Resin compositions, resin pastes, cured products, semiconductor chip packages, and semiconductor devices.

Abstract

To provide a resin composition which from which a cured product that suppresses occurrence of warpage and is excellent in mechanical characteristics can be obtained.SOLUTION: A resin composition contains (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, wherein when the resin composition is cured by a curing method including the following compression molding step and post-cure step, the obtained cured product indicates porosity of 0.002% to 2%, here, the porosity is an area ratio (%) of a void region in an SEM cross-sectional image of the cured product: [compression molding step] a step of arranging the resin composition so as to be joined to a silicon wafer, then compression-molding the resin composition under conditions of a pressure of 15 tons, a temperature of 130°C and 10 minutes, and obtaining a compression molding of the resin composition which is joined to the silicon wafer and has thickness of 300 μm; [post-curing step] a step of heating the obtained compression molding of the resin composition in the nitrogen atmosphere under conditions of a temperature of 150°C and 1 hour, and obtaining a cured product.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The present invention relates to resin compositions, and more particularly to resin pastes. Furthermore, it relates to cured products, semiconductor chip packages, and semiconductor devices formed using the resin composition or resin paste. [Background technology]

[0002] In recent years, the demand for small, high-performance electronic devices such as smartphones and tablet devices has increased, and consequently, there is a growing need for even higher performance insulating materials for semiconductor chip packages used in these small electronic devices. Such insulating materials are known to be formed by curing resin compositions (for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2004-137370 [Overview of the project] [Problems that the invention aims to solve]

[0004] In recent years, when manufacturing semiconductor chip packages, there has been a demand for resin compositions used to form the insulating layer that suppress warping and produce cured products with excellent mechanical properties.

[0005] The object of the present invention is to provide a resin composition or resin paste that can produce a cured product with suppressed warping and excellent mechanical properties; and a cured product formed using the resin composition or resin paste, a semiconductor chip package, and a semiconductor device. [Means for solving the problem]

[0006] The inventors diligently studied to solve the aforementioned problems. As a result, the inventors discovered that the aforementioned problems can be solved by a resin composition containing (A) epoxy resin, (B) curing agent, and (C) inorganic filler, which produces a cured product having voids in a specific range of amounts, and thus completed the present invention. In other words, the present invention includes the following:

[0007] [1] A resin composition comprising (A) epoxy resin, (B) curing agent, and (C) inorganic filler, When the resin composition is cured by a curing method including the following compression molding and post-curing steps, the resulting cured product exhibits a void ratio in the range of 0.002% to 2%. Here, the porosity is the area percentage (%) of the void region in the SEM cross-sectional image of the cured resin composition. <Compression molding process> The process involves positioning the resin composition to bond to a silicon wafer, then compression molding it under conditions of 15 tons of pressure, 130°C, and 10 minutes to obtain a compressed molded body of the resin composition bonded to the silicon wafer with a thickness of 300 μm. <Post-cure process> A process to obtain a cured product by heating a compression molded body of the obtained resin composition under a nitrogen atmosphere at a temperature of 150°C for 1 hour. [2] The resin composition according to [1], wherein the porosity is obtained by calculating the area ratio (%) of the void region to the observation region obtained as a void image by image analysis of an observation region with dimensions of 1,000 pixels in the thickness direction and 1,000 pixels in the in-plane direction in a cross-sectional SEM image at a magnification of 27,000 times. [3] The resin composition according to [1] or [2], wherein the porosity is the arithmetic mean of the area percentage (%) of void regions obtained for 50 SEM cross-sectional images of the cured material. [4] The compression molding process is the following steps (c1) to (c4): (c1) A step of placing a silicon wafer and a resin composition into a mold to which a release film has been attached; (c2) A step of closing the mold within 90 seconds after the resin composition is placed to bond the silicon wafer and the resin composition; (c3) A step of reducing the pressure inside the mold to a degree of reduced pressure within the range of 0 to 0.7 torr; and, (c4) A process to obtain a compressed molded body of a resin composition with a thickness of 300 μm bonded to a silicon wafer by compression molding under the conditions of a pressure of 15 tons, a temperature of 130°C, and 10 minutes. A resin composition according to any one of [1] to [3], comprising the following in this order. [5] The post-curing process is the following steps (p1)~(p2): (p1) A step of obtaining a cured product by placing a compressed molded body of the resin composition removed from the mold into an oven set to 150°C and 1 atmosphere under a nitrogen atmosphere and waiting for 1 hour; and, (p2) Remove the cured material from the oven within 120 seconds after step (p1) and allow it to cool at room temperature and pressure. A resin composition according to any one of [1] to [4], comprising the following in this order. [6] The resin composition according to any one of [1] to [5], wherein the resin porosity, which is the area ratio of the void region in the resin component region to the observed region obtained by excluding the void region within the region defined by the outer shape region of the inorganic filler (B) from the void region obtained as a void image by image analysis, is in the range of 0.002% to 2%. [7] The resin composition according to any one of [1] to [6], wherein component (C) is 30% by mass or more when the nonvolatile components in the resin composition are taken as 100% by mass. [8] A resin composition according to any one of [1] to [7], wherein component (A) is a liquid epoxy resin (A-1). [9] (E-1) A resin composition according to any one of [1] to [8], comprising a silane coupling agent, wherein the silane coupling agent is of a single type.

[10] (E-1) A resin composition according to any one of [1] to [8], comprising a silane coupling agent, wherein there are multiple types of silane coupling agents.

[11] The resin composition according to any one of [1] to

[10] , wherein the solvent content is 3% by mass or less when the nonvolatile components in the resin composition are considered to be 100% by mass.

[12] The resin composition according to any one of [1] to

[11] , wherein a viscosity measured at 25°C using an E-type viscometer is within a range of 1 Pa·s to 1000 Pa·s.

[13] The resin composition according to any one of [1] to

[12] , wherein a dielectric constant (Dk) of a cured product thereof is less than 3.6.

[14] The resin composition according to any one of [1] to

[13] , wherein a dielectric loss tangent (Df) of a cured product thereof is less than 0.03.

[15] The resin composition according to any one of [1] to

[14] , wherein a strength at break of a cured product thereof is more than 45 MPa.

[16] The resin composition according to any one of [1] to

[15] , wherein a curing degree of the cured product is 95% or more.

[17] The resin composition according to any one of [1] to

[16] , which is for forming an insulating layer of a semiconductor chip package.

[18] The resin composition according to any one of [1] to

[17] , which is for a rewiring formation layer.

[19] A resin paste formed by comprising the resin composition according to any one of [1] to

[18] .

[20] A cured product of the resin composition according to any one of [1] to

[18] or the resin paste according to

[19] .

[21] A cured product of a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, wherein the cured product has a porosity within a range of 0.002% to 2%, and the porosity is an area ratio (%) of void regions in an SEM cross-sectional image of the cured product.

[22] A semiconductor chip package comprising: an insulating layer formed of a cured product of the resin composition according to any one of [1] to

[18] or the resin paste according to

[19] , or an insulating layer formed of the cured product according to

[20] or

[21] .

[23] The semiconductor chip package according to

[22] , wherein the insulating layer is a rewiring formation layer.

[24] The semiconductor chip package according to

[22] or

[23] , which is a fan-out type package.

[25] A semiconductor device comprising the semiconductor chip package according to any one of

[22] to

[24] . Advantageous Effects of Invention

[0008] According to the present invention, a resin composition or resin paste can be obtained that suppresses warping and yields a cured product with excellent mechanical properties; a cured product formed using the resin composition or resin paste, a semiconductor chip package, and a semiconductor device can be provided. [Brief explanation of the drawing]

[0009] [Figure 1] Figure 1 is a schematic cross-sectional view showing the configuration of a fan-out type WLP as an example of a semiconductor chip package according to one embodiment of the present invention. [Figure 2] Figure 2 is a photograph of a cross-sectional SEM image of the cured product of Example 8, as displayed in the analysis software. [Figure 3] Figure 3 is a photograph showing the void region in the SEM cross-sectional image of Figure 2, colored red. [Modes for carrying out the invention]

[0010] The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and may be implemented with modifications as appropriate without departing from the scope of the claims and their equivalents.

[0011] [Resin composition] The resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, and is characterized in that it produces a cured product having voids in a specific range of amounts.

[0012] In detail, when the resin composition of the present invention is cured by a curing method including the following compression molding and post-curing steps, the resulting cured product exhibits a void ratio in the range of 0.002% to 2%. <Compression molding process> The process involves positioning the resin composition to bond to a silicon wafer, then compression molding it under conditions of 15 tons of pressure, 130°C, and 10 minutes to obtain a compressed molded body of the resin composition bonded to the silicon wafer with a thickness of 300 μm. <Post-cure process> A process to obtain a cured product by heating a compression molded body of the obtained resin composition under a nitrogen atmosphere at a temperature of 150°C for 1 hour.

[0013] The "porosity," used as an indicator of the amount of voids in the cured product, represents the area ratio (%) of voids in the cross-section of the cured product. In this invention, it is expressed as the area ratio (%) of the void region in the SEM cross-sectional image of the cured product. While it is also conceivable to evaluate the amount of voids contained in the cured product by volume ratio (%), the inventors have found that the above porosity, in relation to area ratio (%), allows for a simple and accurate evaluation and definition of the composition of a resin composition that produces a cured product with excellent mechanical properties, thus suppressing warping, as is the effect of this invention.

[0014] When determining the porosity, the area percentage of the void region may be calculated for the entire SEM cross-sectional image, or it may be calculated for a specific region in the SEM cross-sectional image, preferably of a predetermined size or larger, more preferably of a specific size. From the viewpoint of accurately evaluating and defining the porosity in relation to whether the effects of the present invention can be achieved (hereinafter, the same applies when referring to "the viewpoint of accurately evaluating and defining the porosity"), it is preferable to calculate the area percentage of the void region for an observation region of a predetermined size or larger, preferably of a specific size, in the SEM cross-sectional image (the preferred size of the observation region will be described later).

[0015] The SEM cross-sectional image may be an SEM image of a longitudinal section of the cured resin composition, or an SEM image of a cross-sectional surface of the cured resin composition. A longitudinal section is a section that includes the thickness dimension. The longitudinal section may be a section along a direction perpendicular to the main surface of the cured resin composition, or, if a member having a plane (e.g., a silicon wafer) is joined to the cured resin composition on that plane, it may be a section along a direction perpendicular to the plane of the member. A cross-sectional surface is a section perpendicular to the longitudinal section, that is, a section parallel to the in-plane direction. The cross-sectional surface may be a section parallel to the main surface of the cured resin composition, or, if a member having a plane (e.g., a silicon wafer) is joined to the cured resin composition on that plane, it may be a section parallel to the plane of the member. From the viewpoint of easily obtaining cross-sections, it is preferable that the SEM cross-sectional image is an SEM image of a longitudinal section of the cured resin composition.

[0016] From the viewpoint of accurately evaluating and defining the porosity, it is preferable to pre-define the magnification during SEM observation and the size of the observation area in the SEM cross-sectional image. For example, the magnification during SEM observation is preferably 20,000x or more, more preferably 25,000x or more, 26,000x or more, or 27,000x or more, and the size of the observation area in the SEM cross-sectional image may be preferably 800 pixels square or more, more preferably 900 pixels square or more, or 1,000 pixels square or more, in terms of the number of pixels. From the viewpoint of accurately evaluating and defining the porosity, the upper limit of the magnification during SEM observation is preferably 50,000x or less, more preferably 49,000x or less, 48,000x or less, or 47,000x or less, and the upper limit of the size of the observation area in the SEM cross-sectional image is not particularly limited when calculating the area ratio (%) of the porosity, but may be preferably 1,300 pixels square or less, more preferably 1,200 pixels square or less, or 1,100 pixels square or less, in terms of the number of pixels. In one preferred embodiment, the void ratio is obtained by performing image analysis on an observation area of ​​1000 pixels square (1000 pixels in thickness direction × 1000 pixels in plane direction) in a cross-sectional SEM image of the cured material at a magnification of 27000x, and calculating the area ratio (%) of the void area to the observation area obtained as a void image.

[0017] From the viewpoint of accurately evaluating and defining the porosity, it is preferable to adopt the arithmetic mean of the porosity calculated for multiple SEM cross-sectional images and observation areas as the porosity. Therefore, in one preferred embodiment, the porosity is the arithmetic mean of the area percentage (%) of the void regions obtained for 50 SEM cross-sectional images of the hardened material.

[0018] Typically, the porosity can be measured according to the method described in the section on measuring the porosity of the cured material below. When obtaining SEM cross-sectional images of 50 locations on the cured material, it is preferable to cross-section (preferably longitudinal cross-sections) of multiple test pieces of a single sample. Alternatively, cross-section (preferably longitudinal cross-sections) may be performed multiple times on a single test piece.

[0019] The following describes the compression molding process and post-curing process performed when preparing a cured sample for determining the porosity.

[0020] <Compression molding process> In the compression molding process, the resin composition is positioned to bond to the silicon wafer, and then compressed and molded under conditions of a pressure of 15 tons, a temperature of 130°C, and 10 minutes to obtain a compressed molded body of the resin composition with a thickness of 300 μm bonded to the silicon wafer.

[0021] The compression molding process may be carried out using any apparatus, including molds, as long as it can compress and mold the silicon wafer and the resin composition under the above conditions to produce a compressed molded body of the resin composition bonded to the silicon wafer. For example, the compression molding process may be carried out using a compression molding machine configured to include a pair of separable molds.

[0022] Preferably, the pair of molds is one in which a silicon wafer can be placed, either in a mold located vertically downward or in a mold located vertically upward. In one embodiment, the compression molding process is performed using a compression molding machine configured to include a pair of separable molds, where the silicon wafer is placed in the mold located vertically downward, and the resin composition is placed between the mold located vertically upward and the silicon wafer. In another embodiment, the compression molding process is performed using a compression molding machine configured to include a pair of separable molds, where the silicon wafer is placed in the mold located vertically upward, and the resin composition is placed between the mold located vertically downward and the silicon wafer. The silicon wafer and the resin composition may be placed separated from each other, or they may be placed in contact with each other. That is, regarding the positional relationship between the silicon wafer and the resin composition, as long as they are arranged so that they can be joined together, the silicon wafer may be placed above the resin composition, or the resin composition may be placed above the silicon wafer.

[0023] It is preferable to place the silicon wafer and resin composition in a mold whose interior has been preheated to 130°C. Although the mold is heated to 130°C, the interior of the mold may be heated to a temperature within a range of up to +5°C during or prior to the compression molding process.

[0024] In the compression molding process, it is preferable to quickly reach a pressure of 15 tons after the start of pressurization, for example, within 60 seconds. The pressurization start point may be defined as the time when the mold closing operation begins or the time when the distance between the pair of molds begins to narrow, and this time may be measured accordingly. It is preferable that the mold closing operation is started quickly. The 10 minutes, which is one of the conditions in the compression molding process, usually refers to the time the resin composition is exposed to a temperature of 130°C, but it is preferable that this refers to the elapsed time after reaching a pressure of 15 tons.

[0025] The silicon wafer is not limited to any size that allows for obtaining a cured resin composition with measurable porosity, but in the compression molding process, it is preferable to place a silicon wafer with a thickness of 775 μm and a diameter of 12 inches in the mold. If it is necessary to remove the compressed resin composition from the silicon wafer, it is preferable to apply a release treatment to the silicon wafer beforehand.

[0026] Although the thickness of the compressed molded body of the resin composition is stated to be 300 μm, it is not strictly necessary for it to be 300 μm. In the compression molding process, the compression molding may be carried out in such a way that variations in the thickness of the compressed molded body of the resin composition are permitted within a range of ±5 μm.

[0027] From the perspective of accurately evaluating and defining the void ratio, the compression molding process consists of the following steps (c1) to (c4): (c1) A step of placing a silicon wafer and a resin composition into a mold to which a release film has been attached; (c2) A step of closing the mold within 90 seconds after the resin composition is placed to bond the silicon wafer and the resin composition; (c3) A step of reducing the pressure inside the mold to a degree of reduced pressure within the range of 0 to 0.7 torr; and, (c4) A process to obtain a compressed molded body of a resin composition with a thickness of 300 μm bonded to a silicon wafer by compression molding under the conditions of a pressure of 15 tons, a temperature of 130°C, and 10 minutes. It is particularly preferable to include these steps in this order. A compression molding process that includes steps (c1) to (c4) in this order is also called a "standardized compression molding process".

[0028] Regarding the standardized compression molding process, in step (c1), the arrangement of the silicon wafer and the resin composition is as described above. In one embodiment, the compression molding process is carried out using a compression molding machine configured to include a pair of separable molds, and the silicon wafer is placed on the surface of the mold located vertically downward. Other embodiments are as described above.

[0029] As the release film used in process (c1), a commercially available product that has not been embossed or otherwise processed, specifically a commercially available product with a mirror finish, can be used from the viewpoint of obtaining a cured resin composition with a uniform thickness of 300 μm. An example of such a commercially available product is AGC's "Aflex® 50N 390NT" (mirror finish).

[0030] In step (c2), the mold is closed within 90 seconds after the resin composition is placed to bond the silicon wafer and the resin composition. The start of mold closing refers to the point at which the distance between the pair of molds narrows when performing the compression molding process using a compression molding machine configured to include a pair of separable molds.

[0031] In step (c3), the degree of reduced pressure refers to the vacuum level that should be achieved as a result of the reduced pressure. The degree of reduced pressure is preferably in the range of 0 to 0.7 torr, and in one embodiment, it is 0.2 torr.

[0032] Step (c4) is the same as the one described in the compression molding step above, so we will omit its explanation.

[0033] The standardized compression molding process is not limited to the above steps (c1) to (c4) in this order, but typically, the compression molding process described in the later-described examples can be adopted as the standardized compression molding process.

[0034] <Post-cure process> In the post-curing process, the compressed molded body of the obtained resin composition is heated under a nitrogen atmosphere at a temperature of 150°C for 1 hour to obtain a cured product.

[0035] From the perspective of accurately evaluating and defining the porosity, the post-curing process consists of the following steps (p1) to (p2): (p1) A step of obtaining a cured product by placing a compressed molded body of the resin composition removed from the mold into an oven set to 150°C and 1 atmosphere under a nitrogen atmosphere and waiting for 1 hour; and, (p2) Remove the cured material from the oven within 120 seconds after step (p1) and allow it to cool at room temperature and pressure. It is particularly preferable to include these steps in this order. A post-cure process that includes steps (p1) and (p2) in this order is also called a "standardized post-cure process".

[0036] Regarding the standardization post-curing process, it is preferable to set the oven to a predetermined nitrogen atmosphere, temperature of 150°C, and atmospheric pressure prior to process (p1), so that the compressed molded body of the resin composition can be quickly placed into the oven in process (p1). Furthermore, the silicon wafer may remain attached to the compressed molded body of the resin composition when it is placed into the oven.

[0037] In step (p2), the cured product should be removed from the oven promptly to avoid continued unintended heating in step (p1). For this purpose, the specified 120 seconds is preferably 110 seconds or less, and more preferably 100 seconds or less. The cured product removed from the oven may be allowed to cool in a normal temperature and pressure environment, for example, an environment with a pressure of 1 atmosphere ± 1 atmosphere and a temperature of 23°C ± 5°C, preferably a pressure of 1 atmosphere ± 0.5 atmospheres and a temperature of 23°C ± 5°C. The humidity in such an environment is preferably 40-60%, for example 50%. In this step, it is preferable to confirm that the surface temperature of the cured product has reached 23°C, but it may be considered to have reached room temperature after a predetermined time (for example 6 hours).

[0038] The cured product (resin composition layer) obtained through step (p2) preferably has a thickness of less than ±5% of its thickness before post-curing, and more preferably within the range of 300 μm ± 5 μm. Furthermore, it is preferable to carry out the post-curing process such that the degree of curing of the cured product (resin composition layer) is measured by differential scanning calorimetry using a differential scanning calorimetry device (DSC7020 manufactured by Hitachi High-Tech Science Corporation) to be 95% or higher, more preferably 96% or higher.

[0039] The standardized post-curing process is not limited to the above steps (p1) to (p2) in this order, but typically, the post-curing process described in the examples below can be adopted as the standardized post-curing process.

[0040] For the cured material to be evaluated for porosity, it is preferable to carry out the aforementioned compression molding process and post-curing process so that the degree of curing is 95% or higher, and more preferably so that it is 96% or higher. The degree of curing can be measured by differential scanning calorimetry using a differential scanning calorimetry device (DSC7020, manufactured by Hitachi High-Tech Science Corporation).

[0041] The resin composition of the present invention exhibits a porosity in the range of 0.002% to 2% in its cured product. As a result, the resin composition of the present invention can produce a cured product that suppresses warping and has excellent mechanical properties. Furthermore, the resin composition of the present invention that exhibits a porosity in the range of 0.002% to 2% after curing tends to produce a cured product with excellent dielectric properties.

[0042] From the viewpoint of obtaining a cured product with more suppressed warping, the void ratio is preferably 0.002% or more, more preferably 0.0025% or more, and even more preferably 0.003% or more. From the viewpoint of obtaining a cured product with superior mechanical properties, the void ratio is preferably 2% or less, more preferably 1.95% or less, and even more preferably 1.9% or less.

[0043] It is also preferable to evaluate the following resin porosity in place of or together with the above porosity. The resin porosity represents the area ratio (%) of the void region in the resin component region to the observed region, obtained by excluding the void region within the region defined by the outer shape region of the inorganic filler (C) described below from the void region obtained as a void image by image analysis when obtaining the above porosity. Unless otherwise specified, the resin component refers to the non-volatile components in the resin composition other than the inorganic filler (C), and the resin component region refers to the region other than the inorganic filler region in the cured product of the resin composition. When the above compression molding process and post-cure process are carried out using a resin composition containing an inorganic filler that substantially does not contain voids, i.e., a solid inorganic filler, the above porosity and the above resin porosity can usually take the same value. In this case, the resin porosity is preferably in the range of 0.002% to 2%, similar to the above porosity.

[0044] When the aforementioned compression molding process and post-curing process are carried out using a resin composition containing an inorganic filler that contains voids (so-called hollow filler) as the inorganic filler, the resin porosity is usually smaller than the above porosity because the voids in the inorganic filler are not counted. In this case, the resin porosity is preferably in the range of 0.0025% to 1.95%, and more preferably in the range of 0.003% to 1.9%. However, from the viewpoint of improving the accuracy of porosity measurement, it is preferable not to use hollow filler as the inorganic filler. From this viewpoint, even when the resin composition contains hollow filler, its content is more preferably less than 0.005% by mass, even more preferably 0.003% by mass or less, and particularly preferably 0.001% by mass or less, when the non-volatile components of the resin composition are taken as 100% by mass.

[0045] [Composition of the resin composition] The resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler. The resin composition of the present invention may contain components other than (A), (B), and (C), such as (D) a curing accelerator, (E-1) a silane coupling agent, (E-2) a reactive component, (E-3) a non-reactive additive, other additives, and solvents, as long as the above-mentioned porosity range is satisfied after curing. Here, the presence or absence and degree of influence of each component constituting the resin composition on void generation differ, and the degree of influence on void generation increases or decreases depending on the combination of components. The following describes a suitable resin composition for satisfying the above-mentioned porosity range after curing, but the suitable types and suitable content ranges change depending on the combination of components. As long as the above-mentioned porosity range is satisfied after curing, the types (combinations thereof) and content of the components constituting the resin composition are not limited to the specific types and ranges shown below.

[0046] [(A) Epoxy resin] The resin composition of the present invention comprises (A) an epoxy resin. (A) refers to a resin having epoxy groups.

[0047] (A) Examples of epoxy resins 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; phenol novolac-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 having a butadiene structure; alicyclic epoxy resin; alicyclic epoxy resin having an ester skeleton; poly Examples include cyclic epoxy resins; spiro-ring-containing epoxy resins; cyclohexane-type epoxy resins; cyclohexanedimethanol-type epoxy resins; trimethylol-type epoxy resins; tetraphenylethane-type epoxy resins; epoxy resins containing condensed ring skeletons such as naphthylene ether-type epoxy resins, tert-butyl-catechol-type epoxy resins, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, and naphthol novolac-type epoxy resins; isocyanurate-type epoxy resins; epoxy resins containing alkylene oxy skeletons and butadiene skeletons; epoxy resins containing fluorene structures; and the like. (A) Epoxy resins may be used individually or in combination of two or more types.

[0048] (A) The epoxy resin may contain an aromatic structure from the viewpoint of obtaining a cured product with excellent heat resistance. An aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatics and aromatic heterocyclics. Examples of epoxy resins containing aromatic structures include 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, bisquilenol type epoxy resin, glycidylamine type epoxy resin having an aromatic structure, glycidyl ester type epoxy resin having an aromatic structure, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having an aromatic structure, epoxy resin having a butadiene structure having an aromatic structure, alicyclic epoxy resin having an aromatic structure, heterocyclic epoxy resin, spiro-ring containing epoxy resin having an aromatic structure, cyclohexanedimethanol type epoxy resin having an aromatic structure, naphthylene ether type epoxy resin, trimethylol type epoxy resin having an aromatic structure, and tetraphenylethane type epoxy resin having an aromatic structure.

[0049] Among epoxy resins containing aromatic structures, it is preferable to include an epoxy resin containing a condensed ring structure from the viewpoint of obtaining a cured product with excellent heat resistance. Examples of condensed rings in epoxy resins containing a condensed ring structure include naphthalene rings, anthracene rings, and phenanthrene rings, with naphthalene rings being particularly preferred. Therefore, it is preferable that the epoxy resin (A) contains a naphthalene-type epoxy resin containing a naphthalene ring structure. The amount of naphthalene-type epoxy resin relative to 100% by mass of the total amount of epoxy resin (A) is preferably 10% by mass or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

[0050] (A) The epoxy resin may contain a glycidylamine type epoxy resin from the viewpoint of improving the heat resistance and metal adhesion of the cured product.

[0051] (A) The epoxy resin may include an epoxy resin having a butadiene structure.

[0052] The resin composition preferably contains (A) an epoxy resin having two or more epoxy groups per molecule. The proportion of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the nonvolatile component of (A) epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0053] Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition of this embodiment may contain only (A-1) liquid epoxy resin, or only (A-2) solid epoxy resin, or a combination of liquid epoxy resin and solid epoxy resin, but it is preferable to contain at least liquid epoxy resin.

[0054] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0055] Preferred 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, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, epoxy resin having a butadiene structure, epoxy resin containing an alkylene oxy skeleton and a butadiene skeleton, epoxy resin containing a fluorene structure, and dicyclopentadiene type epoxy resin. Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, alicyclic epoxy resin having an ester skeleton, epoxy resin having a butadiene structure, epoxy resin containing an alkylene oxy skeleton and a butadiene skeleton, epoxy resin containing a fluorene structure, and dicyclopentadiene type epoxy resin are particularly preferred.

[0056] Specific examples of liquid epoxy resins include: DIC Corporation's "HP4032," "HP4032D," and "HP4032SS" (naphthalene-type epoxy resin); Mitsubishi Chemical Corporation's "828US," "828EL," "jER828EL," "825," and "Epicote 828EL" (bisphenol A-type epoxy resin); Mitsubishi Chemical Corporation's "jER807" and "1750" (bisphenol F-type epoxy resin); Mitsubishi Chemical Corporation's "jER152" (phenol novolac-type epoxy resin); Mitsubishi Chemical Corporation's "630," "630LSD," and "604" (glycidylamine-type epoxy resin); ADEKA Corporation's "ED-523T" (glycyrol-type epoxy resin); ADEKA Corporation's "EP-3950L" and "EP-3980S" (glycidylamine-type epoxy resin); and ADEKA Corporation's "EP-4088S" (dicyclopentadiene-type epoxy resin). Examples include: resins; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., Ltd.; "EX-991L" (alkylene oxy skeleton-containing epoxy resin) and "EX-992L" (polyether-containing epoxy resin) manufactured by Nagase ChemteX Co., Ltd.; "Celoxide 2021P" (alicyclic epoxy resin with an ester skeleton) manufactured by Daicel Corporation; "PB-3600" manufactured by Daicel Corporation; "JP-100" and "JP-200" (epoxy resins with a butadiene structure) manufactured by Nippon Soda Co., Ltd.; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; and "EG-280" (fluorene structure-containing epoxy resin) manufactured by Osaka Gas Chemical Co., Ltd.

[0057] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups per molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups per molecule is more preferred.

[0058] Preferred solid epoxy resins include bixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, and tetraphenylethane-type epoxy resin.

[0059] Specific examples of solid epoxy resins include DIC's "HP4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); DIC's "N-690" (cresol novolac-type epoxy resin); DIC's "N-695" (cresol novolac-type epoxy resin); and DIC's "HP-7200," "HP-7200HH," and "HP-7200H" (dicyclopentadiene-type epoxy resins). ;DIC Corporation's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd.'s "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC7000L" (naphthol novolac type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) Epoxy resins; "ESN475V" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol novolac-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation Examples include "YX7700" (xylene structure-containing novolac type epoxy resin) from [company name]; "PG-100" and "CG-500" from Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) from Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) from Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A type epoxy resin) from Mitsubishi Chemical Corporation; and "jER1031S" (tetraphenylethane type epoxy resin) from Mitsubishi Chemical Corporation.

[0060] (A) The amount of liquid epoxy resin (A-1) relative to 100% by mass of the total amount of epoxy resin is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and especially preferably 100% by mass.

[0061] (A) 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., and even more preferably 110 g / eq. to 1000 g / eq. The epoxy equivalent is the mass of the resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0062] (A) The weight-average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 200 to 3000, and even more preferably 400 to 1500. The weight-average molecular weight of the resin can be measured as a polystyrene equivalent by gel permeation chromatography (GPC).

[0063] The amount of epoxy resin (A) relative to 100% by mass of nonvolatile components in the resin composition is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, particularly preferably 1.5% by mass or more, preferably 45% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

[0064] The amount of (A) epoxy resin relative to 100% by mass of the resin components in the resin composition is not particularly limited, but is preferably 10% by mass or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, and particularly preferably 60% by mass or less. Unless otherwise specified, the resin components in the resin composition refer to the non-volatile components in the resin composition other than (C) inorganic fillers.

[0065] [(B) Hardener] The resin composition of the present invention contains (B) a curing agent. The (B) curing agent typically has the function of curing the resin composition by reacting with (A) epoxy resin. Examples of this (B) curing agent include active ester curing agents, phenolic curing agents, benzoxazine curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, and cyanate ester curing agents. In one embodiment, at least one selected from the group consisting of acid anhydride curing agents, amine curing agents, and phenolic curing agents is used as the (B) curing agent. When using an acid anhydride curing agent, an amine curing agent, or a phenolic curing agent, warping of the cured product can usually be suppressed. The curing agent may be used alone or in combination of two or more types. As the (B) curing agent, one or more selected from (B-1) liquid curing agents and (B-2) solid curing agents can be used, and it is preferable to use (B-1) liquid curing agents. In one embodiment, the (B) curing agent consists of (B-1) liquid curing agents. "Liquid hardening agent" refers to a hardening agent that is liquid at 20°C, and "solid hardening agent" refers to a hardening agent that is solid at 20°C.

[0066] Examples of acid anhydride-based curing agents include curing agents having one or more acid anhydride groups in one molecule, with curing agents having two or more acid anhydride groups in one molecule being preferred. Specific examples of acid anhydride-based curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexen-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride, and bensofenone. Examples of acid anhydrides include tetracarboxylic acid dianhydrides, biphenyltetracarboxylic acid dianhydrides, naphthalenetetracarboxylic acid dianhydrides, oxydiphthalic acid dianhydrides, 3,3'-4,4'-diphenylsulfonetetracarboxylic acid dianhydrides, 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 polymer-type acid anhydrides such as styrene-maleic acid resin copolymerized with styrene and maleic acid. Examples of commercially available acid anhydride-based curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" from Shin Nippon Rika Co., Ltd.; "YH-306" and "YH-307" from Mitsubishi Chemical Corporation; and "HN-2200" and "HN-5500" from Hitachi Chemical Co., Ltd.

[0067] Examples of amine-based curing agents include curing agents having one or more, preferably two or more, amino groups in one molecule. Specific examples include aliphatic amines, polyetheramines, alicyclic amines, and aromatic amines, with aromatic amines being preferred. The amine-based curing agent is preferably a primary amine or a secondary amine, with primary amines being more preferred. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 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, and 2,2-bis(3-amino-4-hydroxy Examples include bis(4-(4-aminophenoxy)phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 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, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. Amine-based curing agents may be commercially available products, such as "SEIKACURE-S" from Seika Corporation, "KAYABOND C-200S," "KAYABOND C-100," "KAYAHARD AA," "KAYAHARD AB," and "KAYAHARD AS" from Nippon Kayaku Co., Ltd., "Epicure W" from Mitsubishi Chemical Corporation, and "DTDA" from Sumitomo Seika Co., Ltd.

[0068] Examples of phenolic curing agents include those having one or more, preferably two or more, hydroxyl groups bonded to aromatic rings such as benzene rings and naphthalene rings per molecule. Among these, compounds having hydroxyl groups bonded to benzene rings are preferred. Furthermore, from the viewpoint of heat resistance and water resistance, phenolic curing agents having a novolac structure are preferred. Moreover, from the viewpoint of adhesion, nitrogen-containing phenolic curing agents are preferred, and triazine skeleton-containing phenolic curing agents are more preferred. In particular, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, triazine skeleton-containing phenol novolac curing agents are preferred.

[0069] Specific examples of phenolic curing agents include "MEH-7700," "MEH-7810," "MEH-7851," and "MEH-8000H" from Meiwa Kasei Co., Ltd.; "NHN," "CBN," and "GPH" from Nippon Kayaku Co., Ltd.; "TD-2090," "TD-2090-60M," "LA-7052," "LA-7054," "LA-1356," "LA-3018," "LA-3018-50P," "EXB-9500," "HPC-9500," "KA-1160," "KA-1163," and "KA-1165" from DIC Corporation; "GDP-6115L," "GDP-6115H," and "ELPC75" from Gun-ei Chemical Co., Ltd.; and "2,2-diallylbisphenol A" from Sigma-Aldrich Corporation.

[0070] (B) The active group equivalent of the curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., even more preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The active group equivalent represents the mass of the curing agent per equivalent of one active group.

[0071] (B) The amount of curing agent is preferably determined according to the number of active groups of the (A) epoxy resin. For example, the number of active groups of the (B) curing agent is preferably 0.1 or more, more preferably 0.3 or more, even more preferably 0.5 or more, preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.0 or less, when the number of epoxy groups of the (A) epoxy resin is set to 1. Here, "(A) number of epoxy groups" refers to the sum of all values ​​obtained by dividing the mass of the nonvolatile components of the (A) epoxy resin present in the resin composition by the epoxy equivalent. Also, "(B) number of active groups" refers to the sum of all values ​​obtained by dividing the mass of the nonvolatile components of the (B) curing agent present in the resin composition by the active group equivalent.

[0072] The amount of (B) curing agent relative to 100% by mass of nonvolatile components in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 1.0% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0073] [(C) Inorganic filler] The resin composition of the present invention contains (C) an inorganic filler. The cured product of the resin composition containing (C) an inorganic filler can usually have a low coefficient of thermal expansion.

[0074] Inorganic compounds are used as inorganic fillers. Examples of inorganic fillers 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. Spherical silica is preferred as silica. (C) Inorganic fillers may be used individually or in combination of two or more types.

[0075] (C) As the inorganic filler, one or more types selected from solid inorganic fillers and hollow inorganic fillers can be used. "Solid inorganic filler" means an inorganic filler that does not substantially have voids or cavities, and "hollow inorganic filler" means an inorganic filler that contains voids or cavities. In one embodiment, (C) the inorganic filler consists of a solid inorganic filler.

[0076] (B) 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, preferably 5 μm or less, more preferably 4.5 μm or less, and even more preferably 4.1 μm or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

[0077] The average particle size of component (C) can be measured by a laser diffraction-scattering method based on Mie scattering theory. Specifically, a volume-based particle size distribution of the inorganic filler can be created using a laser diffraction-scattering particle size distribution analyzer, and the median diameter can be used as the average particle size. A sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them using ultrasound for 10 minutes. The sample can be measured using a laser diffraction-type particle size distribution analyzer with blue and red light source wavelengths, using a flow cell method to measure the volume-based particle size distribution of the inorganic filler (C), and the average particle size can be calculated as the median diameter from the obtained particle size distribution. An example of a laser diffraction-type particle size distribution analyzer is the "LA-960" manufactured by Horiba, Ltd.

[0078] (C) The specific surface area of ​​the inorganic filler is preferably 1 m². 2 / g or more, more preferably 1.5m 2 / g or more, more preferably 2m 2 / g or more, particularly preferably 3m 2 It must be 1 / g or more. There is no particular upper limit, but preferably 60m 2 / g or less, 50m 2 / g or less or 40m 2 The value is less than or equal to / g. The specific surface area is obtained by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mountec Co., Ltd.) according to the BET method, and then calculating the specific surface area using the BET multipoint method.

[0079] (C) Examples of commercially available inorganic fillers include "SP60-05", "SP507-05", and "ST7010-2" from Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" from Admatex Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" from Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "SO-C5", "SO-C6", "FE9 series", "FEB series", and "FED series" from Admatex Co., Ltd.; and "DAW-03", "DAW-10", "FB-105FD", and "UFP-30" from Denka Co., Ltd. Commercial products may be used after being crushed, mixed, classified, or a combination thereof to adjust to an appropriate particle size distribution as described above.

[0080] (C) The inorganic filler may be treated with a surface treatment agent to enhance moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. Furthermore, the surface treatment agent may be used alone or in any combination of two or more types.

[0081] Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

[0082] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent is preferably within a specific range. 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 the surface treatment agent, more preferably surface-treated with 0.2 parts by mass to 3 parts by mass of the surface treatment agent, and still more preferably surface-treated with 0.3 parts by mass to 2 parts by mass of the surface treatment agent.

[0083] 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. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is 0.02 mg / m 2 or more is preferable, and 0.1 mg / m 2 or more is more preferable, and 0.2 mg / m 2 or more is even more preferable. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition, 1 mg / m 2 or less is preferable, and 0.8 mg / m 2 or less is more preferable, and 0.5 mg / m 2 or less is even more preferable.

[0084] The amount of carbon per unit surface area of ​​an inorganic filler can be measured after surface treatment of the inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solids, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. A carbon analyzer such as the "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0085] The amount of (C) inorganic filler relative to 100% by mass of nonvolatile components in the resin composition is not particularly limited, but from the viewpoint of increasing the porosity in the resin component region of the cured product, it is 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably more than 50% by mass, and may be 70% by mass or more, 75% by mass or more, or 76% by mass or more. The amount of (C) inorganic filler is not particularly limited, but it may be 96% by mass or less, 95% by mass or less, 94% by mass or less, or 93% by mass or less relative to 100% by mass of nonvolatile components in the resin composition. A cured product of a resin composition containing an amount of (C) inorganic filler in this range can effectively reduce the coefficient of thermal expansion.

[0086] [(D) Curing accelerator] The resin composition of the present invention may further contain (D) a curing accelerator as an optional component. The curing accelerator (D) allows for efficient adjustment of the curing time of the resin composition.

[0087] (D) Examples of curing accelerators include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among these, imidazole-based curing accelerators are preferred. One type of curing accelerator may be used alone, or two or more types may be used in combination.

[0088] Examples of phosphorus-based curing accelerators include riphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

[0089] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, 1,8-diazabicyclo[5,4,0]undecene-7,4-dimethylaminopyridine, and 2,4,6-tris(dimethylaminomethyl)phenol, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

[0090] 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'-undecylimidazolyl-(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 isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-F Examples include imidazole compounds such as phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds with epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

[0091] Commercially available imidazole-based curing accelerators may be used, such as "P200-H50" from Mitsubishi Chemical Corporation, and "Curesol 2MZ", "2E4MZ", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", "Cl1Z-A", "2MZ-OK", "2MA-OK", "2MA-OK-PW", and "2PHZ" from Shikoku Chemicals, Inc.

[0092] Examples of guanidine-based curing accelerators 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]deca-5-ene, and 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene. Examples include ro[4.4.0]deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, and the like, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]deca-5-ene being preferred.

[0093] Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0094] The amount of (D) curing accelerator relative to 100% by mass of nonvolatile components in the resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.

[0095] [(E-1) Silane coupling agent] The resin composition of the present invention may further contain (E-1) a silane coupling agent as an optional component. However, when the silane coupling agent is used as a surface treatment agent for an inorganic filler, the inorganic filler treated with the surface treatment agent is classified as component (C) above. By including the silane coupling agent as component (E-1), bonding between the resin component and the inorganic filler can be expected.

[0096] Examples of silane coupling agents include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate coupling agents. Among these, epoxysilane coupling agents containing epoxy groups and mercaptosilane coupling agents containing mercapto groups are preferred, and epoxysilane coupling agents are particularly preferred. Furthermore, one type of silane coupling agent may be used alone, or two or more types may be used in combination. In one embodiment, the (E-1) component contains a single type of silane coupling agent. In other embodiments, the (E-1) component contains multiple types, for example, two types of silane coupling agents. The resin composition of the present invention preferably contains multiple types of silane coupling agents, and it is preferable that the silane coupling agent used as a surface treatment agent for component (C) and the silane coupling agent used as component (E-1) together contain multiple types of silane coupling agents.

[0097] As a silane coupling agent, commercially available products may be used, for example. Examples of commercially available silane coupling agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. Examples include "Hexamethyldisilazane", Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent), Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM503" (3-methacryloxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM5783", etc.

[0098] The amount of (E-1) silane coupling agent relative to 100% by mass of nonvolatile components in the resin composition is 0% by mass or more, 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more, or 10% by mass or less, 5% by mass or less, or 3% by mass or less.

[0099] The amount of (E-1) silane coupling agent in the resin composition is 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, or 0.2% by mass or more, or 15% by mass or less, 10% by mass or less, or 5% by mass or less, relative to 100% by mass of the resin component.

[0100] [(E-2) Reactive component] The resin composition of the present invention may further contain an optional reactive component (E-2). Components (A), (B), (D), and (E-1) are excluded from the (E-2) component. The (E-2) component has a reactive functional group and is expected to react with component (A) and / or with other (E-2) components. The reactive functional group may become reactive upon heating or light irradiation. By including the (E-2) component in the resin composition, the (E-2) component can be incorporated into the crosslinked structure composed of component (A). The (E-2) component may be used alone or in combination of two or more types.

[0101] Examples of reactive functional groups include -OH, -NH2, and -COOH. However, compounds containing an epoxy group as a reactive functional group are classified as component (A). Furthermore, the reactive functional group may also be a group having an ethylenically unsaturated bond. Examples of groups containing an ethylenically unsaturated bond include compounds having radical polymerizable groups such as vinyl group, allyl group, 1-butenyl group, 2-butenyl group, acryloyl group, methacryloyl group, fumaroyl group, maleoyl group, vinylphenyl group, styryl group, cinnamoyl group, and maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl group).

[0102] Examples of component (E-2) include (E-2-1) radical polymerizable compounds and (E-2-2) polyether skeleton-containing compounds having reactive functional groups.

[0103] [(E-2-1) Radical polymerizable compound] The resin composition of the present invention may further contain an (E-2-1) radical polymerizable compound as an optional component.

[0104] (E-2-1) As radical polymerizable compounds, compounds having an ethylenically unsaturated bond can be used. Examples of such (E-2-1) radical polymerizable compounds include compounds having radical polymerizable groups such as vinyl group, allyl group, 1-butenyl group, 2-butenyl group, acryloyl group, methacryloyl group, fumaroyl group, maleoyl group, vinylphenyl group, styryl group, cinnamoyl group, and maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl group). (E-2-1) radical polymerizable compounds may be used individually or in combination of two or more types.

[0105] (E-2-1) Specific examples of radical polymerizable compounds include (meth)acrylic radical polymerizable compounds having one or more acryloyl groups and / or methacryloyl groups; styrene radical polymerizable compounds having one or more vinyl groups directly bonded to aromatic carbon atoms; allyl radical polymerizable compounds having one or more allyl groups; maleimide radical polymerizable compounds having one or more maleimide groups; and so on. Among these, (meth)acrylic radical polymerizable compounds are preferred.

[0106] (E-2-1) radical polymerizable compounds preferably contain a polyalkylene oxide structure. By using (E-2-1) radical polymerizable compounds containing a polyalkylene oxide structure, the flexibility of the cured resin composition can be increased.

[0107] The polyalkylene oxide structure is given by formula (1):-(R f O) n - can be expressed as. In equation (1), n ​​usually represents an integer of 2 or more. This integer n is preferably 4 or more, more preferably 9 or more, even more preferably 11 or more, and usually 101 or less, preferably 90 or less, more preferably 68 or less, even more preferably 65 or less. In equation (1), R fEach of these independently represents an alkylene group which may have substituents. The number of carbon atoms in the alkylene group is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 5 or less, even more preferably 4 or less, even more preferably 3 or less, and particularly preferably 2. Examples of substituents that the alkylene group may have include halogen atoms, -OH, alkoxy groups, primary or secondary amino groups, aryl groups, -NH2, -CN, -COOH, -C(O)H, -NO2, etc. However, it is preferable that the alkyl group does not have substituents. Specific examples of polyalkylene oxide structures include polyethylene oxide structures, polypropylene oxide structures, poly-n-butylene oxide structures, poly(ethylene oxide-co-propylene oxide) structures, poly(ethylene oxide-ran-propylene oxide) structures, poly(ethylene oxide-alt-propylene oxide) structures, and poly(ethylene oxide-block-propylene oxide) structures.

[0108] (E-2-1) The number of polyalkylene oxide structures contained in one molecule of a radical polymerizable compound may be 1 or 2 or more. (E-2-1) The number of polyalkylene oxide structures contained in one molecule of a radical polymerizable compound is preferably 2 or more, more preferably 4 or more, even more preferably 9 or more, particularly preferably 11 or more, preferably 101 or less, more preferably 90 or less, even more preferably 68 or less, and particularly preferably 65 or less. (E-2-1) When a radical polymerizable compound contains 2 or more polyalkylene oxide structures in one molecule, these polyalkylene oxide structures may be the same or different from each other.

[0109] Examples of commercially available (E-2-1) radical polymerizable compounds containing a polyalkylene oxide structure include the monofunctional acrylates "AM-90G", "AM-130G", and "AMP-20GY" manufactured by Shin Nakamura Chemical Industry Co., Ltd.; the difunctional acrylates "A-1000", "A-B1206PE", "A-BPE-20", and "A-BPE-30"; the monofunctional methacrylates "M-20G", "M-40G", "M-90G", "M-130G", and "M-230G"; and the difunctional methacrylates "23G", "BPE-900", "BPE-1300N", and "1206PE". Other examples include "Light Ester BC," "Light Ester 041MA," "Light Acrylate EC-A," and "Light Acrylate EHDG-AT" from Kyoeisha Chemical Co., Ltd.; "FA-023M" from Hitachi Chemical Co., Ltd.; and "Bremmer® PME-4000," "Bremmer® 50POEO-800B," "Bremmer® PLE-200," "Bremmer® PLE-1300," "Bremmer® PSE-1300," "Bremmer® 43PAPE-600B," and "Bremmer® ANP-300" from NOF Corporation. In one embodiment, "M-130G" or "BPE-1300N" is used as the (E-2-1) radical polymerizable compound containing a polyalkylene oxide structure.

[0110] (E-2-1) The ethylenically unsaturated bond equivalent of the radical polymerizable compound is preferably 20 g / eq. to 3000 g / eq., more preferably 50 g / eq. to 2500 g / eq., even more preferably 70 g / eq. to 2000 g / eq., and particularly preferably 90 g / eq. to 1500 g / eq. The ethylenically unsaturated bond equivalent represents the mass of the radical polymerizable compound per ethylenically unsaturated bond equivalent.

[0111] (E-2-1) The weight-average molecular weight (Mw) of the radical polymerizable compound is preferably 150 or more, more preferably 250 or more, even more preferably 400 or more, preferably 40000 or less, more preferably 10000 or less, even more preferably 5000 or less, and particularly preferably 3000 or less.

[0112] With respect to 100% by mass of nonvolatile components in the resin composition, the amount of (E-2-1) radical polymerizable compound is 0% by mass or more, 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more, or 15% by mass or less, 10% by mass or less, or 8% by mass or less.

[0113] The amount of the (E-2-1) radical polymerizable compound in the resin composition is 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, or 0.2% by mass or more, or 25% by mass or less, 20% by mass or less, or 15% by mass or less, based on 100% by mass of the resin component.

[0114] [(E-2-2) Compounds containing a polyether skeleton with a reactive functional group] The resin composition of the present invention may further contain a polyether skeleton-containing compound having an (E-2-2) reactive functional group as an optional component. The polyether skeleton-containing compound having an (E-2-2) reactive functional group can suppress warping of the cured product of the resin composition. The polyether skeleton-containing compound having an (E-2-2) reactive functional group may be used alone or in combination of two or more types.

[0115] (E-2-2) Compounds containing a polyether skeleton having a reactive functional group represent polymer compounds having a polyether skeleton. These (E-2-2) compounds containing a polyether skeleton having a reactive functional group do not contain the components (A) to (E-2-1) described above. The polyether skeleton contained in the (E-2-2) compound containing a polyether skeleton having a reactive functional group is preferably a polyoxyalkylene skeleton composed of one or more monomer units selected from ethylene oxide units and propylene oxide units. Therefore, it is preferable that the (E-2-2) compound containing a polyether skeleton having a reactive functional group does not contain a polyether skeleton containing monomer units with 4 or more carbon atoms, such as butylene oxide units and phenylene oxide units. Furthermore, the (E-2-2) compound containing a polyether skeleton having a reactive functional group may contain a hydroxyl group as a reactive functional group.

[0116] (E-2-2) Compounds containing a polyether skeleton having a reactive functional group may also contain a silicone skeleton. Examples of silicone skeletons include polydialkylsiloxane skeletons such as polydimethylsiloxane skeletons; polydiarylsiloxane skeletons such as polydiphenylsiloxane skeletons; polyalkylarylsiloxane skeletons such as polymethylphenylsiloxane skeletons; polydialkyl-diarylsiloxane skeletons such as polydimethyl-diphenylsiloxane skeletons; polydialkyl-alkylarylsiloxane skeletons such as polydimethyl-methylphenylsiloxane skeletons; and polydiaryl-alkylarylsiloxane skeletons such as polydiphenyl-methylphenylsiloxane skeletons. Polydialkylsiloxane skeletons are preferred, and polydimethylsiloxane skeletons are particularly preferred. (E-2-2) Compounds containing a silicone skeleton, such as polyoxyalkylene-modified silicones, and alkyl etherified polyoxyalkylene-modified silicones (polyoxyalkylene-modified silicones in which at least a portion of the polyether skeleton terminals are alkoxy groups).

[0117] (E-2-2) Compounds containing a polyether skeleton having a reactive functional group may also contain a polyester skeleton. An aliphatic polyester skeleton is preferred. The hydrocarbon chains contained in the aliphatic polyester skeleton may be linear or branched, but branched is preferred. The number of carbon atoms in the polyester skeleton may be, for example, 4 to 16. Since the polyester skeleton may be formed from polycarboxylic acids, lactones, or their anhydrides, a (E-2-2) compound containing a polyether skeleton having a reactive functional group and containing a polyester skeleton may have a carboxyl group at the end of the molecule, but it is preferable that it has a hydroxyl group as a reactive functional group at the end of the molecule.

[0118] (E-2-2) Compounds containing a polyether skeleton having a reactive functional group include, for example, linear polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol; polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene glyceryl ether, polyoxyethylene trimethylolpropane ether, polyoxypropylene trimethylolpropane ether, polyoxyethylene polyoxypropylene trimethylolpropane ether, polyoxyethylene diglyceryl ether, polyoxypropylene diglyceryl ether, polyoxyethylene polyoxypropylene diglyceryl ether, polyoxyethylene topentaerythritol ether, polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene pentaerythritol ether, and polyoxyethylene sorbitol. Polyoxyalkylene glycols (polyalkylene glycols) such as polyoxypropylene sorbitol and polyoxyethylene polyoxypropylene sorbitol; polyoxyalkylene alkyl ethers such as polyoxyethylene monoalkyl ether, polyoxyethylene dialkyl ether, polyoxypropylene monoalkyl ether, polyoxypropylene dialkyl ether, polyoxyethylene polyoxypropylene monoalkyl ether, and polyoxyethylene polyoxypropylene dialkyl ether; polyoxyalkylene esters (including acetate ester, propionic acid ester, butyrate ester, (meth)acrylic acid ester, etc.) such as polyoxyethylene monoester, polyoxyethylene diester, polypropylene glycol monoester, polypropylene glycol diester, polyoxyethylene polyoxypropylene monoester, and polyoxyethylene polyoxypropylene diester;Polyoxyalkylene alkyl ether esters such as polyoxyethylene monoester, polyoxyethylene diester, polyoxypropylene monoester, polyoxypropylene diester, polyoxyethylene polyoxypropylene monoester, polyoxyethylene polyoxypropylene diester, polyoxyethylene alkyl ether ester, polyoxyethylene alkyl ether ester, polyoxyethylene polyoxypropylene alkyl ether ester (including acetate ester, propionic acid ester, butyrate ester, (meth)acrylic acid ester, etc.); polyoxyalkylene alkylamines such as polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene polyoxypropylene alkylamine; polyoxyalkylene alkylamides such as polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene polyoxypropylene alkylamide; polyoxyethylene dimethicone, Examples include polyoxyalkylene-modified silicones such as polyoxypropylene dimethicone, polyoxyethylene polyoxypropylene dimethicone, polyoxyethylene polydimethylsiloxyalkyl dimethicone, polyoxypropylene polydimethylsiloxyalkyl dimethicone, and polyoxyethylene polyoxypropylene polydimethylsiloxyalkyl dimethicone; and alkyl etherified polyoxyalkylene-modified silicones (polyoxyalkylene-modified silicones in which at least part of the polyether skeleton ends are alkoxy groups), such as polyoxyethylene alkyl ether dimethicone, polyoxypropylene alkyl ether dimethicone, polyoxyethylene polyoxypropylene alkyl ether dimethicone, polyoxyethylene alkyl ether polydimethylsiloxyalkyl dimethicone, and polyoxyethylene polyoxypropylene alkyl ether polydimethylsiloxyalkyl dimethicone.

[0119] (E-2-2) The number-average molecular weight of the polyether skeleton-containing compound having reactive functional groups is preferably 500 to 40,000, more preferably 500 to 20,000, and even more preferably 500 to 10,000. (E-2-2) The weight-average molecular weight of the polyether skeleton-containing compound is preferably 500 to 40,000, more preferably 500 to 20,000, and even more preferably 500 to 10,000. The number-average molecular weight and weight-average molecular weight can be measured as polystyrene equivalent values ​​by gel permeation chromatography (GPC).

[0120] (E-2-2) The polyether skeleton-containing compound having a reactive functional group is preferably liquid at 25°C. (E-2-2) The viscosity of the polyether skeleton-containing compound having a reactive functional group at 25°C is preferably 100,000 mPa·s or less, more preferably 50,000 mPa·s or less, even more preferably 30,000 mPa·s or less, even more preferably 10,000 mPa·s or less, even more preferably 5,000 mPa·s or less, even more preferably 4,000 mPa·s or less, even more preferably 3,000 mPa·s or less, even more preferably 2,000 mPa·s or less, and particularly preferably 1,500 mPa·s or less. (E-2-2) The lower limit of the viscosity of the polyether skeleton-containing compound having a reactive functional group at 25°C is preferably 10 mPa·s or more, more preferably 20 mPa·s or more, even more preferably 30 mPa·s or more, even more preferably 40 mPa·s or more, and particularly preferably 50 mPa·s or more. Viscosity can be measured using a Type B viscometer and expressed as viscosity (mPa·s).

[0121] (E-2-2) Examples of commercially available polyether skeleton-containing compounds having reactive functional groups include, for example, NOF Corporation's "Pronon #102", "Pronon #104", "Pronon #201", "Pronon #202B", "Pronon #204", "Pronon #208", "Unilube 70DP-600B", and "Unilube 70DP-950B" (polyoxyethylene polyoxypropylene glycol); and ADEKA Corporation's "Pluronic® L-23", "Luronic L-31", "Pluronic L-44", "Pluronic L-61", "Adeka Pluronic L-62", "Pluronic L-64", "Pluronic L-71", "Pluronic L-72", "Pluronic L-101", "Pluronic L-121", "Pluronic P-84", "Pluronic P-85", "Pluronic P-103", "Pluronic F-68", "Pluronic F-88", "Pluronic F-108", "Pluronic "Nick 25R-1", "Pluronic 25R-2", "Pluronic 17R-2", "Pluronic 17R-3", "Pluronic 17R-4" (polyoxyethylene polyoxypropylene glycol); "KF-6011", "KF-6011P", "KF-6012", "KF-6013", "KF-6015", "KF-6016", "KF-6017", "KF-6017P", "KF-6043", "KF-6004" manufactured by Shin-Etsu Silicone Co., Ltd. Examples include "KF351A", "KF352A", "KF353", "KF354L", "KF355A", "KF615A", "KF945", "KF-640", "KF-642", "KF-643", "KF-644", "KF-6020", "KF-6204", "X22-4515", "KF-6028", "KF-6028P", "KF-6038", "KF-6048", and "KF-6025" (polyoxyalkylene-modified silicone). (E-2-2) As a polyether skeleton-containing compound having a reactive functional group, a polyether polyol synthesized by the <synthesis of reactive component e2e ("polyether polyol A")> described later, or a modified version thereof, may be used.

[0122] The amount of the polyether skeleton-containing compound having an (E-2-2) reactive functional group, relative to 100% by mass of the nonvolatile components in the resin composition, is 0% by mass or more, 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more, or 15% by mass or less, 10% by mass or less, or 8% by mass or less, or 15% by mass or less, 10% by mass or less, or 8% by mass or less.

[0123] The amount of the polyether skeleton-containing compound having an (E-2-2) reactive functional group, relative to 100% by mass of the resin component in the resin composition, is 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, or 0.2% by mass or more, or 25% by mass or less, 20% by mass or less, or 15% by mass or less.

[0124] [(E-3) Non-reactive additives] The resin composition of the present invention may further contain an optional component, (E-3), a non-reactive additive. Component (C), component (E-2), and any other additives described later are excluded from component (E-3). Unlike component (E-2), component (E-3) does not have reactive functional groups at its terminals or side chains, and is an additive component that is not typically expected to react with component (A) and / or with other components (E-2). However, it is permissible for component (E-3) to react with other components at sites other than its terminals or side chains. A typical example of component (E-3) is a high molecular weight component. High molecular weight components can function as plasticizers. Examples of commercially available components (E-3) include butadiene homopolymers "B-1000," "B-2000," and "B-3000" manufactured by Nippon Soda Co., Ltd. Component (E-3) may be used alone or in combination of two or more types.

[0125] The number-average molecular weight of component (E-3) is preferably 500 to 40,000, more preferably 500 to 20,000, and even more preferably 500 to 10,000. The weight-average molecular weight of component (E-3) is preferably 500 to 40,000, more preferably 500 to 20,000, and even more preferably 500 to 10,000. The number-average molecular weight and weight-average molecular weight can be measured as polystyrene equivalent values ​​by gel permeation chromatography (GPC).

[0126] Component (E-3) is liquid at 25°C, or the viscosity of component (E-3) at 45°C is preferably 100,000 mPa·s or less, more preferably 50,000 mPa·s or less, even more preferably 30,000 mPa·s or less, even more preferably 10,000 mPa·s or less, even more preferably 5,000 mPa·s or less, even more preferably 4,000 mPa·s or less, even more preferably 3,000 mPa·s or less, even more preferably 2,000 mPa·s or less, particularly preferably 1,500 mPa·s or less or 500 mPa or less. The lower limit of the viscosity at 25°C of the polyether skeleton-containing compound having a reactive functional group (E-2-2) is preferably 0.5 mPa·s or more, more preferably 1 mPa·s or more, even more preferably 2 mPa·s or more, even more preferably 3 mPa·s or more, particularly preferably 4 mPa·s or more. The viscosity may be the viscosity (mPa·s) obtained by measuring with a B-type viscometer.

[0127] The amount of component (E-3) relative to 100% by mass of nonvolatile components in the resin composition is not limited as long as the porosity of the cured resin composition is within the range described above, but is 0% by mass or more, 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more, 15% by mass or less, 10% by mass or less, or 8% by mass or less, 15% by mass or less, 10% by mass or less, or 8% by mass or less, and is preferably 4% by mass or less from the viewpoint of obtaining a cured product with excellent mechanical strength.

[0128] The amount of component (E-3) relative to 100% by mass of the resin component in the resin composition is not limited as long as the porosity of the cured product of the resin composition is within the range described above, but is 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, or 0.2% by mass or more, and from the viewpoint of obtaining a cured product with excellent mechanical strength, is preferably 25% by mass or less, 20% by mass or less, or 15% by mass or less.

[0129] [(F) Radical polymerization initiator] The resin composition of the present invention may further contain (F) a radical polymerization initiator as an optional component. A thermal polymerization initiator that generates free radicals upon heating is preferred as the (F) radical polymerization initiator. When the resin composition contains an (E-2-1) radical polymerizable compound, it usually contains the (F) radical polymerization initiator. The (F) radical polymerization initiator may be used alone or in combination of two or more types.

[0130] (F) Examples of radical polymerization initiators include peroxide-based radical polymerization initiators and azo-based radical polymerization initiators. Among these, peroxide-based radical polymerization initiators are preferred.

[0131] Examples of peroxide-based radical polymerization initiators include hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; dialkylperoxide compounds such as tert-butylcumyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, dicumyl peroxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexine; dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, and bis(4-tert-butylcyclohexyl)peroxydicarbonate. Examples include diacyl peroxide compounds such as peroxides; peroxyester compounds such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxylaurate, (1,1-dimethylpropyl)2-ethyl perhexanoate, tert-butyl 2-ethyl perhexanoate, tert-butyl 3,5,5-trimethyl perhexanoate, tert-butyl peroxy-2-ethylhexyl monocarbonate, and tert-butyl peroxymaleic acid.

[0132] Examples of azo radical polymerization initiators include azonitrile compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitride), 1-[(1-cyano-1-methylethyl)azo]formamide, and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile; 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], and 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide]. Examples include azoamide compounds such as methyl)ethyl[propionamide], 2,2'-azobis[2-methyl-N-[2-(1-hydroxybutyl)]-propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(2-methylpropionamide) dihydrate, 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); and alkylazo compounds such as 2,2'-azobis(2,4,4-trimethylpentane) and 2,2'-azobis(2-methylpropane).

[0133] (F) The radical polymerization initiator is preferably one that has intermediate temperature activity. Specifically, the (F) radical polymerization initiator is preferably one whose 10-hour half-life temperature T10 (°C) is in a specific low temperature range. The 10-hour half-life temperature T10 is preferably 50°C to 110°C, more preferably 50°C to 100°C, and even more preferably 50°C to 80°C. Examples of commercially available (F) radical polymerization initiators include "Luperox 531M80" from Arkema Fuji, "Perhexyl® O" from NOF Corporation, and "MAIB" from Fujifilm Wako Pure Chemical Industries, Ltd.

[0134] The amount of (F) radical polymerization initiator relative to 100% by mass of nonvolatile components in the resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, particularly preferably 0.05% by mass or more, preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.

[0135] [(G) Other additives] In addition to the components (A) to (F) described above, the resin composition of the present invention may further contain any additives as optional non-volatile components. Examples of such additives include: organic fillers such as rubber particles, polyamide fine particles, and silicone particles; thermoplastic resins such as polycarbonate resin, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polysulfone resin, and polyester resin; organometallic compounds such as organocenium compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; and bentonite, montmorillonite, etc. Examples of additives include: thickeners; defoamers such as silicone-based defoamers, acrylic-based defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion fertilizers such as triazole-based adhesion fertilizers, tetrazole-based adhesion fertilizers, and triazine-based adhesion fertilizers; antioxidants such as hindered phenol-based antioxidants and hindered amine-based antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants; and flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide). Additives may be used individually or in combination of two or more in any ratio. In one embodiment, the resin composition includes a hollow organic filler as an organic filler. However, from the viewpoint of improving the accuracy of porosity measurement, it is preferable not to use hollow organic fillers as organic fillers. From this viewpoint, even when the resin composition contains hollow organic fillers, the content is more preferably less than 0.005% by mass, even more preferably 0.003% by mass or less, and particularly preferably 0.001% by mass or less, when the nonvolatile components of the resin composition are taken as 100% by mass.

[0136] [(H) Solvent] The resin composition of the present invention may further contain (H) any solvent as a volatile component. Examples of (H) solvents include organic solvents. The solvent may be used alone or in combination of two or more in any ratio. The amount of solvent is preferably small. The solvent content, when the non-volatile components of the resin composition are considered to be 100% by mass, is preferably 3% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less as a volatile component, and it is particularly preferable that there be no solvent (0% by mass).

[0137] [Method for producing resin compositions] The resin composition of the present invention can be produced, for example, by mixing the components described above. The components described above may be mixed some or all at the same time, or sequentially. The temperature may be set appropriately during the mixing of each component, and thus heating and / or cooling may be performed temporarily or throughout the process. Furthermore, stirring or shaking may be performed during the mixing of each component.

[0138] [Properties of resin compositions] Typically, the resin composition described above is thermosetting. Therefore, a cured product can be obtained by curing the resin composition with heat. The porosity (area %) of this cured product is, as previously mentioned, in the range of 0.002% to 2%, preferably in the range of 0.0025% to 1.95%, and more preferably in the range of 0.003% to 1.9%. This makes it possible to provide a resin composition or resin paste that suppresses warping and yields a cured product with excellent mechanical properties; a cured product formed using the resin composition or resin paste, a semiconductor chip package, and a semiconductor device.

[0139] The resin composition is preferably in paste form. Such a paste-like resin composition (hereinafter also referred to as "resin paste") can be easily molded using a compression mold. The viscosity of the paste-like resin composition at 25°C may be in the range of 1 Pa·s to 1000 Pa·s, preferably in the range of 20 Pa·s to 900 Pa·s, and more preferably in the range of 50 Pa·s to 800 Pa·s. The viscosity can be measured at 25°C using an E-type viscometer.

[0140] The resin composition of the present invention tends to have a low dielectric constant (Dk) value for its cured product. Specifically, the dielectric constant (Dk) value tends to be less than 3.6, preferably 3.5 or less, and more preferably less than 3.5. This makes it possible to provide a cured product with excellent dielectric properties. The lower limit of the dielectric constant (Dk) may be 1.0 or more, or 2.0 or more. The resin composition of the present invention tends to have a low dielectric loss tangent (Df) value for its cured product. Specifically, the dielectric loss tangent (Df) value tends to be less than 0.03, preferably less than 0.025, and more preferably less than 0.02, and may also be less than 0.01, less than 0.008, less than 0.006, or less than 0.005. This makes it possible to provide a cured product with excellent dielectric properties. The lower limit of the dielectric loss tangent (Df) may be 0.0001 or more. The resin composition of the present invention exhibits a tendency for the dielectric constant (Dk) of its cured product to be less than 3.6, preferably 3.5 or less, more preferably less than 3.5, and the dielectric loss tangent (Df) of the cured product to be less than 0.03, preferably less than 0.025, more preferably less than 0.02. This makes it possible to provide a cured product with excellent dielectric properties. The dielectric loss tangent and relative permittivity can be measured by the method described later. Test pieces for measuring the dielectric loss tangent and relative permittivity can be prepared according to the method and curing conditions described later.

[0141] The resin composition of the present invention tends to exhibit a cured product with a thickness of 300 μm that warps less than 2000 μm (2 mm), preferably 1950 μm or less, more preferably 1900 μm or less, and more preferably 1850 μm or less. The amount of warping can be measured by the method described in the Examples section below. Thus, the resin composition of the present invention can produce a cured product with suppressed warping. The amount of warping can be measured by the method described below. Test pieces for measuring the amount of warping can be prepared according to the method and curing conditions described below.

[0142] The resin composition of the present invention tends to have a cured product with a breaking strength of more than 45 MPa, preferably 50 MPa or more, and more preferably 55 MPa or more. Furthermore, the resin composition of the present invention tends to have a cured product with a breaking strength of less than 110 MPa, preferably 108 MPa or less, and more preferably 106 MPa or less. The breaking strength can be measured by the method described in the Examples section below. Thus, the resin composition of the present invention can produce a cured product with excellent mechanical strength. The breaking strength can be measured by the method described below. Test specimens for measuring the breaking strength can be prepared according to the method and curing conditions described below.

[0143] [Uses of resin compositions] The resin composition of the present invention can be suitably used as a resin composition for encapsulating electronic devices such as organic EL devices and semiconductors (a resin composition for encapsulation), and in particular, it can be suitably used as a resin composition for encapsulating semiconductors (a resin composition for semiconductor encapsulation), and preferably as a resin composition for encapsulating semiconductor chips (a resin composition for semiconductor chip encapsulation). Furthermore, the resin composition can be used as an insulating resin composition for insulating layers other than for encapsulation purposes. For example, the above-mentioned resin composition can be suitably used as a resin composition for forming an insulating layer of a semiconductor chip package, such as a redistribution layer (a resin composition for an insulating layer of a semiconductor chip package, a resin composition for a redistribution layer), and as a resin composition for forming an insulating layer of a circuit board (including a printed wiring board) (a resin composition for an insulating layer of a circuit board).

[0144] As described above, the resin composition of the present invention can be used as a material for forming a sealing layer or insulating layer of a semiconductor chip package. Examples of semiconductor chip packages include FC-CSP, MIS-BGA package, ETS-BGA package, fan-out type WLP (Wafer Level Package), fan-in type WLP, fan-out type PLP (Panel Level Package), and fan-in type PLP.

[0145] Furthermore, the aforementioned resin composition may also be used as an underfill material, for example, as a material for MUF (Molding Under Filling) used after connecting a semiconductor chip to a substrate.

[0146] Furthermore, the aforementioned resin composition can be used in a wide range of applications where resin compositions are used, such as sheet-like laminated materials like resin sheets and prepregs, solder resists, die bonding materials, hole-filling resins, and component-embedding resins.

[0147] [Resin sheet] A resin sheet according to one embodiment of the present invention comprises at least a support and a resin composition layer provided on the support, and optionally a protective film. The resin composition layer is a layer containing the resin composition of the present invention. The thickness of the resin composition layer and the thickness of the cured product layer obtained by curing the resin composition layer are arbitrary. The resin sheet can be manufactured, for example, by a known method, and the material used as the support can also be arbitrarily selected.

[0148] The applications of the resin sheet are the same as those of the resin composition of the present invention described above. Examples of applicable circuit board packages include FC-CSP, MIS-BGA packages, and ETS-BGA packages. Applicable semiconductor chip packages include, for example, fan-out type WLP, fan-in type WLP, fan-out type PLP, and fan-in type PLP. The resin sheet may also be used as the material for the MUF used after the semiconductor chip is connected to the substrate. Furthermore, the resin sheet can be used in a wide range of other applications where high insulation reliability is required.

[0149] [Circuit board] A circuit board according to one embodiment of the present invention may contain a cured product of the resin composition of the present invention. The circuit board can be manufactured, for example, by known methods, and the materials used as the substrate and the conductive layer which may be formed on the substrate can be arbitrarily selected.

[0150] In manufacturing a circuit board, after preparing a substrate, a resin composition layer, for example, a resin composition layer containing the resin composition of the present invention, is formed on the substrate by, for example, a known method. For example, the resin composition layer can be formed by compression molding. In compression molding, the substrate and the resin composition are usually placed in a mold, and pressure and, if necessary, heat are applied to the resin composition within the mold to form a resin composition layer on the substrate.

[0151] The specific operation of the compression molding method can be carried out as follows: An upper mold and a lower mold are prepared as molds for compression molding. A resin composition is applied to the substrate. The substrate coated with the resin composition is attached to the lower mold. Then, the upper and lower molds are clamped together, and heat and pressure are applied to the resin composition to perform compression molding.

[0152] Furthermore, the specific operation of the compression molding method may be as follows, for example: An upper mold and a lower mold are prepared as molds for compression molding. The resin composition is placed on the lower mold. A base material and, if necessary, a release film are attached to the upper mold. Then, the upper and lower molds are clamped together so that the resin composition on the lower mold is in contact with the base material attached to the upper mold, and heat and pressure are applied to perform compression molding.

[0153] The molding conditions vary depending on the composition of the resin composition of the present invention, and appropriate conditions can be adopted to achieve good sealing. For example, the mold temperature during molding is preferably 70°C or higher, more preferably 80°C or higher, particularly preferably 90°C or higher, and preferably 200°C or lower. The pressure applied during molding is preferably 1 MPa or higher, more preferably 3 MPa or higher, particularly preferably 5 MPa or higher, preferably 50 MPa or lower, more preferably 30 MPa or lower, and particularly preferably 20 MPa or lower. The curing time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 3 minutes or more, preferably 100 minutes or less, more preferably 90 minutes or less, and in one embodiment, it may be 60 minutes or less, 30 minutes or less, or 20 minutes or less. Normally, the mold is removed after the formation of the resin composition layer. The mold may be removed before or after the heat curing of the resin composition layer.

[0154] After forming a resin composition layer on a substrate, the resin composition layer is heat-cured (post-cured) to form a cured layer. The heat-curing conditions for the resin composition layer may vary depending on the type of resin composition, but the curing temperature is usually in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably in the range of 170°C to 200°C), and the curing time is in the range of 5 minutes to 120 minutes (preferably in the range of 10 minutes to 100 minutes, more preferably in the range of 15 minutes to 90 minutes).

[0155] Before thermal curing the resin composition layer, the resin composition layer may be subjected to a preheating treatment by heating it at a temperature lower than the curing temperature. For example, prior to thermal curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C or higher but less than 120°C (preferably 60°C or higher but 110°C or lower, more preferably 70°C or higher but 100°C or lower) for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

[0156] As described above, a circuit board having a cured layer formed from the cured resin composition of the present invention can be manufactured. Furthermore, the method for manufacturing the circuit board may include any additional steps.

[0157] [Semiconductor chip package] A semiconductor chip package according to one embodiment of the present invention includes a cured product of the resin composition of the present invention. Examples of such semiconductor chip packages include the following:

[0158] The semiconductor chip package according to the first example includes the circuit board described above and a semiconductor chip mounted on the circuit board. This semiconductor chip package can be manufactured by bonding the semiconductor chip to the circuit board.

[0159] The bonding conditions between the circuit board and the semiconductor chip can be any conditions that allow for conductive connection between the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board. For example, conditions used in flip-chip mounting of semiconductor chips can be adopted. Alternatively, for example, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.

[0160] An example of a bonding method is a method of crimping a semiconductor chip onto a circuit board. The crimping conditions are typically a crimping temperature in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and a crimping time in the range of 1 second to 60 seconds (preferably in the range of 5 seconds to 30 seconds).

[0161] Another example of a bonding method is to bond semiconductor chips to a circuit board by reflow soldering. The reflow conditions may be in the range of 120°C to 300°C.

[0162] After bonding the semiconductor chip to the circuit board, the semiconductor chip may be filled with a mold underfill material. The resin composition described above may be used as this mold underfill material.

[0163] A semiconductor chip package according to the second example includes a semiconductor chip and a cured product of the resin composition of the present invention that encapsulates the semiconductor chip. In such a semiconductor chip package, the cured product of the resin composition of the present invention typically functions as a encapsulation layer. An example of a semiconductor chip package according to the second example is a fan-out type WLP.

[0164] Figure 1 is a schematic cross-sectional view showing the configuration of a fan-out type WLP as an example of a semiconductor chip package according to this embodiment. The semiconductor chip package 100 as a fan-out type WLP includes, for example, a semiconductor chip 110; a sealing layer 120 formed to cover the periphery of the semiconductor chip 110; a redistribution formation layer 130 as an insulating layer, provided on the side of the semiconductor chip 110 opposite to the sealing layer 120; a redistribution layer 140 as a conductor layer; a solder resist layer 150; and bumps 160, as shown in Figure 1.

[0165] The manufacturing method for such semiconductor chip packages is (A) A step of laminating a temporary fixing film onto the substrate, (B) A step of temporarily fixing the semiconductor chip onto a temporary fixing film, (C) A process of forming a encapsulation layer on a semiconductor chip, (D) Steps to peel off the substrate and temporary fixing film from the semiconductor chip, (E) A step of forming a redistribution layer on the surface from which the semiconductor chip substrate and temporary fixing film have been peeled off. (F) A step of forming a redistribution layer as a conductor layer on a redistribution formation layer, and (G) A step of forming a solder resist layer on the redistribution layer, This includes the above-mentioned semiconductor chip package manufacturing method. (H) A process of dicing multiple semiconductor chip packages into individual semiconductor chip packages. It may include.

[0166] (Process (A)) Step (A) is a step of laminating a temporary fixing film onto the substrate. The lamination conditions between the substrate and the temporary fixing film may be the same as those for lamination between the substrate and the resin sheet in the manufacturing method of a circuit board.

[0167] Examples of substrates include silicon wafers, glass wafers, glass substrates, metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC), substrates such as FR-4 substrates which are made by impregnating glass fibers with epoxy resin and then heat-curing them, and substrates made of bismaleimide triazine resin such as BT resin.

[0168] The temporary fixing film can be made of any material that can be peeled off from the semiconductor chip and can temporarily fix the semiconductor chip. Examples of commercially available products include Nitto Denko's "Riva Alpha".

[0169] (Process (B)) Step (B) is a step of temporarily fixing the semiconductor chip onto a temporary fixing film. Temporary fixing of the semiconductor chip can be performed using equipment such as a flip-chip bonder or die bonder. The layout and number of semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the number of semiconductor chip packages to be produced, etc. For example, the semiconductor chips may be arranged in a matrix of multiple rows and multiple columns and then temporarily fixed.

[0170] (Process (C)) Step (C) is a step of forming a sealing layer on a semiconductor chip. The sealing layer can be formed by a cured product of the resin composition of the present invention. The sealing layer is usually formed by a method that includes the steps of forming a resin composition layer on a semiconductor chip and thermal curing this resin composition layer to form a cured product layer as a sealing layer. The formation of the resin composition layer on a semiconductor chip can be carried out in the same way as the method for forming a resin composition layer on a substrate described above in [Circuit Board], except that a semiconductor chip is used instead of a substrate.

[0171] After forming a resin composition layer on a semiconductor chip, this resin composition layer is thermally cured to obtain a sealing layer that covers the semiconductor chip. This seals the semiconductor chip with the cured resin composition of the present invention. The thermal curing conditions for the resin composition layer may be the same as those used in the manufacturing method of a circuit board. Furthermore, before thermal curing the resin composition layer, a preheating treatment may be performed on the resin composition layer, which is heated at a temperature lower than the curing temperature. The processing conditions for this preheating treatment may be the same as those used in the manufacturing method of a circuit board.

[0172] (Process (D)) Step (D) is a step of peeling the substrate and temporary fixing film from the semiconductor chip. It is desirable to adopt an appropriate peeling method depending on the material of the temporary fixing film. Examples of peeling methods include peeling by heating, foaming, or expanding the temporary fixing film. Another example of a peeling method is peeling by irradiating the temporary fixing film with ultraviolet light through the substrate to reduce the adhesive strength of the temporary fixing film and then peeling it off.

[0173] In the method of peeling off a temporary fixing film by heating, foaming, or expanding it, the heating conditions are typically 100°C to 250°C for 1 to 90 seconds or 5 to 15 minutes. In the method of peeling off a temporary fixing film by reducing its adhesive strength through ultraviolet irradiation, the ultraviolet irradiation dose is typically 10 mJ / cm². 2 ~1000 mJ / cm 2 That is the case.

[0174] As described above, when the substrate and temporary fixing film are peeled off from the semiconductor chip, the surface of the sealing layer is exposed. The method for manufacturing the semiconductor chip package may include polishing this exposed surface of the sealing layer. Polishing can improve the smoothness of the surface of the sealing layer. The same polishing method as described in the method for manufacturing the circuit board can be used.

[0175] (Process (E)) Step (E) is a step of forming a redistribution-forming layer as an insulating layer on the surface from which the substrate and temporary fixing film of the semiconductor chip have been peeled off. Typically, this redistribution-forming layer is formed on the semiconductor chip and the encapsulation layer.

[0176] Any insulating material can be used for the rewiring layer. When a sealing layer is formed using a cured product of the resin composition of the present invention, the rewiring layer formed on this sealing layer may be formed using a photosensitive resin composition.

[0177] After forming the redistribution layer, via holes are typically formed in the redistribution layer to connect the semiconductor chip and the redistribution layer. When the redistribution layer is formed of a photosensitive resin composition, the method for forming via holes typically involves exposing the surface of the redistribution layer through a mask. Examples of active energy rays include ultraviolet light, visible light, electron beams, and X-rays, with ultraviolet light being particularly preferred. Examples of exposure methods include contact exposure, in which a mask is brought into close contact with the redistribution layer for exposure, and non-contact exposure, in which a parallel light beam is used for exposure without bringing the mask into close contact with the redistribution layer.

[0178] As a result of the aforementioned exposure, a latent image may be formed in the rewiring layer. Subsequently, by developing the film, a portion of the rewiring layer can be removed, forming a via hole as an opening that penetrates the rewiring layer. Development can be performed using either wet or dry development. Examples of development methods include the dip method, paddle method, spray method, brushing method, and scraping method, with the paddle method being preferred from the viewpoint of resolution.

[0179] The shape of the via hole is not particularly limited, but is generally circular (or nearly circular). The top diameter of the via hole is, for example, 50 μm or less, 30 μm or less, 20 μm or less, or 10 μm or less. Here, the top diameter of the via hole refers to the diameter of the via hole opening on the surface of the redistribution formation layer.

[0180] (Process (F)) Step (F) is the step of forming a redistribution layer as a conductor layer on the redistribution formation layer. The method of forming the redistribution layer on the redistribution formation layer may be the same as the method of forming a conductor layer on a cured material layer in the manufacturing method of a circuit board. Alternatively, steps (E) and (F) may be repeated to alternately stack the redistribution layer and the redistribution formation layer (build-up).

[0181] (Process (G)) Step (G) is the step of forming a solder resist layer on the redistribution layer. Any insulating material can be used for the solder resist layer. Among these, photosensitive resins and thermosetting resins are preferred from the viewpoint of ease of manufacturing semiconductor chip packages. Furthermore, the resin composition of the present invention may be used as the thermosetting resin.

[0182] Furthermore, in step (G), bumping may be performed to form bumps as needed. Bumping can be performed by methods such as solder balls or solder plating. The formation of via holes in the bumping process can be done in the same way as in step (E).

[0183] (Process (H)) The method for manufacturing a semiconductor chip package may include step (H) in addition to steps (A) to (G). Step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to form individual pieces. The method of dicing the semiconductor chip packages into individual semiconductor chip packages is not particularly limited.

[0184] A third example of a semiconductor chip package is a semiconductor chip package 100, as shown in Figure 1, in which the redistribution layer 130 or solder resist layer 150 is formed from a cured product of the resin composition of the present invention.

[0185] [Semiconductor device] A semiconductor device comprises a semiconductor chip package. Examples of semiconductor devices include various types of semiconductor devices used in electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft, etc.). [Examples]

[0186] The present invention will be described in detail below with reference to examples. The present invention is not limited to these examples. In the following, "parts" and "%" refer to "parts by mass" and "mass%" respectively, unless otherwise specified. Unless otherwise specified, the temperature and pressure conditions are room temperature (25°C) and atmospheric pressure (1 atm).

[0187] [Example 1] (1) Preparation of resin paste A (B) Component: curing agent ba (acid anhydride-based curing agent "MH-700" manufactured by Shin Nippon Rika Co., Ltd., acid anhydride equivalent: 164 g / eq.) 8 parts, (A) Component: epoxy resin aa (liquid epoxy resin "ZX1059" manufactured by Nippon Steel Chemical & Material Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq.) 2 parts, (A) Component Epoxy resin ab (alicyclic epoxy resin "Celoxide 2021P" manufactured by Daicel Corporation, epoxy equivalent: 136 g / eq.) 2 parts, epoxy resin ac as component (A) (naphthalene-type epoxy resin "HP4032D" manufactured by DIC Corporation, epoxy equivalent: 143 g / eq.) 2 parts, curing accelerator da as component (D) (imidazole-based curing accelerator "2MA-OK-PW" manufactured by Shikoku Chemicals, Inc.) 0.4 parts, (A) component (A) Component: 2 parts epoxy resin ad (Glycidylamine type epoxy resin "EP3950L" manufactured by ADEKA, epoxy equivalent: 95 g / eq.), 2 parts epoxy resin ae (Dicyclopentadiene dimethanol type epoxy resin "EP-4088S" manufactured by ADEKA, epoxy equivalent: 170 g / eq.), 3 parts reactive component e2a (Compound "M-130G" manufactured by Shin Nakamura Chemical Industry Co., Ltd., having a methacryloyl group and polyethylene oxide structure), 0.1 parts radical polymerization initiator (Perhexyl® O manufactured by NOF Corporation, 10-hour half-life temperature T10: 69.9°C), 0.1 parts inorganic filler ca (Silica surface-treated with surface treatment agent "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., true density: 2.6 g / cm³) 3 , average particle size: 1.5μm, specific surface area: 2.78m 2 90 parts of (g; also called "Silica A") and 0.2 parts of the silane coupling agent e1a (Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane)) as component (E-1) were uniformly dispersed using a mixer to prepare a resin composition. The prepared resin composition was in paste form. Hereinafter, the resin composition prepared in this manner, which contains at least component (A), component (B), and component (C), will also be referred to as "Resin Paste A".

[0188] The amount of solvent contained in the prepared resin paste A of Example 1 was 0% by mass (i.e., no solvent) relative to 100% by mass of the non-volatile components of the resin composition. Furthermore, the viscosity of resin paste A of Example 1 was measured at 25°C using an E-type viscometer and was found to be 80 Pa·s. The viscosity measured in this manner is shown in Table 1.

[0189] (2) Measurement and evaluation of the cured product Then, using resin paste A, the cured product was subjected to the measurements and evaluations described later.

[0190] [Example 2] In Example 1, instead of blending 2 parts each of epoxy resin aa ("ZX1059"), epoxy resin ab ("Celoxide 2021P"), epoxy resin ac ("HP4032D"), epoxy resin ad ("EP3950L"), and epoxy resin ae ("EP-4088S") as component (A), 2 parts of epoxy resin aa ("ZX1059") ("Celoxide 2021P") and 2 parts of epoxy resin ac ("HP4032D") were used. Two parts of epoxy resin af (EX-992L, a polyether-containing epoxy resin manufactured by Nagase ChemteX Corporation, epoxy equivalent: 680 g / eq.), two parts of epoxy resin ag (EG-280, a fluorene structure-containing epoxy resin manufactured by Osaka Gas Chemical Co., Ltd., epoxy equivalent: 460 g / eq.), and two parts of epoxy resin ah (EP-3980S, a glycidylamine-type epoxy resin manufactured by ADEKA Corporation, epoxy equivalent: 115 g / eq.) were blended. Furthermore, in Example 1, the amount of curing accelerator da ("2MA-OK-PW") as component (D) was changed from 0.4 parts to 0.5 parts. Furthermore, in Example 1, instead of incorporating 3 parts of reactive component e2a ("M-130G") as component (E-2), 3 parts of reactive component e2b ("BPE-1300N", a bifunctional methacrylate manufactured by Shin Nakamura Chemical Industry Co., Ltd.) were incorporated.

[0191] Resin paste A was prepared in the same manner as in Example 1, except for the matters described above. The amount of solvent contained in the prepared resin paste A of Example 2 was 0% by mass (i.e., 0%) relative to 100% by mass of the non-volatile components of the resin composition. Then, the cured product of resin paste A was measured and evaluated in the same manner as in Example 1.

[0192] [Example 3] In Example 1, the amounts of epoxy resin aa ("ZX1059"), epoxy resin ab ("Celoxide 2021P"), epoxy resin ac ("HP4032D"), epoxy resin ad ("EP3950L"), and epoxy resin ae ("EP-4088S") as component (A) were changed from 2 parts each to 3 parts each. Furthermore, in Example 1, instead of incorporating 0.4 parts of curing agent ba ("MH-700") as component (B), 3 parts of curing agent bb (amine-based curing agent "Kayahard AA" (4,4'-diamino-3,3'-diethyldiphenylmethane) manufactured by Nippon Kayaku Co., Ltd.) were incorporated. Furthermore, in Example 1, instead of incorporating 0.4 parts of curing accelerator da ("2MA-OK-PW") as component (D), 0.4 parts of curing accelerator db (imidazole-based curing accelerator "2E4MZ" manufactured by Shikoku Chemicals Co., Ltd.) were incorporated.

[0193] Resin paste A was prepared in the same manner as in Example 1, except for the matters described above. The amount of solvent contained in the prepared resin paste A of Example 3 was 0% by mass (i.e., 0%) relative to 100% by mass of the non-volatile components of the resin composition. Then, the cured product of resin paste A was measured and evaluated in the same manner as in Example 1.

[0194] [Example 4] In Example 1, instead of blending 2 parts each of epoxy resin aa ("ZX1059"), epoxy resin ab ("Celoxide 2021P"), epoxy resin ac ("HP4032D"), epoxy resin ad ("EP3950L"), and epoxy resin ae ("EP-4088S") as component (A), 3 parts of epoxy resin aa ("ZX1059"), 2 parts of epoxy resin ac ("HP4032D"), and 1 part of epoxy resin ai (epoxidized polybutadiene resin "JP-100" manufactured by Nippon Soda Co., Ltd.) were blended. Furthermore, in Example 1, instead of incorporating 90 parts of inorganic filler ca ("Silica A") as component (C), inorganic filler cb (silica surface-treated with Shin-Etsu Chemical Co., Ltd.'s surface treatment agent "KBM573", true density: 2.6 g / cm³) was used. 3 , average particle size: 4μm, specific surface area: 3.01m 2 It contains 130 parts of silica (also known as "silica B"). Furthermore, in Example 1, the amount of silane coupling agent e1a ("KBM403") as component (E-1) was changed from 0.2 parts to 0.1 parts. Furthermore, components (E-2) and (F) used in Example 1 were not included.

[0195] Resin paste A was prepared in the same manner as in Example 1, except for the matters described above. The amount of solvent contained in the prepared resin paste A of Example 4 was 0% by mass (i.e., 0%) relative to 100% by mass of the non-volatile components of the resin composition. Then, the cured product of resin paste A was measured and evaluated in the same manner as in Example 1.

[0196] [Example 5] In Example 4, instead of using 3 parts epoxy resin aa ("ZX1059"), 2 parts epoxy resin ac ("HP4032D"), and 1 part epoxy resin ai ("JP-100") as component (A), 3 parts epoxy resin aa ("ZX1059"), 1 part epoxy resin ac ("HP4032D"), and 1 part epoxy resin ag ("EG-280") were used. Furthermore, in Example 4, instead of incorporating 0.1 parts of silane coupling agent e1a ("KBM403") as component (E-1), 0.1 parts of silane coupling agent e1a ("KBM403") and 0.1 parts of silane coupling agent e1b ("KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.) were incorporated. In other words, in Example 5, multiple types of silane coupling agents were incorporated. Furthermore, in Example 4, as component (E-2), the reactive component e2c (Shin-Etsu Silicone Co., Ltd.'s polyoxyalkylene-modified silicone resin "KF-6012", viscosity (25℃): 1500 mm) 2 One part of ( / s) was added. In addition, in Example 4, the amount of radical polymerization initiator as component (F) was changed from 0.1 parts to 0 parts. That is, in Example 5, component (F) was not added.

[0197] Resin paste A was prepared in the same manner as in Example 4, except for the matters described above. The amount of solvent contained in the prepared resin paste A of Example 5 was 0% by mass (i.e., 0%) relative to 100% by mass of the non-volatile components of the resin composition. Then, the cured product of resin paste A was measured and evaluated in the same manner as in Example 1.

[0198] [Example 6] In Example 5, instead of incorporating one part of reactive component e2c ("KF-6012") as component (E-2), one part of reactive component e2d ("L-64" polyoxyethylene polyoxypropylene glycol manufactured by ADEKA Corporation) was incorporated.

[0199] Resin paste A was prepared in the same manner as in Example 5, except for the matters described above. The amount of solvent contained in the prepared resin paste A of Example 6 was 0% by mass (i.e., 0%) relative to 100% by mass of the non-volatile components of the resin composition. Then, the cured product of resin paste A was measured and evaluated in the same manner as in Example 1.

[0200] [Example 7] In Example 5, instead of using 3 parts epoxy resin aa ("ZX1059"), 1 part epoxy resin ac ("HP4032D"), and 1 part epoxy resin ag ("EG-280") as component (A), 3 parts epoxy resin aa ("ZX1059"), 1 part epoxy resin ac ("HP4032D"), and 1 part epoxy resin ad ("EP3950L") were used. Furthermore, in Example 5, instead of incorporating one part of reactive component e2c ("KF-6012") as component (E-2), one part of reactive component e2e (also known as "polyether polyol A") was incorporated. Reactive component e2e was obtained by synthesis as described below.

[0201] <Synthesis of reactive component e2e ("polyether polyol A")> In a reaction vessel, 22.6 g of ε-caprolactone monomer (Daicel Corporation's "Praxel M"), 10 g of polypropylene glycol (Fujifilm Wako Pure Chemical Industries' "Polypropylene Glycol, Diol Type, 3,000"), and 1.62 g of 2-tin(II) ethylhexanoate (Fujifilm Wako Pure Chemical Industries) were charged. The mixture was heated to 130°C under a nitrogen atmosphere and stirred for approximately 16 hours to allow the reaction to proceed. The reaction product was dissolved in chloroform, reprecipitated with methanol, and then dried. This yielded a polyester polyol with an aliphatic skeleton and hydroxyl group terminus as the reactive component e2e ("Polyether Polyol A"). GPC analysis revealed that the reactive component e2e ("Polyether Polyol A") had a manganese content of 9000.

[0202] Resin paste A was prepared in the same manner as in Example 5, except for the matters described above. The amount of solvent contained in the prepared resin paste A of Example 7 was 0% by mass (i.e., 0%) relative to 100% by mass of the non-volatile components of the resin composition. Then, the cured product of resin paste A was measured and evaluated in the same manner as in Example 1.

[0203] [Example 8] In Example 3, instead of blending 3 parts each of epoxy resin aa ("ZX1059"), epoxy resin ab ("Celoxide 2021P"), epoxy resin ac ("HP4032D"), epoxy resin ad ("EP3950L"), and epoxy resin ae ("EP-4088S") as component (A), 3 parts of epoxy resin aa ("ZX1059"), 3 parts of epoxy resin ab ("Celoxide 2021P"), 3 parts of epoxy resin ac ("HP4032D"), 2 parts of epoxy resin ad ("EP3950L"), and 1 part of epoxy resin ae ("EP-4088S") were blended. Furthermore, in Example 3, instead of incorporating 90 parts of inorganic filler ca ("silica A") as component (C), 130 parts of inorganic filler cb ("silica B") were incorporated. Furthermore, in Example 3, the amount of silane coupling agent e1a ("KBM403") as component (E-1) was changed from 0.2 parts to 0.3 parts. Furthermore, in Example 3, instead of incorporating 3 parts of reactive component e2a ("M-130G") as component (E-2), 2 parts of reactive component e2e ("Polyether Polyol A") were incorporated, and the amount of radical polymerization initiator as component (F) was changed from 0.1 parts to 0 parts. In other words, in Example 8, component (F) was not incorporated.

[0204] Resin paste A was prepared in the same manner as in Example 3, except for the matters described above. The amount of solvent contained in the prepared resin paste A of Example 8 was 0% by mass (i.e., 0%) relative to 100% by mass of the non-volatile components of the resin composition. Then, the cured product of resin paste A was measured and evaluated in the same manner as in Example 1.

[0205] [Example 9] In Example 8, instead of blending 3 parts each of epoxy resin aa ("ZX1059"), epoxy resin ab ("Celoxide 2021P"), epoxy resin ac ("HP4032D"), epoxy resin ad ("EP3950L"), and epoxy resin ae ("EP-4088S") as component (A), 3 parts of epoxy resin aa ("ZX1059"), 3 parts of epoxy resin ab ("Celoxide 2021P"), 3 parts of epoxy resin ac ("HP4032D"), 2 parts of epoxy resin ad ("EP3950L"), and 1 part of epoxy resin af ("EX-992L") were blended. Furthermore, in Example 8, instead of incorporating 3 parts of curing agent bb ("Kaya Hard AA") as component (B), 3 parts of curing agent bc ("2,2-diallylbisphenol A" manufactured by Sigma-Aldrich) were incorporated. Furthermore, in Example 8, the amount of the inorganic filler cb ("Silica B") as component (C) was changed from 130 parts to 100 parts. Furthermore, in Example 8, instead of incorporating 2 parts of reactive component e2e ("Polyether Polyol A") as component (E-2), 2 parts of reactive component e2c ("KF-6012") were incorporated.

[0206] Resin paste A was prepared in the same manner as in Example 8, except for the matters described above. The amount of solvent contained in the prepared resin paste A of Example 9 was 0% by mass (i.e., 0%) relative to 100% by mass of the non-volatile components of the resin composition. Then, the cured product of resin paste A was measured and evaluated in the same manner as in Example 1.

[0207] [Example 10] In Example 4, instead of using 3 parts epoxy resin aa ("ZX1059"), 2 parts epoxy resin ac ("HP4032D"), and 1 part epoxy resin ai ("JP-100") as component (A), 3 parts epoxy resin aa ("ZX1059") and 2 parts epoxy resin ac ("HP4032D") were used. Furthermore, in Example 4, the amount of the inorganic filler cb ("Silica B") as component (C) was changed from 130 parts to 100 parts. Furthermore, in Example 4, a portion of the reactive component e2f (BMI-689 manufactured by Designer Molecules) was added as component (E-2).

[0208] Resin paste A was prepared in the same manner as in Example 4, except for the matters described above. The amount of solvent contained in the prepared resin paste A of Example 10 was 0% by mass (i.e., 0%) relative to 100% by mass of the non-volatile components of the resin composition. Then, the cured product of resin paste A was measured and evaluated in the same manner as in Example 1.

[0209] [Comparative Example 1] In Example 4, instead of using 3 parts epoxy resin aa ("ZX1059"), 2 parts epoxy resin ac ("HP4032D"), and 1 part epoxy resin ai ("JP-100") as component (A), 3 parts epoxy resin aa ("ZX1059"), 1 part epoxy resin ac ("HP4032D"), and 2 parts epoxy resin ad ("EP3950L") were used. Furthermore, in Example 4, the amount of silane coupling agent e1a ("KBM403") as component (E-1) was changed from 0.1 parts to 0 parts (i.e., not included). In other words, in Comparative Example 1, component (E-1) was not used.

[0210] Resin paste A was prepared in the same manner as in Example 4, except for the matters described above. The amount of solvent contained in the prepared resin paste A of Comparative Example 1 was 0% by mass (i.e., 0%) relative to 100% by mass of the non-volatile components of the resin composition. Then, the cured product of resin paste A was measured and evaluated in the same manner as in Example 1.

[0211] [Comparative Example 2] In Comparative Example 1, a non-reactive additive e3a (butadiene homopolymer "B-2000" manufactured by Nippon Soda Co., Ltd.) was further used as component (E-3).

[0212] Resin paste A was prepared in the same manner as in Comparative Example 1, except for the matters described above. The amount of solvent contained in the prepared resin paste A of Comparative Example 2 was 0% by mass (i.e., 0%) relative to 100% by mass of the non-volatile components of the resin composition. Then, the cured product of resin paste A was measured and evaluated in the same manner as in Example 1.

[0213] [Comparative Example 3] In Comparative Example 2, instead of incorporating 130 parts of inorganic filler ca ("Silica A") as component (C), 120 parts of inorganic filler ca ("Silica A") were used, along with inorganic filler cc (alumina surface-treated with Shin-Etsu Chemical Co., Ltd.'s surface treatment agent "KBM573" and classified to a maximum particle size of 5 μm or less, true density: 3.98 g / cm³). 3 , maximum particle size: 5μm, average particle size: 1.0μm, specific surface area: 3.98m 2 It contains 30 parts of alumina (also known as "alumina A"). In Comparative Example 2, the amount of the non-reactive additive e3a ("B-2000") as component (E-3) was changed from 13 parts to 8 parts.

[0214] Resin paste A was prepared in the same manner as in Comparative Example 2, except for the matters described above. The amount of solvent contained in the prepared resin paste A of Comparative Example 3 was 0% by mass (i.e., 0%) relative to 100% by mass of the non-volatile components of the resin composition. Then, the cured product of resin paste A was measured and evaluated in the same manner as in Example 1.

[0215] <Measurement and evaluation of cured products> The resin paste A obtained in Examples 1-10 and Comparative Examples 1-3 was cured as follows, and then measured and evaluated.

[0216] <Measurement of porosity> (1) Preparation of hardened material The resin paste A obtained in Examples 1-10 and Comparative Examples 1-3 was cured according to a curing method that included the following steps in this order: (1-1) compression molding and (1-2) post-curing. This resulted in cured products with a degree of curing of 95% or higher.

[0217] (1-1) Compression molding process As a compression molding process, the resin composition was positioned to bond to the silicon wafer, and then compressed under conditions of 15 tons of pressure, 130°C, and 10 minutes to obtain a compressed molded body of the resin composition with a thickness of 300 μm bonded to the silicon wafer.

[0218] Specifically, in the compression molding process, the aforementioned standardized compression molding process was adopted, and the following steps (c1) to (c4) were performed in this order. (c1) A process of placing a silicon wafer and a resin composition into a mold to which a release film has been attached. (c2) A process of closing the mold within 90 seconds after the resin composition is placed to bond the silicon wafer and the resin composition. (c3) A process of reducing the pressure inside the mold to a degree of reduced pressure within the range of 0 to 0.7 torr. (c4) A process to obtain a compressed molded body of a resin composition with a thickness of 300 μm bonded to a silicon wafer by compression molding under the conditions of a pressure of 15 tons, a temperature of 130°C, and 10 minutes.

[0219] In process (c1), a compression molding machine (Apic Yamada's "WCM-300" compression molding device) was used, which included a pair of separable molds. In this process, the inside of the molds was heated to the temperature used in process (c4) (mold temperature) of 130°C. A silicon wafer with a thickness of 775 μm and a diameter of 12 inches was used after being treated with a release agent. The silicon wafer was fixed to the surface of the mold located vertically below the pair of molds. The release film was attached to the mold facing the silicon wafer. The release film used was AGC's "Aflex® 50N 390NT" (mirror finish).

[0220] In step (c1), resin paste A obtained in Examples 1 to 10 and Comparative Examples 1 to 3 was used as the resin composition. When placing resin paste A on the silicon wafer, 40 g of resin paste A was weighed and placed in the center of the silicon wafer. The amount of resin paste A used was sufficient to cover the entire surface of the silicon wafer and to form a resin composition layer with a thickness of 300 μm.

[0221] In process (c4), the thickness of the resulting compressed molded body was set to 300 μm. A compression molding machine was used in which the pressure inside the mold increased from 0 tons to 15 tons within 60 seconds. 10 minutes was defined as the elapsed time after reaching a pressure of 15 tons. The compressed molded body (with silicon wafer) obtained in this way will hereinafter also be referred to as "compressed molded body C".

[0222] The compressed molded body C of Example 1 (compressed molded body before post-curing), obtained through the same process as the compression molding process described above, was removed from the mold along with the silicon wafer. Immediately afterward, the degree of hardening of the compressed molded body was measured by differential scanning calorimetry using a differential scanning calorimetry device ("DSC7020" manufactured by Hitachi High-Tech Science Corporation), and it was found to be 85%. The porosity of the compressed molded body C (porosity before post-curing) was measured and found to be 0.005%. The porosity was measured in the same manner as the method for measuring the porosity of the cured product D described later.

[0223] (1-2) Post-curing process As a post-curing step, a process was employed in which the compressed molded body of the obtained resin composition was heated under a nitrogen atmosphere at a temperature of 150°C for 1 hour to obtain a cured product.

[0224] Specifically, in the post-curing process, the standardized post-curing process described above was adopted, and the following steps (p1) to (p2) were performed in this order. (p1) A step of obtaining a cured product by placing a compressed molded body of the resin composition removed from the mold into an oven set to 150°C and 1 atmosphere under a nitrogen atmosphere and waiting for 1 hour; and, (p2) Remove the cured material from the oven within 120 seconds after step (p1) and allow it to cool at room temperature and pressure.

[0225] In step (p1), a Yamato Scientific "DN6101" oven was used. Prior to step (p1), the oven was set to a predetermined nitrogen atmosphere, temperature of 150°C, and atmospheric pressure of 1 atmosphere. Prior to step (p1), the compression molded body to be placed in the oven was the silicon wafer that had been removed from the mold used in step (c4) above (compression molded body C). The thickness of the resin composition layer of the compression molded body C of Example 1 that was placed in the oven was 305 μm.

[0226] In step (p2), the cured material removed from the oven was allowed to cool in the room. The room was at atmospheric pressure (approximately 1 atmosphere), room temperature (approximately 23°C), and humidity was 50%. After 6 hours, it was confirmed that the surface temperature of the cured material had reached 23°C.

[0227] It was confirmed that the thickness of the resin composition layer in the cured product obtained from resin paste A of Example 1, obtained through process (p2), was less than ±5% of the thickness before post-curing (305 μm) and within the range of 300 μm ± 5 μm. Furthermore, the degree of curing of the resin composition layer in the same cured product was measured by differential scanning calorimetry using a differential scanning calorimetry device (DSC7020, Hitachi High-Tech Science Corporation), and was found to be 100%. For the resin composition layers in the cured products of the other examples and comparative examples, it was confirmed that the curing shrinkage was less than ±5% of the thickness before post-curing (300 μm) and that the degree of curing was 95% or higher. Hereinafter, the cured product (with silicon wafer) obtained in this manner will also be referred to as "cured product D".

[0228] (2) Measurement of the void ratio of the hardened material (2-1) Determining the observation area The following procedure was performed to obtain a cross-sectional SEM image of hardened material D. The SEM used was the one attached to the FIB-SEM hybrid system "SMI3050SE" manufactured by SII Nanotechnology (now Hitachi High-Technologies Corporation). First, the cured material D, with the silicon wafer still attached, was cut into 1 cm squares. Then, for each cut piece, a longitudinal section was prepared using the FIB attached to the FIB-SEM hybrid system described above. For the cross-section preparation, the FIB was focused at a position with a width and depth of 30 μm. Next, the obtained cross-section was observed using a scanning electron microscope (SEM) at a magnification of 27,000x, and a region of the observed resin composition layer that was 50 μm or more away from the interface between the silicon wafer and the resin composition layer was selected. The area of ​​the observation region at this time was 1000 pixels in the thickness direction × 1000 pixels in the in-plane direction. The thickness direction refers to the direction parallel to the cross-section of the silicon wafer or the cross-section of the resin composition layer, and the in-plane direction refers to the direction parallel to the surface of the silicon wafer or the formation surface of the resin composition layer. An observation region of 1000 pixels × 1000 pixels corresponds to a region of approximately 9 μm × 9 μm. The observation area defined as described above was obtained as a cross-sectional image using SEM.

[0229] (2-2) Image analysis of void regions Next, the SEM cross-sectional images obtained in (2-1) above were imported into the image analysis software "ImageJ" (hereinafter also referred to as "analysis software"), and image analysis was performed as follows. The version of the "ImageJ" software used was "1.51j8". Note that the latest version of the "ImageJ" analysis software is available from the internet. First, the analysis software was launched and the SEM cross-sectional image was displayed. Figure 2 is a photograph of the SEM cross-sectional image of hardened material D of Example 8 displayed in the analysis software (more specifically, the SEM cross-sectional image of hardened material D of Example 8 used for the third void ratio measurement). Next, the contours of each void region were enclosed in the displayed image using the analysis software's "Freehand selection" command. Then, using the "cut" command included in "Edit," the enclosed contours and the inner regions defined by those contours were cut out so that the void regions could be identified. The same process was performed for all void regions observed in the SEM cross-sectional image. After that, the contrast of the identified void regions (black regions) was adjusted using the "Threshold" command under "Adjust" in "Image" so that only the void regions were black. Subsequently, the interiors of the identified void regions were colored red using the "Red" command. Figure 3 shows a photograph of the SEM cross-sectional image in Figure 2 with the void regions colored red. Then, using the "Measure" command included in the "Analyze" command, the total area (number of pixels) of the red-colored region (void region) was obtained.

[0230] (2-3) Calculation of void ratio Subsequently, the void ratio (%) was calculated by dividing the total area (number of pixels) of the void region obtained in (2-2) above by the number of pixels of the observation region (1000 pixels × 1000 pixels), and then multiplying the resulting value by 100.

[0231] (2-4) Calculation of the average value The above steps (2-1) to (2-3) were repeated 50 times. That is, the observation area was changed 50 times by creating cross-sections (number of observations N=50), and the porosity was calculated. The average value was then calculated by dividing the sum of the obtained porosities by 50. By increasing the number of observations in this way, it is expected that randomness (uneven distribution of components on the observation surface) and arbitrariness (missing counts) will be eliminated. The average values ​​of the calculated porosities are shown in Table 1.

[0232] Provided, however, that SEM cross-sectional images for which porosity should be calculated are selected as described below, and porosity is not calculated for SEM cross-sectional images that do not satisfy the following requirements. First, for the inorganic filler contained in resin paste A prepared in each of the Examples and Comparative Examples, the volume percentage (%) was calculated based on the blending amount and true density thereof. On the other hand, the area percentage (%), which is a value obtained by dividing the number of pixels of the inorganic filler region in the SEM cross-sectional image obtained in (2-1) above by the number of pixels of the observation region (1000 pixels × 1000 pixels) and multiplying by 100, was calculated in the same manner as in (2-2) above. Then, the obtained volume percentage (%) and area percentage (%) of the inorganic filler were compared, and SEM cross-sectional images that satisfy the requirement that the value of the area percentage (%) falls within the range of ±3 of the value of the volume percentage (%) were selected as targets for porosity calculation.

[0233] <Evaluation of Warpage> On a 12-inch silicon wafer, the resin compositions prepared in the Examples and Comparative Examples were compression molded using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes) to form a resin composition layer having a thickness of 300 µm. Thereafter, the resin composition layer was thermally cured by heating at 180°C for 90 minutes. Thus, a sample substrate including the silicon wafer and the cured layer of the resin composition was obtained. The amount of warpage of the sample substrate at 25°C was measured using a shadow moiré measuring apparatus ("Thermoire AXP" manufactured by Akorometrix). The measurement was performed in accordance with JEITA EDX-7311-24, the standard of the Japan Electronics and Information Technology Industries Association. Specifically, with a virtual plane calculated by the least square method for all data of the substrate surface in the measurement region used as a reference plane, the difference between the minimum value and the maximum value in the direction perpendicular to the reference plane was determined as the amount of warpage, and evaluation was performed according to the following criteria. ○: The amount of warpage is less than 2000 µm (2 mm). ×: The amount of warpage is 2 mm or more. The measured amounts of warpage and the evaluation results of low warpage property are shown in Table 1.

[0234] <Evaluation of Long-Term Reliability> 1. Preparation of Cured Product for Evaluation A 300 μm thick resin composition layer was formed on a demolded 12-inch silicon wafer by compression molding of the resin compositions prepared in the examples and comparative examples using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes). The resin composition layer was peeled off the silicon wafer and heated at 180°C for 90 minutes to thermally cure the resin composition layer and obtain cured product A for evaluation.

[0235] 2. Evaluation of long-term reliability Long-term reliability was evaluated by performing an HTS test on the evaluation cured material A, measuring the fracture strength before and after the HTS (High Thermal Storage) test, and calculating the percentage change in fracture strength.

[0236] (1) HTS test Evaluation cured material A was subjected to an HTS test. In the HTS test, evaluation cured material A was held at 150°C for 1000 hours. This yielded the evaluation cured material after the HTS test.

[0237] (2) Measurement of fracture strength before and after HTS test Five test specimens were obtained by cutting the evaluation cured material before the HTS test into No. 1 dumbbell-shaped pieces in a plan view. Similarly, five test specimens were obtained by cutting the evaluation cured material after the HTS test into No. 1 dumbbell-shaped pieces in a plan view. For each test specimen, a tensile test was performed using an Orientec RTC-1250A tensile testing machine under measurement conditions of 23°C and a test speed of 5 mm / min, and the tensile breaking point strength (also simply called "breaking point strength") was determined from the stress-strain curve. The measurements were performed in accordance with JIS K7127:1999. The average value of the breaking point strengths of the five test specimens was defined as the tensile breaking point strength σ0 before the HTS test. The average value of the breaking point strengths of the five test specimens was defined as the tensile breaking point strength σ1 after the HTS test. The percentage change in tensile breaking point strength before and after the HTS test was calculated based on the following formula. Change (%) = {(σ1-σ0) / σ0} × 100 Based on the calculated percentage change, long-term reliability was evaluated according to the following criteria.

[0238] Criteria for evaluating long-term reliability: ○: When the absolute value of the degree of change (%) is less than 10% (the degree of change is small and the long-term reliability is excellent) ×: When the absolute value of the degree of change (%) is 10% or more (the degree of change is large and the long-term reliability is poor) The measured fracture strength and degree of change are shown in Table 1.

[0239] <Evaluation of dielectric properties> A 300 μm thick resin composition layer was formed on a demolded 12-inch silicon wafer by compression molding of the resin compositions prepared in the examples and comparative examples using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes). The resin composition was then peeled from the demolded silicon wafer and heated at 150°C for 90 minutes to thermocure the resin composition and prepare samples. Dielectric constant and dielectric loss tangent were measured at 60 GHz using the Fabry-Perot method. Measurements were performed on three test pieces, and the average values ​​were calculated. Table 1 shows the average values ​​of the measured dielectric constant and dielectric loss tangent.

[0240] The results for Examples 1-10 and Comparative Examples 1-3 are shown in Table 1.

[0241] [Table 1] [Explanation of Symbols]

[0242] 100 semiconductor chip packages 110 semiconductor chips 120 sealing layer 130 Rewiring formation layer 140 Redistribution layer 150 solder resist layers 160 Bump

Claims

1. A resin composition comprising (A) epoxy resin, (B) curing agent, (C) inorganic filler, and (E-1) aminosilane-based silane coupling agent and / or mercaptosilane-based silane coupling agent, When the resin composition is cured by a curing method including the following compression molding and post-curing steps, the resulting cured product exhibits a porosity in the range of 0.002% to 2%, and a breaking strength of 55 MPa or more and less than 110 MPa. Here, the porosity is the area percentage (%) of the void region in the SEM cross-sectional image of the cured resin composition. <Compression molding process> The process involves arranging the resin composition to bond to a silicon wafer, then compression molding it under conditions of 15 tons of pressure, 130°C, and 10 minutes to obtain a compressed molded body of the resin composition bonded to the silicon wafer with a thickness of 300 μm. <Post-cure process> A process to obtain a cured product by heating a compression molded body of the obtained resin composition under a nitrogen atmosphere at a temperature of 150°C for 1 hour.

2. The resin composition according to claim 1, wherein the porosity is obtained by calculating the area ratio (%) of the void region to the observation region obtained as a void image by image analysis of an observation region with dimensions of 1,000 pixels in the thickness direction and 1,000 pixels in the in-plane direction in a cross-sectional SEM image at a magnification of 27,000 times.

3. The resin composition according to claim 1 or 2, wherein the porosity is the arithmetic mean of the area percentage (%) of void regions obtained for 50 SEM cross-sectional images of the cured material.

4. The compression molding process is comprised of the following steps (c1) to (c4): (c1) A step of placing a silicon wafer and a resin composition in a mold to which a release film has been attached; (c2) A step of closing the mold within 90 seconds after the resin composition is placed to bond the silicon wafer and the resin composition; (c3) A step of reducing the pressure inside the mold to a degree of reduced pressure within the range of 0 to 0.7 torr; and, (c4) A step to obtain a compressed molded body of a resin composition with a thickness of 300 μm bonded to a silicon wafer by compression molding under the conditions of a pressure of 15 tons, a temperature of 130°C, and 10 minutes. A resin composition according to any one of claims 1 to 3, comprising the elements in this order.

5. The post-cure process described above consists of the following steps (p1) to (p2): (p1) A step of obtaining a cured product by placing a compressed molded body of the resin composition removed from the mold into an oven set to 150°C and 1 atmosphere under a nitrogen atmosphere and waiting for 1 hour; and, (p2) Remove the cured product from the oven within 120 seconds after step (p1) and allow it to cool in a room temperature and pressure environment. A resin composition according to any one of claims 1 to 4, comprising the elements in this order.

6. The resin composition according to any one of claims 1 to 5, wherein the resin porosity, which indicates the area ratio of the void region in the resin component region to the observed region obtained by excluding the void region within the region defined by the outer shape region of the inorganic filler from the void region obtained as a void image by image analysis, is in the range of 0.002% to 2%.

7. The resin composition according to any one of claims 1 to 6, wherein component (A) is 0.5% by mass or more and 45% by mass or less, when the nonvolatile components in the resin composition are considered to be 100% by mass.

8. The resin composition according to any one of claims 1 to 7, wherein component (C) is 30% by mass or more when the nonvolatile components in the resin composition are considered to be 100% by mass.

9. The resin composition according to any one of claims 1 to 8, wherein component (A) comprises (A-1) a liquid epoxy resin.

10. The resin composition according to any one of claims 1 to 9, wherein the (E-1) component is of a single type.

11. (E-1) A resin composition according to any one of claims 1 to 9, wherein the component is of multiple types.

12. The resin composition according to any one of claims 1 to 11, further comprising a reactive component (E-2) which comprises at least one selected from the group consisting of (i) to (v) below. (i) (meth)acrylic radical polymerizable compounds containing a polyalkylene oxide structure (ii) Maleimide-based radical polymerizable compounds (iii) Polyether skeleton-containing compounds having reactive functional groups and a silicone skeleton (iv) Polyether skeleton-containing compounds having reactive functional groups and a polyester skeleton (v) Polyoxyethylene polyoxypropylene glycol

13. The resin composition according to any one of claims 1 to 12, wherein the solvent content is 3% by mass or less when the nonvolatile components in the resin composition are considered to be 100% by mass.

14. The resin composition according to any one of claims 1 to 13, wherein the viscosity at 25°C, as measured using an E-type viscometer, is in the range of 1 Pa·s to 1000 Pa·s.

15. The resin composition according to any one of claims 1 to 14, wherein the dielectric constant (Dk) of the cured product is less than 3.

6.

16. The resin composition according to any one of claims 1 to 15, wherein the dielectric loss tangent (Df) of the cured product is less than 0.

03.

17. The resin composition according to any one of claims 1 to 16, wherein the degree of curing of the cured product is 95% or more.

18. A resin composition according to any one of claims 1 to 17 for forming an insulating layer of a semiconductor chip package.

19. A resin composition according to any one of claims 1 to 18, for use as a rewiring layer.

20. A resin paste formed comprising the resin composition according to any one of claims 1 to 19.

21. A cured resin composition according to any one of claims 1 to 19 or a cured resin paste according to claim 20.

22. A cured product obtained by curing a resin composition containing (A) epoxy resin, (B) curing agent, (C) inorganic filler, and (E-1) aminosilane-based silane coupling agent and / or mercaptosilane-based silane coupling agent using a curing method including the following compression molding step and post-cure step, wherein the cured product has a porosity in the range of 0.002% to 2%, and a breaking strength of 55 MPa or more and less than 110 MPa, where the porosity is the area ratio (%) of the void region in the SEM cross-sectional image of the cured product. <Compression molding process> The process involves arranging the resin composition to bond to a silicon wafer, then compression molding it under conditions of 15 tons of pressure, 130°C, and 10 minutes to obtain a compressed molded body of the resin composition bonded to the silicon wafer with a thickness of 300 μm. <Post-cure process> A process to obtain a cured product by heating a compression molded body of the obtained resin composition under a nitrogen atmosphere at a temperature of 150°C for 1 hour.

23. A semiconductor chip package comprising an insulating layer made of a resin composition according to any one of claims 1 to 19 or a cured resin paste according to claim 20, or an insulating layer made of a cured product according to claim 21 or claim 22.

24. The semiconductor chip package according to claim 23, wherein the insulating layer is a redistribution forming layer.

25. A semiconductor chip package according to claim 23 or 24, which is a fan-out type package.

26. A semiconductor device comprising a semiconductor chip package according to any one of claims 23 to 25.

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