the manufacturing method according to the first embodiment.

[3. Modified example]
The method for manufacturing a semiconductor device of the present invention may be implemented with further modifications from the embodiments described above. For example, a semiconductor device may be manufactured using a compression molding apparatus equipped with a mold in which a cavity capable of accommodating a substrate is formed. An example of the method will be described below with reference to the drawings.

FIG. 12 is a cross-sectional view schematically showing a state in which a substrate 200 and a resin sheet 300 are installed in a compression molding apparatus 600 used in a method for manufacturing a semiconductor device according to a third embodiment of the present invention. In the third embodiment, the same parts as explained in the first embodiment are given the same reference numerals as in the first embodiment.

As shown in FIG. 12, a compression molding apparatus 600 used in the manufacturing method according to the third embodiment of the present invention includes a first mold 610 that supports a substrate 200 and a cavity 630. The compression molding apparatus 100 is provided in the same manner as the compression molding apparatus 100 described in the first embodiment except that it is formed so as to be able to accommodate the substrate 200.

In the example shown in this embodiment, the cavity 630 is formed large enough to accommodate the substrate 200 and the resin composition layer 320 of the resin sheet 300. Therefore, in this compression molding apparatus 600, a space corresponding to the cavity 630 is formed between the first mold 610 and the second mold 620, and the resin composition layer 320 can be compression molded within this space.

Further, from the viewpoint of pressurizing the inside of the cavity 630, the first mold 610 includes a bottom block 611 and a side block 612 provided in an annular shape so as to surround the bottom block 611. The bottom block 611 is provided movably relative to the side blocks 612. Therefore, in this example, the first mold 610 is provided so that the inside of the cavity 630 can be pressurized by pressing the bottom block 611 upward in the figure.

In the manufacturing method according to the third embodiment of the present invention, the compression molding apparatus 600 described above is used to manufacture a semiconductor device. This manufacturing method is similar to the first embodiment,
Step (I) of preparing the substrate 200;
Step (II) of preparing a resin sheet 300;
The method includes a step (III) of placing the resin composition layer 320 in the cavity 630 and pressurizing the substrate 200 and the resin sheet 300 between the first mold 610 and the second mold 620.

The substrate 200 prepared in step (I) is the same as that described in the first embodiment. In the third embodiment, a prepared substrate 200 is placed in a cavity 630 of a first mold 610, as shown in FIG.

The resin sheet 300 prepared in step (II) is the same as that described in the first embodiment. In the third embodiment, as shown in FIG. 12, a prepared resin sheet 300 is placed on a substrate 200 so that the resin composition layer 320 fits into a cavity 630 when the mold is closed. The resin sheet 300 is installed so that the resin composition layer 320 and the support film 310 are lined up in this order from the substrate 200 side in the thickness direction. The resin sheet 300 may be placed on the substrate 200 after the substrate 200 is placed on the first mold 610, or may be placed on the second substrate 200 before the substrate 200 is placed on the first mold 610. good.

FIG. 13 is a cross-sectional view schematically showing how compression molding is performed using a compression molding apparatus 600 used in the method for manufacturing a semiconductor device according to the third embodiment of the present invention.
In the manufacturing method according to the third embodiment of the present invention, after the step (I) and step (II) described above, as shown in FIG. A step (III) of pressurizing the substrate 200 and the resin sheet 300 between the mold 610 and the second mold 620 is included. This step (III) can be performed in the same manner as in the first embodiment. Therefore, specifically, in step (III), the first mold 610 and the second mold 620 are closed, and the entire resin composition layer 320 is covered with the first mold 610, the substrate 200, and the resin sheet 300. It is housed in a closed space within a cavity 630 surrounded by a support film 310. In this state, the substrate 200 and the resin sheet 300 are pressurized to bond the resin composition layer 320 to the substrate 200, and the resin composition layer 320 is compression-molded. Therefore, the cured body layer 330 can be obtained by curing the resin composition layer 320 by heating as necessary.

Thereafter, the mold is usually opened and the substrate 200, cured material layer 330, and support film 310 are removed from the compression molding apparatus 600. Then, the support film 310 is peeled off as necessary, and a multilayer body including the substrate 200 and the cured body layer 330 can be obtained as in the first embodiment.

According to the manufacturing method according to the third embodiment described above, the same advantages as the manufacturing method according to the first embodiment can be obtained.

The manufacturing method according to the third embodiment may include arbitrary steps like the manufacturing method according to the first embodiment.

[4. Composition of resin composition]
The composition of the resin composition is not particularly limited as long as the resin composition has thermosetting properties.

From the viewpoint of being able to exhibit thermosetting properties, the resin composition usually contains a thermosetting resin. Examples of thermosetting resins include epoxy resins, cyanate ester resins, phenol resins, bismaleimide-triazine resins, polyimide resins, acrylic resins, vinylbenzyl resins, and the like. One type of thermosetting resin may be used alone, or two or more types may be used in combination. Among these, epoxy resin is preferred because it is easy to obtain a cured layer with high sealing ability.

Examples of the epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type Examples include epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, and the like. One type of epoxy resin may be used alone, or two or more types may be used in combination.

It is preferable that the resin composition contains an epoxy resin having two or more epoxy groups in one molecule. The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably It is 70% by mass or more.

Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). ). The resin composition may contain a liquid epoxy resin, a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin; glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. Preferred are alicyclic epoxy resins such as alicyclic epoxy resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, glycidylamine-type epoxy resins, and epoxy resins having a butadiene structure, such as bisphenol A-type epoxy resins and bisphenol F-type epoxy resins. Type epoxy resins are more preferred.

Specific examples of liquid epoxy resins include "HP-4032", "HP-4032D", "HP-4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "jER828EL" manufactured by Mitsubishi Chemical; "825", "Epicote 828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical's "jER807", "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical's "jER152" (phenol novolac type epoxy resin) ); “630” and “630LSD” manufactured by Mitsubishi Chemical Corporation (glycidylamine type epoxy resin); “ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (mixture product of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagasechem "EX-721" (glycidyl ester type epoxy resin) manufactured by Tex; "CEL 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel; "PB-3600" (butadiene structure) manufactured by Daicel epoxy resins); examples include "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resins) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and "EP3950L" (glycidylamine type epoxy resins) manufactured by ADEKA. . These may be used alone or in combination of two or more.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and biphenyl. Type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, and tetraphenylethane type epoxy resins are preferred, and biphenyl type epoxy resins are more preferred.

Specific examples of solid epoxy resins include "HP-4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolak type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200", "HP-7200HH" manufactured by DIC, "HP-7200H" (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" ” (naphthylene ether type epoxy resin); “EPPN-502H” manufactured by Nippon Kayaku Co., Ltd. (trisphenol type epoxy resin); “NC7000L” manufactured by Nippon Kayaku Co., Ltd. (naphthol novolac type epoxy resin); Nippon Kayaku Co., Ltd. "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical; "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical; "ESN485" manufactured by Nippon Steel & Sumikin Chemical ( Naphthol novolac type epoxy resin); “YX4000H”, “YX4000”, “YL6121” manufactured by Mitsubishi Chemical (biphenyl type epoxy resin); “YX4000HK” (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical; manufactured by Mitsubishi Chemical "YX8800" (anthracene type epoxy resin); "PG-100", "CG-500" manufactured by Osaka Gas Chemical; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical; Examples include "YL7800" (fluorene type epoxy resin); "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; and "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical. These may be used alone or in combination of two or more.

When using a liquid epoxy resin and a solid epoxy resin in combination, their quantitative ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.01 to 1:20, more preferably 1:20 by mass. The ratio is 1:0.05 to 1:10, particularly preferably 1:0.1 to 1:1. When the ratio of the liquid epoxy resin to the solid epoxy resin is within the above range, appropriate tackiness can usually be obtained. In addition, sufficient flexibility is usually obtained and handling properties are improved. Furthermore, it is usually possible to obtain a cured product having sufficient breaking strength.

The epoxy equivalent of the epoxy resin is preferably 50 g/eq to 5000 g/eq, more preferably 50 g/eq to 3000 g/eq, even more preferably 80 g/eq to 2000 g/eq, even more preferably 110 g/eq to 1000 g/eq. It is. When the epoxy equivalent is within this range, the crosslinking density of the cured product of the resin composition can be increased. Epoxy equivalent is the mass of resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, even more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

From the viewpoint of obtaining a cured layer exhibiting good mechanical strength and insulation reliability, the amount of the epoxy resin is preferably 1% by mass or more, more preferably 3% by mass based on 100% by mass of the nonvolatile components in the resin composition. % or more, more preferably 5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, particularly preferably 10% by mass or less. In addition, in this specification, unless otherwise specified, the amount of each component in the resin composition represents a value when the nonvolatile components in the resin composition are 100% by mass.

From the viewpoint of obtaining a cured layer exhibiting good mechanical strength and insulation reliability, the content of the epoxy resin is preferably 10% by mass or more, more preferably 15% by mass, based on 100% by mass of the resin component in the resin composition. It is at least 20% by mass, more preferably at least 20% by mass, preferably at most 50% by mass, more preferably at most 40% by mass, particularly preferably at most 30% by mass. The term "resin component" refers to nonvolatile components contained in a resin composition excluding inorganic fillers.

When the resin composition contains an epoxy resin, it is preferable that the resin composition contains a curing agent. The curing agent has a function of curing the resin composition by reacting with the epoxy resin. Examples of the curing agent include active ester curing agents, phenol curing agents, naphthol curing agents, acid anhydride curing agents, benzoxazine curing agents, cyanate ester curing agents, carbodiimide curing agents, and amine curing agents. Examples include agents. Among these, active ester hardeners and phenol hardeners are preferred, and phenol hardeners are particularly preferred, since they can easily provide a cured layer with high sealing performance. Moreover, one type of curing agent may be used alone, or two or more types may be used in combination.

As the active ester curing agent, a compound having one or more active ester groups in one molecule can be used. Among these, active ester curing agents include those containing two or more ester groups with high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. Compounds having the following are preferred. The active ester curing agent is preferably one obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, active ester curing agents obtained from a carboxylic acid compound and a hydroxy compound are preferred, and active ester curing agents obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound are more preferred. .

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

Examples of phenolic compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Examples include benzenetriol, dicyclopentadiene type diphenol compounds, and phenol novolacs. Here, the term "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Preferred specific examples of the active ester curing agent include an active ester curing agent containing a dicyclopentadiene type diphenol structure, an active ester curing agent containing a naphthalene structure, an active ester curing agent containing an acetylated product of phenol novolac, Examples include active ester curing agents containing benzoylated phenol novolacs. Among these, active ester curing agents containing a naphthalene structure and active ester curing agents containing a dicyclopentadiene type diphenol structure are more preferable. "Dicyclopentadiene type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents containing a dicyclopentadiene diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-". "EXB-9416-70BK", "EXB-8150-65T", "EXB-8100L-65T" as an active ester curing agent containing a naphthalene structure. ", "EXB-8150L-65T" (manufactured by DIC Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent containing an acetylated product of phenol novolac; active ester curing agent containing a benzoylated product of phenol novolak "YLH1026" (manufactured by Mitsubishi Chemical Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent that is an acetylated product of phenol novolak; "YLH1026" as an active ester curing agent that is a benzoylated product of phenol novolac. (manufactured by Mitsubishi Chemical Company), "YLH1030" (manufactured by Mitsubishi Chemical Company), "YLH1048" (manufactured by Mitsubishi Chemical Company); and the like.

As the phenolic curing agent and the naphthol curing agent, those having a novolac structure are preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion between the cured body layer and the conductor layer, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic curing agent is more preferable.

Specific examples of phenolic curing agents and naphthol curing agents include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd.; Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH" made by Nippon Steel & Sumikin Chemical Co., Ltd. "SN-170", "SN-180", "SN-190", "SN-475", "SN-485" made by Nippon Steel & Sumikin Chemical Co., Ltd. "SN-495", "SN-495V", "SN-375", "SN-395"; DIC's "TD-2090", "TD-2090-60M", "LA-7052", "LA -7054'', ``LA-1356'', ``LA-3018'', ``LA-3018-50P'', ``EXB-9500'', ``HPC-9500'', ``KA-1160'', ``KA-1163'', ``KA -1165''; "GDP-6115L", "GDP-6115H", and "ELPC75" manufactured by Gunei Kagakusha.

Examples of acid anhydride curing agents include curing agents having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid. Anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride Mellitic acid, pyromellitic anhydride, bensophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1 , 3-dione, ethylene glycol bis(anhydrotrimellitate), and polymeric acid anhydrides such as styrene-maleic acid resin, which is a copolymer of styrene and maleic acid.

Commercially available acid anhydride curing agents include "MH-700" manufactured by Shin Nippon Rika Co., Ltd.

Specific examples of benzoxazine curing agents include "JBZ-OD100" (benzoxazine ring equivalent: 218 g/eq.), "JBZ-OP100D" (benzoxazine ring equivalent: 218 g/eq.), and "ODA" manufactured by JFE Chemical. -BOZ" (benzoxazine ring equivalent 218 g/eq.); "P-d" (benzoxazine ring equivalent 217 g/eq.), "Fa" (benzoxazine ring equivalent 217 g/eq.) manufactured by Shikoku Kasei Kogyo Co., Ltd. ); “HFB2006M” manufactured by Showa Kobunshi Co., Ltd. (benzoxazine ring equivalent: 432 g/eq.); and the like.

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4 '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethyl Bifunctional cyanate resins such as phenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether; Polyfunctional cyanate resins derived from phenol novolacs, cresol novolaks, etc.; prepolymers in which these cyanate resins are partially triazinized; and the like. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (phenol novolak type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), and "BA230" manufactured by Lonza Japan. , "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazinized to form a trimer), and the like.

Specific examples of carbodiimide curing agents include Carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216 g/eq.), V-05 (carbodiimide group equivalent: 262 g/eq.), and V- manufactured by Nisshinbo Chemical Co., Ltd. 07 (carbodiimide group equivalent: 200 g/eq.); V-09 (carbodiimide group equivalent: 200 g/eq.); Stabaxol (registered trademark) P manufactured by Rhein Chemie (carbodiimide group equivalent: 302 g/eq.).

Examples of the amine curing agent include curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine curing agent include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 3,3' - Diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl- 4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane Diamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3- Bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, Examples include bis(4-(3-aminophenoxy)phenyl)sulfone. Commercially available amine curing agents may be used, such as "KAYABOND C-200S", "KAYABOND C-100", "KAYA HARD AA", "KAYA HARD AB", and "KAYABOND C-100" manufactured by Nippon Kayaku Co., Ltd. Examples include "Kayahard AS" and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

The quantitative ratio of the epoxy resin to the curing agent is the ratio of [total number of epoxy groups in the epoxy resin]:[total number of reactive groups in the curing agent], and is preferably in the range of 1:0.01 to 1:10. The ratio is more preferably 1:0.05 to 1:5, and even more preferably 1:0.1 to 1:3. Here, the reactive group of the curing agent is an active hydroxyl group, etc., and differs depending on the type of curing agent. In addition, the total number of epoxy groups in an epoxy resin is the sum of the solid mass of each epoxy resin divided by the epoxy equivalent for all epoxy resins, and the total number of reactive groups in the curing agent is: This value is the sum of the solid mass of each curing agent divided by the reactive group equivalent for all curing agents. By setting the ratio of the epoxy resin to the curing agent within this range, the heat resistance of the cured product of the resin composition is further improved.

The amount of the curing agent is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and preferably 10% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. It is at most 8% by mass, more preferably at most 8% by mass, even more preferably at most 5% by mass.

The resin composition may contain an inorganic filler if necessary. An inorganic compound can be used as the material for the inorganic filler. Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, Magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide , barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica and alumina are preferred, and silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as the silica, spherical silica is preferable. One type of inorganic filler may be used alone, or two or more types may be used in combination.

Commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials; "YC100C" and "YC100C" manufactured by Admatex. YA050C”, “YA050C-MJE”, “YA010C”; “Silfill NSS-3N”, “Silfill NSS-4N”, “Silfill NSS-5N” manufactured by Tokuyama; “SC2500SQ”, “SO-” manufactured by Admatex C4,” “SO-C2,” “SO-C1,” and the like.

The specific surface area of the inorganic filler is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, particularly preferably 3 m ² /g or more. Although there is no particular limit to the upper limit, it is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area can be measured using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) by adsorbing nitrogen gas onto the sample surface and using the BET multi-point method.

The average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less. It is.

The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, it can be measured by creating the particle size distribution of the inorganic filler on a volume basis using a laser diffraction scattering type particle size distribution measuring device, and using the median diameter as the average particle size. The measurement sample can be obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them using ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction particle size distribution measuring device using a light source wavelength of blue and red, and the volume-based particle size distribution of the inorganic filler was measured using a flow cell method. The average particle size can be calculated as the median diameter. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include vinyl silane coupling agents, (meth)acrylic coupling agents, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, Examples include silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, and the like. One type of surface treatment agent may be used alone, or two or more types may be used in any combination.

Commercially available surface treatment agents include, for example, "KBM1003" (vinyltriethoxysilane) manufactured by Shin-Etsu Chemical, "KBM503" (3-methacryloxypropyltriethoxysilane) manufactured by Shin-Etsu Chemical, and "KBM503" (3-methacryloxypropyltriethoxysilane) manufactured by Shin-Etsu Chemical. "KBM403" (3-glycidoxypropyltrimethoxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical, "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical , "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical, "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical, "KBM103" (phenyl trimethoxysilane), "KBM-4803" (long chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical, "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical etc.

The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 parts by mass to 5 parts by mass of a surface treatment agent, and preferably 0.2 parts by mass to 3 parts by mass. Preferably, the surface treatment is carried out in an amount of 0.3 parts by mass to 2 parts by mass.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in sheet form, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and even more preferably 0.5 mg/m ² or less. preferable.

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler whose surface has been treated with a surface treatment agent, and the mixture is subjected to ultrasonic cleaning at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd., etc. can be used.

The content (volume %) of the inorganic filler is preferably 30 volume % or more, more preferably 30 volume % or more, based on 100 volume % of the nonvolatile components in the resin composition, from the viewpoint of lowering the dielectric loss tangent of the cured product of the resin composition. is 40% by volume or more, more preferably 50% by volume or more. Moreover, it is preferably 80 volume% or less, more preferably 70 volume% or less, and even more preferably 60 volume% or less.

The content (mass%) of the inorganic filler is preferably 50% by mass or more, more preferably 50% by mass or more based on 100% by mass of the nonvolatile components in the resin composition, from the viewpoint of lowering the dielectric loss tangent of the cured product of the resin composition. is 60% by mass or more, more preferably 65% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less.

The resin composition may contain an elastomer, if necessary. When using a resin composition containing an elastomer, warping of the cured body layer can be effectively suppressed. One type of elastomer may be used alone, or two or more types may be used in combination.

The elastomer has one or more types selected from polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure in the molecule. A resin having a structure is preferable. Among these, resins having one or more structures selected from a polybutadiene structure, a poly(meth)acrylate structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, or a polycarbonate structure are more preferable. Furthermore, a resin having one or more structures selected from a polybutadiene structure and a polyalkyleneoxy structure is more preferable, and a resin having a polybutadiene structure is particularly preferable. "(Meth)acrylate" is a term that includes methacrylates and acrylates and combinations thereof. These structures may be included in the main chain or in the side chain.

The elastomer preferably has a high molecular weight from the viewpoint of reducing warping of the cured body layer. The number average molecular weight (Mn) of the elastomer is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 3,000 or more, and even more preferably 5,000 or more. The upper limit is preferably 1,000,000 or less, more preferably 900,000 or less. The number average molecular weight (Mn) is a polystyrene equivalent number average molecular weight measured using GPC (gel permeation chromatography).

The elastomer preferably has a functional group that can react with the epoxy resin, from the viewpoint of curing the resin composition by reacting with the epoxy resin and increasing peel strength. Functional groups that can react with the epoxy resin include functional groups that appear when heated.

In one preferred embodiment, the functional group capable of reacting with the epoxy resin is one or more selected from the group consisting of a hydroxy group, a carboxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group. is a functional group. Among these, the functional group is preferably a hydroxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, or a urethane group, and more preferably a hydroxy group, an acid anhydride group, a phenolic hydroxyl group, or an epoxy group. A hydroxyl group is particularly preferred. However, when an epoxy group is included as a functional group, the number average molecular weight (Mn) is preferably 5,000 or more.

A preferred embodiment of the elastomer is a resin containing a polybutadiene structure, and the polybutadiene structure may be included in the main chain or in the side chain. Note that the polybutadiene structure may be partially or entirely hydrogenated. A resin containing a polybutadiene structure is called a polybutadiene resin.

Specific examples of polybutadiene resins include "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", and "Ricon 131MA" manufactured by Clay Valley. 20”, “Ricon 184MA6” (polybutadiene containing acid anhydride groups), “GQ-1000” manufactured by Nippon Soda Co., Ltd. (polybutadiene with hydroxyl and carboxyl groups introduced), “G-1000”, “G-2000”, “G-3000” (polybutadiene containing acid anhydride groups) hydroxyl group polybutadiene), “GI-1000”, “GI-2000”, “GI-3000” (hydrogenated polybutadiene with hydroxyl groups at both ends), “FCA-061L” manufactured by Nagase ChemteX (hydrogenated polybutadiene skeleton epoxy resin), etc. can be mentioned. In one embodiment, a linear polyimide made from a hydroxyl group-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (polyimide described in JP2006-37083A and WO2008/153208), a phenolic hydroxyl group Containing butadiene and the like can be mentioned. The content of the butadiene structure in the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. For details of the polyimide resin, the descriptions in JP-A No. 2006-37083 and International Publication No. 2008/153208 can be referred to, the contents of which are incorporated herein.

A preferred embodiment of the elastomer is a resin containing a poly(meth)acrylate structure. A resin containing a poly(meth)acrylate structure is called a poly(meth)acrylic resin. Examples of poly(meth)acrylic resins include Teisan Resin manufactured by Nagase ChemteX, "ME-2000", "W-116.3", "W-197C", "KG-25", and "ME-2000" manufactured by Negami Kogyo Co., Ltd. KG-3000'', etc.

A preferred embodiment of the elastomer is a resin containing a polycarbonate structure. A resin containing a polycarbonate structure is called a polycarbonate resin. Examples of polycarbonate resins include "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and "C-1090", "C-2090", and "C-3090" (polycarbonate diol) manufactured by Kuraray Corporation. It will be done. It is also possible to use linear polyimides made from hydroxyl-terminated polycarbonates, diisocyanate compounds, and tetrabasic acid anhydrides. The content of carbonate structure in the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. For details of the polyimide resin, the description in International Publication No. 2016/129541 can be referred to, the contents of which are incorporated herein.

Another embodiment of the elastomer is a resin containing a siloxane structure. A resin containing a siloxane structure is called a siloxane resin. Examples of siloxane resins include "SMP-2006," "SMP-2003PGMEA," and "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone, linear polyimides made from amine-terminated polysiloxanes and tetrabasic acid anhydrides (International Publication No. 2010/053185, JP 2002-12667, JP 2000-319386, etc.).

Another embodiment of the elastomer is a resin containing an alkylene structure or an alkyleneoxy structure. A resin containing an alkylene structure is called an alkylene resin, and a resin containing an alkyleneoxy structure is called an alkyleneoxy resin. The polyalkyleneoxy structure is preferably a polyalkyleneoxy structure having 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure having 3 to 10 carbon atoms, and even more preferably a polyalkyleneoxy structure having 5 to 6 carbon atoms. Specific examples of alkylene resins and alkyleneoxy resins include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers.

Another embodiment of the elastomer is a resin containing an isoprene structure. A resin containing an isoprene structure is called an isoprene resin. Specific examples of isoprene resins include "KL-610" and "KL613" manufactured by Kuraray.

Another embodiment of the elastomer is a resin containing an isobutylene structure. A resin containing an isobutylene structure is called an isobutylene resin. Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation.

From the viewpoint of obtaining a resin composition with a low melt viscosity, the amount of the elastomer is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass, based on 100% by mass of the nonvolatile components in the resin composition. It is at least 30% by mass, more preferably at most 25% by mass, and even more preferably at most 20% by mass. Further, when the amount of the elastomer is within the above range, a cured layer that has excellent dielectric loss tangent and adhesion to the conductor layer and can suppress warpage is usually obtained.

From the viewpoint of obtaining a resin composition with a low melt viscosity, the amount of the elastomer is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass, based on 100% by mass of the resin component in the resin composition. It is at least 70% by mass, more preferably at most 60% by mass, even more preferably at most 50% by mass. Further, when the amount of the elastomer is within the above range, a cured layer that has excellent dielectric loss tangent and adhesion to the conductor layer and can suppress warpage is usually obtained.

The resin composition may contain a curing accelerator, if necessary. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like. One type of curing accelerator may be used alone, or two or more types may be used in combination.

Examples of the phosphorus curing accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo. Examples include (5,4,0)-undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferred.

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds and epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole curing accelerator, commercial products may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation, "1B2PZ" (1-benzyl-2-phenylimidazole) manufactured by Shikoku Kasei Co., Ltd., etc. can be mentioned.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc., and dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

Examples of the metal hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples include organic zinc complexes such as , organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

The amount of the curing accelerator is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. The content is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, even more preferably 0.1% by mass or less.

The resin composition may further contain arbitrary components in addition to the components described above. Optional components include, for example, thermoplastic resins; flame retardants; organic fillers such as rubber particles; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; thickeners; antifoaming agents; leveling agents. ; adhesion imparting agent; coloring agent such as pigment; maleimide compound described in JP-A-2019-044128; and the like. One type of arbitrary components may be used alone, or two or more types may be used in combination.

The resin composition may contain a solvent, but the amount thereof is preferably small. The amount of solvent contained in the resin composition is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.01% by mass, based on 100% by mass of nonvolatile components in the resin composition. % by mass or less. Among these, it is particularly preferable that the resin composition does not contain a solvent.

[5. Composition of support film]
Examples of the support film include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferred.

When using a film made of a plastic material as the support film, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polyesters such as polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic polymers such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), Examples include ether ketone, polyimide, polypropylene, polystyrene, and the like. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When using metal foil as the support film, examples of the metal foil include copper foil, aluminum foil, etc., with copper foil being preferred. As the copper foil, a foil made of a single metal such as copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. May be used.

The support film may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface to be bonded to the resin composition layer.

As the support film, a support film with a release layer may be used, which has a release layer on the surface to be bonded to the resin composition layer. Examples of the release agent used in the release layer of the support film with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . The supporting film with a release layer may be a commercially available product, such as "SK-1" manufactured by Lintec, which is a PET film having a release layer containing an alkyd resin mold release agent as a main component. Examples include "AL-5", "AL-7", "Lumirror T60" manufactured by Toray Industries, "Purex" manufactured by Teijin, and "Unipeel" manufactured by Unitika.

[6. Applications of semiconductor devices]
According to the manufacturing method described above, a semiconductor device including a cured body layer can be manufactured. Examples of semiconductor devices including such a cured body layer include printed wiring boards, semiconductor chip packages, multi-chip packages, package-on-packages, wafer-level packages, panel-level packages, system-in-packages, and the like. In these semiconductor devices, the cured body layer can function, for example, as an insulating layer or a sealing layer.

Semiconductor devices manufactured in this manner are suitable for use in, for example, electrical products (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, aircraft, etc.). It can be used for

Hereinafter, the present invention will be specifically explained by showing examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Further, the operations described below were performed in an environment of normal temperature and normal pressure unless otherwise specified.

[Method for measuring melt viscosity of resin composition layer]
The melt viscosity of the resin compositions used in the Examples and Comparative Examples described below was measured using a dynamic viscoelasticity measuring device (Rheosol-G3000, manufactured by UBM). Specifically, 1 g of the sample resin composition was heated at a heating rate of 5°C/min from a starting temperature of 60°C to 200°C using a circular parallel plate with a diameter of 18 mm, and the measurement temperature interval was The melt viscosity was measured under the conditions of 2.5° C., frequency of 1 Hz, and strain of 5 degrees. From the measurement results thus obtained, the melt viscosity at the temperature (120° C.) during compression molding, which will be described later, was read.

[Method of measuring elastic modulus of support film]
The elastic modulus of the support film used in the Examples and Comparative Examples described below was measured as a storage elastic modulus by DMA. The measurement was performed at the temperature (120° C.) during compression molding, which will be described later.

[Production Example 1: Production of Elastomer A]
In a reaction vessel, 69 g of difunctional hydroxy group-terminated polybutadiene (Nippon Soda Co., Ltd. "G-3000", number average molecular weight = 3000, hydroxy group equivalent = 1800 g/eq.) and an aromatic hydrocarbon mixed solvent (Idemitsu Petroleum) were placed in a reaction vessel. 40 g of "Ipsol 150" (manufactured by Kagaku Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When the mixture became uniform, the temperature was raised to 60° C., and while stirring, 8 g of isophorone diisocyanate (“IPDI” manufactured by Evonik Degussa Japan, isocyanate group equivalent = 113 g/eq.) was added, and the reaction was carried out for about 3 hours.

Next, 23 g of cresol novolac resin (KA-1160 manufactured by DIC Corporation, hydroxyl equivalent = 117 g/eq.) and 60 g of ethyl diglycol acetate (manufactured by Daicel Corporation) were added to the reaction product, and the temperature was raised to 150° C. with stirring. The temperature was raised and the reaction was carried out for about 10 hours. The disappearance of the NCO peak at 2250 cm ^-1 was confirmed by FT-IR. Confirmation of disappearance of the NCO peak was regarded as the end point of the reaction, and the temperature of the reaction product was lowered to room temperature. Then, the reaction product was filtered through a 100 mesh filter cloth to obtain an elastomer having a butadiene structure and a phenolic hydroxyl group (phenolic hydroxyl group-containing butadiene resin: 50% by mass of non-volatile components). Elastomer A had a number average molecular weight of 5900 and a glass transition temperature of -7°C.

[Production Example 2: Production of resin varnish]
1 part of biphenyl-type epoxy resin (“NC3000” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 276 g/eq.), bisphenol-type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type) product, epoxy equivalent 169 g/eq.) 5 parts, spherical silica surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle size 0.5 μm, specific surface area 5.8 m ² /g) , "SO-C2" manufactured by Admatex) 65 parts, 20 parts of elastomer A, 4 parts of maleimide compound ("BMI-689" manufactured by Designer Molecules), cresol novolac resin ("KA-1160" manufactured by DIC) , phenolic hydroxyl group equivalent: 117 g/eq), 0.05 part of a curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., "1B2PZ"), and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotating mixer. A resin varnish was produced.

A portion of the resin varnish was weighed out and dried to obtain a resin composition. The melt viscosity η _C of this resin composition at a temperature of 120° C. during compression molding, which will be described later, was measured and found to be 4000 poise.

[Example 1]
(Preparation of board)
An FR-4 board with a width of 32 cm and a length of 32 cm was prepared.

(Manufacture of resin sheet)
A long support film ("AL5" manufactured by Lintec, elastic modulus 4.6 GPa, thickness 38 μm, width 40 cm) comprising a polyethylene terephthalate film and a release layer provided on the surface of this polyethylene terephthalate film was prepared. did. The resin varnish produced in Production Example 2 was intermittently applied to a plurality of square areas (width 29 cm, length 29 cm, area 841 cm ² ) on one side of this support film using an applicator. The resin composition layer was dried at an average temperature of 100° C.) to form a resin composition layer having a uniform thickness (300 μm). When viewed from the thickness direction, a blank area with no resin composition layer was formed around the entire circumference of each resin composition layer. Thereafter, the support film was cut into a square with a length of 40 cm and a width of 40 cm (area: 1600 cm ² ) to obtain a resin sheet. The above cutting was performed so that the resin composition layer was located at the center of the support film when the resulting resin sheet was viewed from the thickness direction. Therefore, the width of the margin portion of the support film was 5.5 cm at any position of the resin composition layer.

(compression molding)
As shown in FIG. 1, a compression molding apparatus 100 including a first mold 110 and a second mold 120 as molds was prepared. A cavity 130 having a square opening (length: 30 cm, width: 30 cm, opening area: 900 cm ² ) was formed on the side of the second mold 120 facing the first mold 110 . As shown in FIG. 6, an FR-4 substrate 200 was placed on the first mold 110, and a resin sheet 300 was placed on the second mold 120. Thereafter, the first mold 110 and the second mold 120 were closed, and the inside of the cavity 130 was pressurized to perform compression molding. The compression molding described above was performed under the conditions of a mold temperature of 120° C., a pressure of 7 MPa, and a cure time of 5 minutes.

After compression molding, the mold was opened to obtain a molded body comprising an FR-4 substrate, a cured layer formed of a cured resin composition, and a support film in this order.

[Example 2]
The long support film on which the resin composition layer was formed was cut so that the resulting square support film had a length of 37.5 cm and a width of 37.5 cm (area: 1406 cm ² ). Except for the above matters, a resin sheet and a molded body were manufactured by compression molding in the same manner as in Example 1.

[Example 3]
The type of long support film was changed to a polystyrene film (Kurabo Industries, Ltd. "Oidis CA-F10", elastic modulus 3.1 GPa, thickness 50 μm). Further, the long support film on which the resin composition layer was formed was cut so that the size of the square support film obtained after cutting was 33 cm long and 33 cm wide (area 1089 cm ² ). Except for the above matters, a resin sheet and a molded body were manufactured by compression molding in the same manner as in Example 1.

[Example 4]
The type of long support film was changed to a fluororesin film ("Aflex 50 MW" manufactured by AGC Corporation, elastic modulus 0.8 GPa, thickness 50 μm). Further, the thickness of the resin composition layer formed on the support film was changed to 500 μm. Furthermore, the long support film on which the resin composition layer was formed was cut so that the size of the square support film obtained after cutting was 37.5 cm long and 37.5 cm wide (area 1406 cm ² ). . Except for the above matters, a resin sheet and a molded body were manufactured by compression molding in the same manner as in Example 1.

[Example 5]
The type of long support film was changed to a polyethylene naphthalate film (Teijin Co., Ltd. "Teonex", elastic modulus 6.1 GPa, thickness 50 μm). Further, the thickness of the resin composition layer formed on the support film was changed to 100 μm. Furthermore, the long support film on which the resin composition layer was formed was cut so that the size of the square support film obtained after cutting was 37.5 cm long and 37.5 cm wide (area 1406 cm ² ). . Except for the above matters, a resin sheet and a molded body were manufactured by compression molding in the same manner as in Example 1.

[Comparative example 1]
The thickness of the resin composition layer formed on the support film was changed to 150 μm. In addition, the long support film on which the resin composition layer was formed was cut so that the size of the square support film obtained after cutting was the same as the resin composition layer (length 29 cm, width 29 cm, area 841 cm ² ). I went to The supporting film of the resin film thus obtained had no blank space. Except for the above matters, a resin sheet and a molded body were manufactured by compression molding in the same manner as in Example 1.

[evaluation]
<Evaluation of unevenness of cured body layer>
The support film was peeled off from the molded bodies obtained in Examples and Comparative Examples (i.e., molded bodies comprising an FR-4 substrate, a cured body layer formed of a cured body of a resin composition, and a support film in this order). Ta. Thereafter, the surface of the cured product layer was observed to check for the presence or absence of irregularities formed by the support film biting into it. If there were no irregularities, it was determined to be "good", and if there were irregularities, it was determined to be "bad".

<Evaluation of mold stains>
After compression molding, the mold was observed to check for adhesion of the resin composition. When there was no adhesion of the resin composition, it was judged as "good", and when there was adhesion of the resin composition, it was judged as "poor".

<Compression moldability evaluation>
The molded bodies obtained in Examples and Comparative Examples (i.e., molded bodies comprising an FR-4 substrate, a cured body layer formed of a cured body of a resin composition, and a support film in this order) were peeled off from the support film. I observed it before. If there were no wrinkles on the support film within the processing area of the mold, it was judged as "good". A sample in which the support film had wrinkles and slight traces due to the wrinkles appeared on the surface of the cured layer was judged to be "fair."

[result]
The results of the above Examples and Comparative Examples are shown in the table below.

100 Compression molding device 110 First mold 120 Second mold 121 Bottom block 122 Side block 130 Cavity 130U Cavity opening 140 Gap between second mold and substrate 200 Substrate 200D Surface of substrate 300 Resin sheet 310 Support film 310U Support One side of the film 310E End of support film 311 Support portion 312 Margin portion 320 Resin composition layer 330 Cured material layer 340 Multilayer body 400 Long resin sheet 410 Resin sheet manufacturing apparatus 420 Long support film 421 Long Support part of support film 422 Margin part of long support film 430 Coating device 440 Resin varnish 450 Drying device 500 Compression molding device 600 Compression molding device 610 First mold 611 Bottom block 612 Side block 620 Second mold 630 Cavity W ₁₃₀ Width of cavity W ₂₀₀ Width of substrate W ₃₁₀ Width of support film W ₃₁₂ Width of margin W ₃₂₀ Width of resin composition layer

Claims (10)

A compression molding apparatus is used, which includes a first mold capable of supporting a substrate, and a second mold provided opposite to the first mold, and in which a cavity is formed in at least one of the first mold and the second mold. A method for manufacturing a semiconductor device, comprising:
The manufacturing method includes:
preparing the substrate;
a step of preparing a resin sheet comprising a support film and a resin composition layer formed of a thermosetting resin composition on the support film;
a step of placing the resin composition layer in the cavity and pressurizing the substrate and the resin sheet between the first mold and the second mold,
The support film includes a support portion on which the resin composition layer is formed and a margin portion on which the resin composition layer is not formed,
When viewed from the thickness direction, the margin portion is located around the entire circumference of the support portion,
The elastic modulus E ₀ of the support film at 120° C. is 0.8 GPa or more,
A semiconductor device, wherein the product (t×E ₀ ) of the thickness t of the support film and the elastic modulus E ₀ of the support film is 10 [μm·GPa] or more and 300 [μm·GPa] or less. Production method. 2. The method of manufacturing a semiconductor device according to claim 1, wherein in the step of pressurizing the substrate and the resin sheet, the margin portion of the support film protrudes from the cavity all around the cavity. The method for manufacturing a semiconductor device according to claim 1 or 2, wherein the elastic modulus E ₀ of the support film at 120° C. is 6.0 GPa or less. Any one of claims 1 to 3, wherein the resin composition layer has a capacity that can fill the inside of the cavity when the resin composition layer is pressurized in the step of pressurizing the substrate and the resin sheet. A method for manufacturing a semiconductor device according to . The method for manufacturing a semiconductor device according to claim 1, wherein the resin composition has a melt viscosity η ₀ of 300 poise or more and 20,000 poise or less at 120° C. The method for manufacturing a semiconductor device according to claim 1, wherein the resin composition layer has a thickness of 10 μm or more and 500 μm or less. comprising a support film and a resin composition layer formed of a thermosetting resin composition on the support film,
The support film includes a support portion on which the resin composition layer is formed and a margin portion on which the resin composition layer is not formed,
When viewed from the thickness direction, the margin portion is located around the entire circumference of the support portion,
The elastic modulus E ₀ of the support film at 120° C. is 0.8 GPa or more and 6.0 GPa or less,
A resin sheet, wherein the product (t×E ₀ ) of the thickness t of the support film and the elastic modulus E ₀ of the support film is 10 [μm·GPa] or more and 300 [μm·GPa] or less . The resin sheet according to claim 7, wherein the resin composition has a melt viscosity η ₀ of 300 poise or more and 20,000 poise or less at 120°C. The product (η ₀ ×E ₀ ) of the melt viscosity η ₀ of the resin composition at 120° C. and the elastic modulus E ₀ of the support film is 20.0×10 ³ [poise·GPa] or less. The resin sheet according to claim 7 or 8. The product (η ₀ ×t×E ₀ ) of the melt viscosity η ₀ of the resin composition at 120° C., the thickness t of the support film, and the elastic modulus E ₀ of the support film is 10.0× The resin sheet according to any one of claims 7 to 9 , which has a thickness of 10 ⁵ [μm·poise·GPa] or less.

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