Resin composition, resin paste, cured product, semiconductor chip package and semiconductor device

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 a resin composition, particularly a resin paste, and further to a cured product, a semiconductor chip package, and a semiconductor device formed using the resin composition or the resin paste. [Background technology]

[0002] In recent years, the demand for small, highly functional electronic devices such as smartphones and tablet devices has been increasing, and accordingly, insulating materials for semiconductor chip packages used in these small electronic devices are required to have higher functionality. As such insulating materials, those formed by curing a resin composition are known (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2004-137370 A Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, in the manufacture of semiconductor chip packages, there has been a demand for resin compositions for forming insulating layers that are less susceptible to warping and that provide cured products that have excellent mechanical properties.

[0005] An object of the present invention is to provide a resin composition or resin paste which is capable of suppressing the occurrence of warping and giving a cured product having excellent mechanical properties; and to provide a cured product, a semiconductor chip package, and a semiconductor device formed using the resin composition or resin paste. [Means for solving the problem]

[0006] The present inventors have conducted extensive research to solve the above problems, and as a result, have found that the above problems can be solved by a resin composition that contains (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, and that produces a cured product having voids in a specific range, thereby completing the present invention. That is, the present invention includes the following.

[0007] [1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, When the resin composition is cured by a curing method including the following compression molding step and post-cure step, the resulting cured product exhibits a porosity in the range of 0.002% to 2%, Here, the porosity is the area ratio (%) of void regions in a SEM cross-sectional image of a cured resin composition. <Compression molding process> A process of placing the resin composition so as to be bonded to the silicon wafer, and then compressing and molding the composition under conditions of a pressure of 15 tons, a temperature of 130°C, and a time of 10 minutes to obtain a compression molded product of the resin composition bonded to the silicon wafer and having a thickness of 300 μm. <Post-cure process> A process of heating the compression molded resin composition obtained under nitrogen atmosphere at 150°C for 1 hour to obtain a cured product. [2] The resin composition described in [1], wherein the porosity is obtained by calculating the area ratio (%) of the void area obtained as a void image by performing image analysis on an observation area of ​​1000 pixels in the thickness direction and 1000 pixels in the in-plane direction in a SEM cross-sectional 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 ratio (%) of void regions obtained in 50 SEM cross-sectional images of the cured material. [4] The compression molding step includes the following steps (c1) to (c4): (c1) placing a silicon wafer and a resin composition in a mold having a release film attached thereto; (c2) a step of closing the mold within 90 seconds after placing the resin composition to bond the silicon wafer and the resin composition; (c3) reducing the pressure inside the mold to a reduced pressure within a range of 0 to 0.7 torr; and (c4) A process of compression molding under conditions of a pressure of 15 tons, a temperature of 130°C, and a time of 10 minutes to obtain a compression molded body of the resin composition having a thickness of 300 μm bonded to the silicon wafer. The resin composition according to any one of [1] to [3], comprising, in this order: [5] The post-cure step comprises the following steps (p1) to (p2): (p1) a step of placing the compression molded resin composition removed from the mold in an oven set at a temperature of 150° C. and 1 atmospheric pressure in a nitrogen atmosphere and waiting for one hour to obtain a cured product; and (p2) A process of removing the cured product from the oven within 120 seconds after step (p1) and allowing it to cool in a room temperature and normal pressure environment. The resin composition according to any one of [1] to [4], comprising, in this order: [6] The resin composition according to any one of [1] to [5], wherein the resin porosity, which indicates the area ratio of the void area in the resin component region obtained by excluding the void area within the region defined by the outline region of the inorganic filler (B) from the void area obtained as a void image by image analysis, to the observation region, is within the range of 0.002% to 2%. [7] The resin composition according to any one of [1] to [6], wherein the component (C) is 30 mass % or more, based on 100 mass % of the non-volatile components in the resin composition. [8] The resin composition according to any one of [1] to [7], wherein the component (A) contains an epoxy resin (A-1) in a liquid form. [9] The resin composition according to any one of [1] to [8], comprising (E-1) a silane coupling agent, the silane coupling agent being of a single type.

[10] The resin composition according to any one of [1] to [8], comprising (E-1) a silane coupling agent, wherein the silane coupling agent is of multiple types.

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

[10] , wherein the content of the solvent is 3 mass% or less, based on 100 mass% of non-volatile components in the resin composition.

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

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

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

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

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

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

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

[14] , wherein the break strength of the cured product exceeds 45 MPa.

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

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

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

[16] 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 use in a rewiring formation layer.

[19] A resin paste formed by containing 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 comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, the cured product having a porosity in the range of 0.002% to 2%, where the porosity is the area ratio (%) of void regions in a SEM cross-sectional image of the cured product.

[22] A semiconductor chip package comprising an insulating layer made 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 made of the cured product according to

[20] or

[21] .

[23] The semiconductor chip package according to

[22] , wherein the insulating layer is a redistribution 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] . Effect of the Invention

[0008] According to the present invention, it is possible to provide a resin composition or resin paste which is capable of suppressing the occurrence of warping and giving a cured product having excellent mechanical properties; and a cured product, a semiconductor chip package, and a semiconductor device formed using the resin composition or resin paste. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a cross-sectional view showing a schematic configuration of a fan-out type WLP as an example of a semiconductor chip package according to an embodiment of the present invention. [Diagram 2] FIG. 2 is a photograph of an SEM cross-sectional image of the cured product of Example 8 displayed by analysis software. [Diagram 3] FIG. 3 is a photograph showing the state in which the void regions in the SEM cross-sectional image of FIG. 2 are colored red. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0011] [Resin composition] The resin composition of the present invention is characterized by containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, and producing a cured product having voids in a specific range of amount.

[0012] Specifically, when the resin composition of the present invention is cured by a curing method including the following compression molding step and post-cure step, the resulting cured product exhibits a porosity in the range of 0.002% to 2%. <Compression molding process> A process of placing the resin composition so as to be bonded to the silicon wafer, and then compressing and molding the composition under conditions of a pressure of 15 tons, a temperature of 130°C, and a time of 10 minutes to obtain a compression molded product of the resin composition bonded to the silicon wafer and having a thickness of 300 μm. <Post-cure process> A process of heating the compression molded resin composition obtained under nitrogen atmosphere at 150°C for 1 hour to obtain a cured product.

[0013] The "porosity" used as an index of the amount of voids in a cured product represents the area ratio (%) of voids in the cross section of the cured product, and in the present invention, it is represented by the area ratio (%) of the void region in the SEM cross-sectional image of the cured product. Here, the amount of voids contained in the cured product can be considered to be evaluated by the volume ratio (%), but the present inventors have found that the above porosity related to the area ratio (%) can easily and accurately evaluate and define the constitution of a resin composition that exhibits the effect of the present invention, that is, suppressing the occurrence of warping and providing a cured product with excellent mechanical properties.

[0014] In determining the porosity, the area percentage (%) of the void region may be calculated for the entire SEM cross-sectional image, or the area percentage (%) of the void region may be calculated for a specific region in the SEM cross-sectional image, preferably an observation region of a predetermined size or more, more preferably 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 to the case 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 more, preferably 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 product of the resin composition, or may be an SEM image of a transverse section of the cured product of the resin composition. The longitudinal section is a section including a dimension in the thickness direction. The longitudinal section may be a section along a direction perpendicular to the main surface of the cured product of the resin composition, or may be a section along a direction perpendicular to the plane of the member when a member (e.g., a silicon wafer) having a flat surface is bonded to the cured product of the resin composition at the plane. The transverse section is a section perpendicular to the longitudinal section, that is, a section parallel to the in-plane direction. The transverse section may be a section parallel to the main surface of the cured product of the resin composition, or may be a section parallel to the plane of the member when a member (e.g., a silicon wafer) having a flat surface is bonded to the cured product of the resin composition at the plane. From the viewpoint of easily performing cross-section extraction, the SEM cross-sectional image is preferably an SEM image of a longitudinal section of the cured product of the resin composition.

[0016] From the viewpoint of evaluating and defining the porosity with high accuracy, it is preferable to predefine 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 20,000 times or more, more preferably 25,000 times or more, 26,000 times or more, or 27,000 times or more, and the size of the observation area in the SEM cross-sectional image may be, in terms of the number of pixels, preferably 800 pixel squares or more, more preferably 900 pixel squares or more, or 1000 pixel squares or more. From the viewpoint of evaluating and defining the porosity with high accuracy, the upper limit of the magnification during SEM observation is preferably 50,000 times or less, more preferably 49,000 times or less, 48,000 times or less, or 47,000 times or less, and the upper limit of the size of the observation area in the SEM cross-sectional image is not particularly limited in calculating the area ratio (%) of the void area, but may be, in terms of the number of pixels, preferably 1300 pixel squares or less, more preferably 1200 pixel squares or less, or 1100 pixel squares or less. In a preferred embodiment, the porosity is obtained by performing image analysis on an observation area of ​​1000 pixels square (1000 pixels in the thickness direction × 1000 pixels in the in-plane direction) in an SEM cross-sectional image of the cured product at a magnification of 27,000 times, and calculating the area ratio (%) of the void area obtained as a void image to the observation area.

[0017] From the viewpoint of evaluating and defining the porosity with high accuracy, it is preferable to adopt the arithmetic mean value of the porosity calculated for a plurality of SEM cross-sectional images and observation regions as the porosity. Therefore, in a preferred embodiment, the porosity is the arithmetic mean value of the area ratio (%) of the void region obtained for 50 SEM cross-sectional images of the cured material.

[0018] Typically, the porosity can be measured according to the method described in the section on measuring the porosity of the cured product below. When obtaining SEM cross-sectional images of 50 points of the cured product, it is preferable to perform cross-sectional exposure (preferably vertical cross-sectional exposure) of multiple test pieces of a single sample. In addition, cross-sectional exposure (preferably vertical cross-sectional exposure) may be performed multiple times for one test piece.

[0019] The compression molding step and post-cure step carried out in preparing a cured sample for determining the porosity will be described below.

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

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

[0022] As the pair of dies, it is preferable that the silicon wafer can be placed on either one of the die located vertically below and the die located vertically above. In one embodiment, the compression molding process is performed using a compression molding machine configured to include a pair of dies that can be separated, the silicon wafer is placed on the die located vertically below, and the resin composition is placed between the die located vertically above and the silicon wafer. In another embodiment, the compression molding process is performed using a compression molding machine configured to include a pair of dies that can be separated, the silicon wafer is placed on the die located vertically above, and the resin composition is placed between the die located vertically below and the silicon wafer. The silicon wafer and the resin composition may be placed apart from each other, or the silicon wafer and the resin composition may be placed in contact with each other. That is, with regard to the positional relationship between the silicon wafer and the resin composition, as long as the two are arranged so as to be bondable, the silicon wafer may be placed above the resin composition, or the resin composition may be placed above the silicon wafer.

[0023] The silicon wafer and the resin composition are preferably placed in a mold whose inside has been heated in advance to 130° C. Although the temperature to which the mold is heated has been described as 130° C., the inside of the mold may be heated during or prior to the compression molding step so that a fluctuation within a range of up to +5° C. is permitted.

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

[0025] The size of the silicon wafer is not limited as long as it is possible to obtain a cured product of the resin composition whose porosity can be measured, but in the compression molding step, it is preferable to place a silicon wafer having a thickness of 775 μm and a diameter of 12 inches in a mold. When it is necessary to remove the compression molded product of the resin composition from the silicon wafer, it is preferable to subject the silicon wafer to a mold release treatment.

[0026] Although the thickness of the compression molded body of the resin composition is set to 300 μm, it does not have to be exactly 300 μm, and in the compression molding process, compression molding may be performed so as to allow variation in the thickness of the compression molded body of the resin composition within a range of ±5 μm.

[0027] In order to accurately evaluate and define the porosity, the compression molding process includes the following steps (c1) to (c4): (c1) placing a silicon wafer and a resin composition in a mold having a release film attached thereto; (c2) a step of closing the mold within 90 seconds after placing the resin composition to bond the silicon wafer and the resin composition; (c3) reducing the pressure inside the mold to a reduced pressure within a range of 0 to 0.7 torr; and (c4) A process of compression molding under conditions of a pressure of 15 tons, a temperature of 130°C, and a time of 10 minutes to obtain a compression molded body of the resin composition having a thickness of 300 μm bonded to the silicon wafer. It is particularly preferable that the steps (c1) to (c4) are included in this order. A compression molding process including the steps (c1) to (c4) in this order is also called a "standardized compression molding process".

[0028] Regarding the standardized compression molding step, in step (c1), the arrangement of the silicon wafer and the resin composition is as described above, and in one embodiment, the compression molding step is performed using a compression molding machine including a pair of separable dies, and the silicon wafer is placed on the surface of the dies located vertically below. Other embodiments are as described above.

[0029] The release film used in step (c1) may be a commercially available product that has not been embossed, specifically a mirror-finished product, 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 "Aflex (registered trademark) 50N 390NT" (mirror-finished) manufactured by AGC.

[0030] In step (c2), the mold is closed within 90 seconds after placing the resin composition to bond the silicon wafer and the resin composition. When the compression molding step is performed using a compression molding machine including a pair of separable molds, the start of mold closing refers to the narrowing of the separation distance between the pair of molds.

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

[0032] The step (c4) is the same as that explained in the compression molding step described above, and therefore the explanation thereof will be omitted.

[0033] The standardized compression molding process is not limited as long as it includes the above steps (c1) to (c4) in this order. Typically, the standardized compression molding process may be the compression molding process described in the examples below.

[0034] <Post-cure process> In the post-cure step, the compression molded product of the obtained resin composition is heated in a nitrogen atmosphere at a temperature of 150° C. for one hour to obtain a cured product.

[0035] From the viewpoint of accurately evaluating and specifying the porosity, the post-cure process includes the following steps (p1) to (p2): (p1) a step of placing the compression molded resin composition removed from the mold in an oven set at a temperature of 150° C. and 1 atmospheric pressure in a nitrogen atmosphere and waiting for one hour to obtain a cured product; and (p2) A process of removing the cured product from the oven within 120 seconds after step (p1) and cooling it in a room temperature and pressure environment. It is particularly preferable that the steps (p1) and (p2) are included in this order. A post-cure step including the steps (p1) and (p2) in this order is also called a "standardized post-cure step".

[0036] Regarding the standardized post-cure step, it is preferable to set the oven to a preset state of nitrogen atmosphere, temperature of 150°C and pressure of 1 atm prior to step (p1), so that the compression molded product of the resin composition can be quickly introduced into the oven in step (p1). Also, the compression molded product of the resin composition to be introduced into the oven may have the silicon wafer still attached.

[0037] In step (p2), the cured product may be quickly removed from the oven to avoid unintended continuation of heating in step (p1), and the above-mentioned 120 seconds or less specified for this purpose is preferably 110 seconds or less, more preferably 100 seconds or less. The cured product removed from the oven may be allowed to cool in a room temperature and pressure environment, for example, an environment with a pressure of 1 atm ± 1 atm and a temperature of 23°C ± 5°C, preferably an environment with a pressure of 1 atm ± 0.5 atm and a temperature of 23°C ± 5°C. The humidity in such an environment is preferably 40 to 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 that the temperature has reached room temperature after a predetermined time (for example, 6 hours) has passed.

[0038] The thickness of the cured product (resin composition layer) obtained through step (p2) is preferably less than ±5% of the thickness before post-cure, more preferably within the range of 300 μm ±5 μm. In addition, it is preferable to carry out the post-cure step so that the degree of cure of the cured product (resin composition layer) is 95% or more, more preferably 96% or more, when measured by differential scanning calorimetry using a differential scanning calorimeter ("DSC7020" manufactured by Hitachi High-Tech Science Corporation).

[0039] The standardized post-cure process is not limited as long as it includes the above steps (p1) to (p2) in this order. Typically, the post-cure process described in the examples below can be adopted as the standardized post-cure process.

[0040] The cured product to be evaluated for porosity is preferably subjected to the above-mentioned compression molding step and post-cure step so that the degree of cure is 95% or more, and more preferably 96% or more. The degree of cure can be measured by differential scanning calorimetry using a differential scanning calorimeter (Hitachi High-Tech Science Corporation's "DSC7020").

[0041] The resin composition of the present invention has a porosity of 0.002% to 2% in the cured product. This allows the resin composition of the present invention to suppress the occurrence of warping and to obtain a cured product with excellent mechanical properties. In addition, the resin composition of the present invention that has a porosity of 0.002% to 2% after curing tends to be able to obtain a cured product with excellent dielectric properties.

[0042] From the viewpoint of obtaining a cured product in which the occurrence of warping is further suppressed, the porosity 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 porosity 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 instead of or together with the porosity. The resin porosity indicates the area ratio (%) of the void region in the resin component region obtained by excluding the void region in the region defined by the outline region of the inorganic filler (C) described later from the void region obtained as a void image by image analysis when obtaining the porosity. Unless otherwise specified, the resin component represents the components other than the inorganic filler (C) among the non-volatile components in the resin composition, 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 compression molding step and the post-cure step are performed using a resin composition containing an inorganic filler that does not substantially contain voids as the inorganic filler, that is, a solid inorganic filler, the porosity and the resin porosity can usually take the same numerical value. In this case, the resin porosity is preferably within the range of 0.002% to 2%, similar to the porosity.

[0044] When the compression molding step and the post-cure step are carried out using a resin composition containing an inorganic filler containing voids (so-called hollow filler) as the inorganic filler, the resin void ratio is usually smaller than the void ratio because the voids in the inorganic filler are not counted. In this case, the resin void ratio 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 increasing the accuracy of the void ratio measurement, it is preferable not to use a hollow filler as the inorganic filler, and from this viewpoint, even if the resin composition contains a hollow filler, the content thereof is more preferably less than 0.005% by mass, 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 100% by mass.

[0045] [Composition of 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 the (A), (B), and (C) components, 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 porosity range is satisfied after curing. Here, the presence or absence and the degree of influence of each component constituting the resin composition on the generation of voids differ, and the degree of influence on the generation of voids increases or decreases depending on the combination of components. Below, the composition of a resin composition suitable for satisfying the above porosity range after curing will be described, but the suitable type and suitable content range will change depending on the combination of components. As long as the above porosity range is satisfied after curing, the type (combination) and content of the components constituting the resin composition are not limited to the specific type and range shown below.

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

[0047] Examples of the (A) epoxy resin include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, phenol novolac type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, alicyclic epoxy resins having an ester skeleton, and composite epoxy resins. Examples of the epoxy resins include acyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, naphthylene ether type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, naphthol novolac type epoxy resins, and other epoxy resins containing a condensed ring skeleton, isocyanurate type epoxy resins, alkyleneoxy skeleton and butadiene skeleton-containing epoxy resins, and fluorene structure-containing epoxy resins. The (A) epoxy resins may be used alone or in combination of two or more.

[0048] From the viewpoint of obtaining a cured product having excellent heat resistance, the (A) epoxy resin may contain an epoxy resin containing an aromatic structure. The aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatic rings and aromatic heterocycles. Examples of epoxy resins containing an aromatic structure include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, bisxylenol type epoxy resins, glycidylamine type epoxy resins having an aromatic structure, glycidyl ester type epoxy resins having an aromatic structure, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins having an aromatic structure, epoxy resins having a butadiene structure having an aromatic structure, alicyclic epoxy resins having an aromatic structure, heterocyclic epoxy resins, spiro ring-containing epoxy resins having an aromatic structure, cyclohexane dimethanol type epoxy resins having an aromatic structure, naphthylene ether type epoxy resins, trimethylol type epoxy resins having an aromatic structure, and tetraphenylethane type epoxy resins having an aromatic structure.

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

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

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

[0052] The resin composition preferably contains, as the (A) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. The proportion of the epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the non-volatile components of the (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 a temperature of 20° C. (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20° C. (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition of the present embodiment may contain, as the epoxy resin, only a liquid epoxy resin (A-1), or only a solid epoxy resin (A-2), or a combination of a liquid epoxy resin and a solid epoxy resin, but it is preferable that the resin composition contains at least a liquid epoxy resin.

[0054] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0055] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, epoxy resin having a butadiene structure, epoxy resin containing an alkyleneoxy skeleton and a butadiene skeleton, epoxy resin containing a fluorene structure, and dicyclopentadiene type epoxy resin are preferred. Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy resin having an ester skeleton, epoxy resin having a butadiene structure, epoxy resin containing an alkyleneoxy 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 "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", and "Epikote 828EL" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", and "604" (glycidylamine type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycirol type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resins) manufactured by ADEKA Corporation; and "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Corporation. epoxy resin); "ZX1059" manufactured by Nippon Steel Chemical & Material Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase ChemteX Corporation (glycidyl ester type epoxy resin); "EX-991L" (alkyleneoxy skeleton-containing epoxy resin) and "EX-992L" (polyether-containing epoxy resin) manufactured by Nagase ChemteX Corporation; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; "PB-3600" manufactured by Daicel Corporation, "JP-100" and "JP-200" (epoxy resin having a butadiene structure) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EG-280" (fluorene structure-containing epoxy resin) manufactured by Osaka Gas Chemical Co., Ltd., and the like.

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

[0058] As the solid epoxy resin, 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 are preferred.

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

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

[0061] The epoxy equivalent of the (A) 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 a resin containing one equivalent of an epoxy group. This epoxy equivalent can be measured according to JIS K7236.

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

[0063] The amount of the (A) epoxy resin relative to 100 mass% of the non-volatile components in the resin composition is not particularly limited, but is preferably 0.5 mass% or more, more preferably 1 mass% or more, and particularly preferably 1.5 mass% or more, and is preferably 45 mass% or less, more preferably 40 mass% or less, and particularly preferably 30 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, and is preferably 80% by mass or less, more preferably 70% by mass or less, particularly preferably 60% by mass or less. Unless otherwise specified, the resin components in the resin composition refer to the components other than (C) inorganic filler among the non-volatile components in the resin composition.

[0065] [(B) Hardener] The resin composition of the present invention includes a curing agent (B). The curing agent (B) usually has a function of reacting with the epoxy resin (A) to cure the resin composition. Examples of the curing agent (B) 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 curing agent (B). When an acid anhydride curing agent, an amine curing agent, or a phenolic curing agent is used, 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 curing agent (B), one or more selected from the group consisting of a liquid curing agent (B-1) and a solid curing agent (B-2) can be used, and it is preferable to use a liquid curing agent (B-1). In one embodiment, the curing agent (B) consists of a liquid curing agent (B-1). "Liquid hardener" refers to a hardener that is liquid at a temperature of 20°C, and "solid hardener" refers to a hardener that is solid at a temperature of 20°C.

[0066] Examples of the acid anhydride curing agent include a curing agent having one or more acid anhydride groups in one molecule, and a curing agent having two or more acid anhydride groups in one molecule is preferable.Specific examples of the acid anhydride curing agent 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-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone. Examples of the acid anhydrides include tetracarboxylic dianhydrides, biphenyltetracarboxylic dianhydrides, naphthalenetetracarboxylic dianhydrides, oxydiphthalic dianhydrides, 3,3'-4,4'-diphenylsulfonetetracarboxylic 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 polymeric acid anhydrides such as styrene-maleic acid resins in which styrene and maleic acid are copolymerized. Examples of commercially available acid anhydride-based hardeners include "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by New Japan Chemical Co., Ltd.; "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Co., Ltd.; and "HN-2200" and "HN-5500" manufactured by Hitachi Chemical Co., Ltd.

[0067] The amine-based curing agent may, for example, be a curing agent having one or more, preferably two or more, amino groups in one molecule.Specific examples thereof include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc., and among these, aromatic amines are preferred.The amine-based curing agent is preferably a primary amine or secondary amine, more preferably a primary amine. 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'-diaminodiphenylether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propanediamine, and the like. bis(4-aminophenoxy)phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, and the like. As the amine-based curing agent, commercially available products may be used, and examples thereof include "SEIKACURE-S" manufactured by Seika Corporation, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., "Epicure W" manufactured by Mitsubishi Chemical Corporation, and "DTDA" manufactured by Sumitomo Seika Chemicals Co., Ltd.

[0068] The phenol-based curing agent includes a curing agent having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring in one molecule. Among them, a compound having a hydroxyl group bonded to a benzene ring is preferred. In addition, from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolac structure is preferred. Furthermore, from the viewpoint of adhesion, a nitrogen-containing phenol-based curing agent is preferred, and a triazine skeleton-containing phenol-based curing agent is more preferred. In particular, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a triazine skeleton-containing phenol novolac curing agent is preferred.

[0069] Specific examples of phenol-based curing agents include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd.; "NHN", "CBN", and "GPH" manufactured by 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" manufactured by DIC Corporation; "GDP-6115L", "GDP-6115H", and "ELPC75" manufactured by Gun-ei Chemical Co., Ltd.; and "2,2-diallyl bisphenol A" manufactured by Sigma-Aldrich Corporation.

[0070] The active group equivalent of the (B) curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., further 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 the active group.

[0071] The amount of the (B) curing agent is preferably determined by determining the number of active groups according to the number of epoxy 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, and even more preferably 0.5 or more, and is 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 taken as 1. Here, the "number of epoxy groups of the (A) epoxy resin" refers to the total value of all values ​​obtained by dividing the mass of the non-volatile components of the (A) epoxy resin present in the resin composition by the epoxy equivalent. In addition, the "number of active groups of the (B) curing agent" refers to the total value of all values ​​obtained by dividing the mass of the non-volatile components of the (B) curing agent present in the resin composition by the active group equivalent.

[0072] Relative to 100% by mass of non-volatile components in the resin composition, the amount of (B) curing agent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 1.0% by mass or more, and is 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 an inorganic filler (C). A cured product of the resin composition containing the inorganic filler (C) can usually have a small thermal expansion coefficient.

[0074] As the inorganic filler, an inorganic compound is used. Examples of the inorganic filler 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. In addition, spherical silica is preferred as the silica. (C) The inorganic filler may be used alone or in combination of two or more types.

[0075] As the (C) inorganic filler, one or more types selected from solid inorganic fillers and hollow inorganic fillers can be used. The term "solid inorganic filler" refers to an inorganic filler that does not substantially have voids or holes, and the term "hollow inorganic filler" refers to an inorganic filler that contains voids or holes. In one embodiment, the (C) inorganic filler is made of a solid inorganic filler.

[0076] From the viewpoint of significantly obtaining the desired effects of the present invention, the average particle size of the (B) inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and is preferably 5 μm or less, more preferably 4.5 μm or less, and even more preferably 4.1 μm or less.

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

[0078] (C) The specific surface area of ​​the inorganic filler is preferably 1 m 2 / g or more, more preferably 1.5m 2 / g or more, more preferably 2m 2 / g or more, particularly preferably 3m 2 / g or more. There is no particular upper limit, but it is preferably 60m 2 / g or less, 50m 2 / g or less or 40m 2 The specific surface area is determined by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.) according to the BET method, and 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" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs Co., Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", and "Silfill NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "SO-C5", "SO-C6", "FE9 series", "FEB series", and "FED series" manufactured by Admatechs Co., Ltd.; and "DAW-03", "DAW-10", "FB-105FD", and "UFP-30" manufactured by Denka Co., Ltd. The commercially available products may be used after being adjusted to an appropriate particle size distribution by pulverizing, mixing, classifying, or a combination thereof so as to have the above-mentioned particle size distribution.

[0080] (C) The inorganic filler may be treated with a surface treatment agent in order to improve moisture resistance and dispersibility. Examples of the surface treatment agent 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. The surface treatment agent may be used alone or in any combination of two or more.

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

[0082] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with 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 0.2 parts by mass to 3 parts by mass, and even more preferably 0.3 parts by mass to 2 parts by mass.

[0083] The degree of surface treatment with 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 set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition, it is more preferable that the content is 1 mg / m 2 Less than 0.8 mg / m is preferred. 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0084] The amount of carbon per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent 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 solid content, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. The carbon analyzer that can be used is the "EMIA-320V" manufactured by Horiba, Ltd.

[0085] The amount of the inorganic filler (C) relative to 100% by mass of the non-volatile 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 the inorganic filler (C) is not particularly limited, but 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 the non-volatile components in the resin composition. The cured product of the resin composition containing the inorganic filler (C) in such an amount range can effectively reduce the thermal expansion coefficient.

[0086] [(D) Curing accelerator] The resin composition of the present invention may further contain a curing accelerator (D) as an optional component. The curing accelerator (D) enables the curing time of the resin composition to be efficiently adjusted.

[0087] (D) Examples of the curing accelerator 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. The curing accelerators may be used alone or in combination of two or more.

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

[0089] Examples of the amine curing accelerator 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, of which 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferred.

[0090] Examples of the imidazole curing accelerator 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 isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-furan Examples of the imidazole compounds include imidazole compounds such as 2-ethyl-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 and epoxy resins. Of these, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

[0091] As the imidazole-based curing accelerator, commercially available products may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation, and "Curezol 2MZ", "2E4MZ", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", "Cl1Z-A", "2MZ-OK", "2MA-OK", "2MA-OK-PW", and "2PHZ" manufactured by Shikoku Chemical Industry Co., Ltd.

[0092] Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene. Examples of such biguanide include o-[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide. Of these, dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

[0093] Examples of metal-based curing 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 octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

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

[0095] [(E-1) Silane coupling agent] The resin composition of the present invention may further contain a silane coupling agent (E-1) as an optional component. However, when the silane coupling agent is used as a surface treatment agent for inorganic fillers, the inorganic fillers treated with the surface treatment agent are classified as the above-mentioned component (C). By containing the silane coupling agent as the component (E-1), it is expected that the resin component and the inorganic filler will bond.

[0096] Examples of the silane coupling agent include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate coupling agents. Among them, epoxysilane coupling agents containing an epoxy group and mercaptosilane coupling agents containing a mercapto group are preferred, and epoxysilane coupling agents are particularly preferred. The silane coupling agents may be used alone or in combination of two or more. In one embodiment, the component (E-1) contains a single type of silane coupling agent. In another embodiment, the component (E-1) 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 preferably contains multiple types of silane coupling agents, including the silane coupling agent used as the surface treatment agent of the component (C) and the silane coupling agent used as the component (E-1).

[0097] As the silane coupling agent, for example, a commercially available product may be used. 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 " (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", and the like.

[0098] Relative to 100% by mass of non-volatile components in the resin composition, the amount of (E-1) silane coupling agent 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, and is 10% by mass or less, 5% by mass or less, or 3% by mass or less.

[0099] Relative to 100% by mass of the resin component in the resin composition, the amount of the (E-1) silane coupling agent 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 is 15% by mass or less, 10% by mass or less, or 5% by mass or less.

[0100] [(E-2) Reactive component] The resin composition of the present invention may further contain a reactive component (E-2) as an optional component. The component (E-2) excludes the components (A), (B), (D) and (E-1). The component (E-2) has a reactive functional group and is expected to react with the component (A) and / or with the components (E-2). The reactive functional group may be one that exhibits reactivity upon heating or light irradiation. By including the component (E-2) in the resin composition, the component (E-2) can be incorporated into the crosslinked structure formed by the component (A). The component (E-2) may be used alone or in combination of two or more.

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

[0102] Examples of the component (E-2) include (E-2-1) a radically polymerizable compound and (E-2-2) a polyether skeleton-containing compound having a reactive functional group.

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

[0104] As the radical polymerizable compound (E-2-1), a compound having an ethylenically unsaturated bond can be used. As such a radical polymerizable compound (E-2-1), for example, a compound having a radical polymerizable group such as a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, an acryloyl group, a methacryloyl group, a fumaroyl group, a maleoyl group, a vinylphenyl group, a styryl group, a cinnamoyl group, and a maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) can be mentioned. As the radical polymerizable compound (E-2-1), one type may be used alone, or two or more types may be used in combination.

[0105] Specific examples of the radical polymerizable compound (E-2-1) 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 an aromatic carbon atom; allyl radical polymerizable compounds having one or more allyl groups; maleimide radical polymerizable compounds having one or more maleimide groups; etc. Among these, (meth)acrylic radical polymerizable compounds are preferred.

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

[0107] The polyalkylene oxide structure is represented by the formula (1): -(R f O) n In formula (1), n ​​generally represents an integer of 2 or more. This integer n is preferably 4 or more, more preferably 9 or more, and even more preferably 11 or more, and is generally 101 or less, preferably 90 or less, more preferably 68 or less, and even more preferably 65 or less. In formula (1), R feach independently represents an alkylene group which may have a substituent. The number of carbon atoms of the alkylene group is preferably 1 or more, more preferably 2 or more, and 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 the substituent that the alkylene group may have include a halogen atom, -OH, an alkoxy group, a primary or secondary amino group, an aryl group, -NH2, -CN, -COOH, -C(O)H, and -NO2. However, it is preferable that the alkyl group does not have a substituent. Specific examples of the polyalkylene oxide structure include a polyethylene oxide structure, a polypropylene oxide structure, a poly n-butylene oxide structure, a poly(ethylene oxide-co-propylene oxide) structure, a poly(ethylene oxide-ran-propylene oxide) structure, a poly(ethylene oxide-alt-propylene oxide) structure, and a poly(ethylene oxide-block-propylene oxide) structure.

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

[0109] Examples of commercially available products of the radical polymerizable compound (E-2-1) containing a polyalkylene oxide structure include monofunctional acrylates "AM-90G", "AM-130G", and "AMP-20GY" manufactured by Shin-Nakamura Chemical Co., Ltd.; bifunctional acrylates "A-1000", "A-B1206PE", "A-BPE-20", and "A-BPE-30"; monofunctional methacrylates "M-20G", "M-40G", "M-90G", "M-130G", and "M-230G"; and bifunctional 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" manufactured by Kyoeisha Chemical Co., Ltd.; "FA-023M" manufactured by Hitachi Chemical Co., Ltd.; and "Blenmer (registered trademark) PME-4000", "Blenmer (registered trademark) 50POEO-800B", "Blenmer (registered trademark) PLE-200", "Blenmer (registered trademark) PLE-1300", "Blenmer (registered trademark) PSE-1300", "Blenmer (registered trademark) 43PAPE-600B", and "Blenmer (registered trademark) ANP-300" manufactured by NOF Corporation. In one embodiment, "M-130G" or "BPE-1300N" is used as the radical polymerizable compound (E-2-1) containing a polyalkylene oxide structure.

[0110] The ethylenically unsaturated bond equivalent of the radical polymerizable compound (E-2-1) is preferably 20 g / eq. to 3000 g / eq., more preferably 50 g / eq. to 2500 g / eq., further 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 equivalent of the ethylenically unsaturated bond.

[0111] The weight average molecular weight (Mw) of the radically polymerizable compound (E-2-1) is preferably 150 or more, more preferably 250 or more, even more preferably 400 or more, and is preferably 40,000 or less, more preferably 10,000 or less, even more preferably 5,000 or less, and particularly preferably 3,000 or less.

[0112] Relative to 100% by mass of non-volatile components in the resin composition, the amount of the radically polymerizable compound (E-2-1) 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, and is 15% by mass or less, 10% by mass or less, or 8% by mass or less.

[0113] Relative to 100% by mass of the resin component in the resin composition, the amount of the radically polymerizable compound (E-2-1) 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 is 25% by mass or less, 20% by mass or less, or 15% by mass or less.

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

[0115] The polyether skeleton-containing compound having a reactive functional group (E-2-2) represents a polymer compound having a polyether skeleton. The polyether skeleton-containing compound having a reactive functional group (E-2-2) does not include the above-mentioned components (A) to (E-2-1). The polyether skeleton contained in the polyether skeleton-containing compound having a reactive functional group (E-2-2) is preferably a polyoxyalkylene skeleton composed of one or more monomer units selected from ethylene oxide units and propylene oxide units. Therefore, the polyether skeleton-containing compound having a reactive functional group (E-2-2) preferably does not include a polyether skeleton containing a monomer unit having 4 or more carbon atoms, such as a butylene oxide unit or a phenylene oxide unit. The polyether skeleton-containing compound having a reactive functional group (E-2-2) may also contain a hydroxyl group as a reactive functional group.

[0116] The polyether skeleton-containing compound (E-2-2) having a reactive functional group may 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; polydiaryl-alkylarylsiloxane skeletons such as polydiphenyl-methylphenylsiloxane skeletons, and the like, with polydialkylsiloxane skeletons being preferred, and polydimethylsiloxane skeletons being particularly preferred. The polyether skeleton-containing compound (E-2-2) containing a silicone skeleton may be, for example, polyoxyalkylene-modified silicone, alkyl-etherified polyoxyalkylene-modified silicone (polyoxyalkylene-modified silicone in which at least a part of the polyether skeleton terminal is an alkoxy group), and the like.

[0117] (E-2-2) The polyether skeleton-containing compound having a reactive functional group may contain a polyester skeleton. The polyester skeleton is preferably an aliphatic polyester skeleton. The hydrocarbon chain contained in the aliphatic polyester skeleton may be linear or branched, but is preferably branched. The number of carbon atoms contained in the polyester skeleton may be, for example, 4 to 16. Since the polyester skeleton can be formed from a polycarboxylic acid, a lactone, or an anhydride thereof, (E-2-2) the polyether skeleton-containing compound having a reactive functional group containing a polyester skeleton may have a carboxyl group at the molecular end, but preferably has a hydroxyl group as a reactive functional group at the molecular end.

[0118] (E-2-2) Examples of the polyether skeleton-containing compound having a reactive functional group include linear polyoxyalkylene glycols (linear polyalkylene 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 pentaerythritol ether, polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene pentaerythritol ether, and polyoxyethylene sorbitol. polyoxyalkylene glycols (polyalkylene glycols) such as polyoxyethylene sorbitol, polyoxypropylene sorbitol, and other multi-chain polyoxyalkylene glycols (multi-chain polyalkylene glycols); polyoxyethylene monoalkyl ethers, polyoxyethylene dialkyl ethers, polyoxypropylene monoalkyl ethers, polyoxypropylene dialkyl ethers, polyoxyethylene polyoxypropylene monoalkyl ethers, and polyoxyethylene polyoxypropylene dialkyl ethers; polyoxyalkylene esters such as polyoxyethylene monoesters, polyoxyethylene diesters, polypropylene glycol monoesters, polypropylene glycol diesters, polyoxyethylene polyoxypropylene monoesters, and polyoxyethylene polyoxypropylene diesters (including acetates, propionates, butyrates, (meth)acrylates, and the like);Polyoxyalkylene alkyl ether esters (including acetates, propionates, butyrates, (meth)acrylates, etc.) such as polyoxyethylene monoesters, polyoxyethylene diesters, polyoxypropylene monoesters, polyoxypropylene diesters, polyoxyethylene polyoxypropylene monoesters, polyoxyethylene polyoxypropylene diesters, polyoxyethylene alkyl ether esters, polyoxypropylene alkyl ether esters, and polyoxyethylene polyoxypropylene alkyl ether esters; polyoxyalkylene alkylamines such as polyoxyethylene alkylamines, polyoxypropylene alkylamines, and polyoxyethylene polyoxypropylene alkylamines; polyoxyalkylene alkylamides such as polyoxyethylene alkylamides, polyoxypropylene alkylamides, and polyoxyethylene polyoxypropylene alkylamides; polyoxyethylene dimethicone, poly Polyoxyalkylene-modified silicones such as polyoxypropylene dimethicone, polyoxyethylene polyoxypropylene dimethicone, polyoxyethylene polydimethylsiloxy alkyl dimethicone, polyoxypropylene polydimethylsiloxy alkyl dimethicone, and polyoxyethylene polyoxypropylene polydimethylsiloxy alkyl dimethicone; alkyl etherified polyoxyalkylene-modified silicones (polyoxyalkylene-modified silicones in which at least a portion of the polyether skeleton terminal is an alkoxy group) such as polyoxyethylene alkyl ether dimethicone, polyoxypropylene alkyl ether dimethicone, polyoxyethylene polyoxypropylene alkyl ether dimethicone, polyoxyethylene alkyl ether polydimethylsiloxy alkyl dimethicone, and polyoxyethylene polyoxypropylene alkyl ether polydimethylsiloxy alkyl dimethicone;

[0119] The number average molecular weight of the polyether skeleton-containing compound (E-2-2) having a reactive functional group is preferably 500 to 40000, more preferably 500 to 20000, and even more preferably 500 to 10000. The weight average molecular weight of the polyether skeleton-containing compound (E-2-2) is preferably 500 to 40000, more preferably 500 to 20000, and even more preferably 500 to 10000. The number average molecular weight and weight average molecular weight can be measured as polystyrene-equivalent values ​​by gel permeation chromatography (GPC).

[0120] The polyether skeleton-containing compound having a reactive functional group (E-2-2) is preferably liquid at 25° C. The viscosity of the polyether skeleton-containing compound having a reactive functional group (E-2-2) 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. The lower limit of the viscosity of the polyether skeleton-containing compound having a reactive functional group (E-2-2) 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. The viscosity may be a viscosity (mPa·s) obtained by measurement using a Brookfield viscometer.

[0121] (E-2-2) Commercially available polyether skeleton-containing compounds having a reactive functional group include, for example, "Pronon #102", "Pronon #104", "Pronon #201", "Pronon #202B", "Pronon #204", "Pronon #208", "Unilube 70DP-600B", and "Unilube 70DP-950B" (polyoxyethylene polyoxypropylene glycol) manufactured by NOF Corporation; "Pluronic (registered trademark) L-23" and "Pluronic (registered trademark) L-23" manufactured by ADEKA Corporation; Pluronic 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 Pluronic 25R-1, Pluronic 25R-2, Pluronic 17R-2, Pluronic 17R-3, Pluronic 17R-4 (polyoxyethylene polyoxypropylene glycol); Shin-Etsu Silicone's KF-6011, KF-6011P, KF-6012, KF-6013, KF-6015, KF-6016, KF-6017, KF-6017P, KF-6043, KF-6004, Examples of the polyether skeleton-containing compound having a reactive functional group (E-2-2) include polyether polyols or modified products thereof synthesized by the synthesis of reactive component e2e ("polyether polyol A") described below.

[0122] Relative to 100% by mass of non-volatile components in the resin composition, the amount of (E-2-2) a polyether skeleton-containing compound having a reactive functional group 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, and is 15% by mass or less, 10% by mass or less, or 8% by mass or less, and 15% by mass or less, 10% by mass or less, or 8% by mass or less.

[0123] Relative to 100% by mass of the resin component in the resin composition, the amount of the (E-2-2) polyether skeleton-containing compound having a reactive functional group 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 is 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 a non-reactive additive (E-3) as an optional component. The component (C), the component (E-2), and the optional additives described below are excluded from the component (E-3). Unlike the component (E-2), the component (E-3) does not have a reactive functional group at the end or side chain, and is an additive component that is not usually expected to react with the component (A) and / or with the components (E-2). However, it is acceptable that the component (E-3) may react with other components at a site other than the end or side chain. A typical example of the component (E-3) is a high molecular weight component. The high molecular weight component can function as a plasticizer. Examples of commercially available products of the component (E-3) include butadiene homopolymers "B-1000", "B-2000", and "B-3000" manufactured by Nippon Soda Co., Ltd. One type of the component (E-3) may be used alone, or two or more types may be used in combination.

[0125] The number average molecular weight of the component (E-3) is preferably 500 to 40000, more preferably 500 to 20000, and even more preferably 500 to 10000. The weight average molecular weight of the component (E-3) is preferably 500 to 40000, more preferably 500 to 20000, and even more preferably 500 to 10000. The number average molecular weight and weight average molecular weight can be measured as polystyrene-equivalent values ​​by gel permeation chromatography (GPC).

[0126] The component (E-3) is liquid at 25°C, or the component (E-3) has a viscosity at 45°C of preferably 100000mPa·s or less, more preferably 50000mPa·s or less, even more preferably 30000mPa·s or less, even more preferably 10000mPa·s or less, even more preferably 5000mPa·s or less, even more preferably 4000mPa·s or less, even more preferably 3000mPa·s or less, even more preferably 2000mPa·s or less, particularly preferably 1500mPa·s or less or 500mPa 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 0.5mPa·s or more, more preferably 1mPa·s or more, even more preferably 2mPa·s or more, even more preferably 3mPa·s or more, and particularly preferably 4mPa·s or more. The viscosity may be a viscosity (mPa·s) obtained by measurement using a B-type viscometer.

[0127] The amount of the (E-3) component, relative to 100% by mass of the nonvolatile components in the resin composition, is not limited as long as the porosity of the cured product of the resin composition is within the above-mentioned range, 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, and is 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 the (E-3) component, 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 above-mentioned range, 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 is preferably 25% by mass or less, 20% by mass or less, or 15% by mass or less, from the viewpoint of obtaining a cured product with excellent mechanical strength.

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

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

[0131] Examples of the peroxide radical polymerization initiator include hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; dialkyl peroxide 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-hexyne; dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, and bis(4-tert-butylcyclohexyl)peroxydica. diacyl peroxide compounds such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, tert-hexylperoxyisopropyl monocarbonate, tert-butyl peroxylaurate, (1,1-dimethylpropyl)2-ethylperhexanoate, tert-butyl 2-ethylperhexanoate, tert-butyl 3,5,5-trimethylperhexanoate, tert-butylperoxy-2-ethylhexyl monocarbonate, tert-butylperoxymaleic acid, and other peroxy ester compounds.

[0132] Examples of the azo radical polymerization initiator 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-carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, and 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile; 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], and the like. azo amide compounds such as 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); alkyl azo compounds such as 2,2'-azobis(2,4,4-trimethylpentane) and 2,2'-azobis(2-methylpropane); and the like.

[0133] The radical polymerization initiator (F) is preferably one having a medium temperature activity. Specifically, the radical polymerization initiator (F) preferably has a 10-hour half-life temperature T10 (°C) 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 products of such radical polymerization initiator (F) include "Luperox 531M80" manufactured by Arkema Fuji Co., Ltd., "Perhexyl (registered trademark) O" manufactured by NOF Corporation, and "MAIB" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

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

[0135] [(G) Other additives] The resin composition of the present invention may further contain any additive as an optional non-volatile component in addition to the above-mentioned components (A) to (F). Examples of such additives include organic fillers such as rubber particles, polyamide fine particles, and silicone particles; thermoplastic resins such as polycarbonate resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, and polyester resins; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, 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 bentone, montmorillonite, etc. Examples of the additives include thickeners; silicone-based antifoaming agents, acrylic-based antifoaming agents, fluorine-based antifoaming agents, vinyl resin-based antifoaming agents, and other defoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenol-based antioxidants and hindered amine-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, and red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide). The additives may be used alone or in combination of two or more in any ratio. In an embodiment, the resin composition contains a hollow organic filler as the organic filler. However, from the viewpoint of improving the accuracy of the porosity measurement, it is preferable not to use a hollow organic filler as the organic filler. From this viewpoint, even if the resin composition contains a hollow organic filler, the content thereof is more preferably less than 0.005 mass%, even more preferably 0.003 mass% or less, and particularly preferably 0.001 mass% or less, when the non-volatile components of the resin composition are taken as 100 mass%.

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

[0137] [Method of producing resin composition] The resin composition of the present invention can be produced, for example, by mixing the above-mentioned components. The above-mentioned components may be mixed partially or entirely at the same time, or may be mixed in sequence. In the process of mixing each component, the temperature may be appropriately set, and thus heating and / or cooling may be performed temporarily or throughout. In addition, stirring or shaking may be performed in the process of mixing each component.

[0138] [Characteristics of resin composition] Usually, the above-mentioned resin composition has thermosetting properties. Therefore, a cured product can be obtained by curing the resin composition with heat. The porosity (area %) of this cured product is 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%, as described above. This makes it possible to provide a resin composition or resin paste that can suppress the occurrence of warping and can give 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 a 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 small dielectric constant (Dk) value of the cured product. Specifically, the dielectric constant (Dk) value tends to be less than 3.6, preferably 3.5 or less, more preferably less than 3.5. This can provide a cured product with excellent dielectric properties. The lower limit of the dielectric constant (Dk) can be 1.0 or more or 2.0 or more. The resin composition of the present invention tends to have a small dielectric loss tangent (Df) value of the cured product. Specifically, the dielectric loss tangent (Df) value tends to be less than 0.03, preferably less than 0.025, more preferably less than 0.02, and may be less than 0.01, less than 0.008, less than 0.006, or less than 0.005. This can provide a cured product with excellent dielectric properties. The lower limit of the dielectric loss tangent (Df) can be 0.0001 or more. The resin composition of the present invention shows a tendency that the dielectric constant (Dk) value of the cured product is less than 3.6, preferably 3.5 or less, more preferably less than 3.5, and the dielectric loss tangent (Df) value of the cured product is 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 the relative dielectric constant can be measured by the method described below. A test piece for measuring the dielectric loss tangent and the relative dielectric constant can be prepared according to the method and curing conditions described below.

[0141] The resin composition of the present invention tends to cause a warpage of less than 2000 μm (2 mm) in a cured product having a thickness of 300 μm, preferably 1950 μm or less, more preferably 1900 μm or less, more preferably 1850 μm or less. The warpage can be measured by the method described in the Examples section below. In this way, the resin composition of the present invention can provide a cured product in which the occurrence of warpage is suppressed. The warpage can be measured by the method described below. A test piece for measuring the warpage can be prepared according to the method and curing conditions described below.

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

[0143] [Applications of resin composition] The resin composition of the present invention can be suitably used as a resin composition (resin composition for encapsulation) for encapsulating electronic devices such as organic EL devices and semiconductors, and can be particularly suitably used as a resin composition for encapsulating semiconductors (resin composition for semiconductor encapsulation), preferably a resin composition for encapsulating semiconductor chips (resin composition for semiconductor chip encapsulation). In addition, the resin composition can be used as a resin composition for insulating applications for insulating layers other than encapsulation. For example, the resin composition can be suitably used as a resin composition for forming an insulating layer of a semiconductor chip package, for example, a rewiring formation layer (resin composition for the insulating layer of a semiconductor chip package, resin composition for the rewiring formation layer), and a resin composition for forming an insulating layer of a circuit board (including a printed wiring board) (resin composition for the 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 an insulating layer of a semiconductor chip package. Examples of the semiconductor chip package 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] The resin composition may also be used as an underfill material, for example, as a material for MUF (Molding Under Filling) that is used after a semiconductor chip is connected to a substrate.

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

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

[0148] The use of the resin sheet is the same as the use of the resin composition of the present invention described above. Examples of packages using applicable circuit boards include FC-CSP, MIS-BGA packages, and ETS-BGA packages. Examples of applicable semiconductor chip packages include 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 a material for MUF used after connecting a semiconductor chip to a substrate. Furthermore, the resin sheet can be used in a wide range of other applications requiring high insulation reliability.

[0149] [Circuit board] The circuit board according to one embodiment of the present invention may include a cured product of the resin composition of the present invention. The circuit board can be produced, for example, according to a known method, and the materials used as the substrate and the conductor layer that may be formed on the substrate are also 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 according to a known method. For example, the resin composition layer can be formed by a compression molding method. In the compression molding method, the substrate and the resin composition are usually placed in a mold, and pressure and, if necessary, heat are applied to the resin composition in the mold to form a resin composition layer on the substrate.

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

[0152] In addition, the specific operation of the compression molding method may be, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. A resin composition is placed on the lower mold. Also, a substrate (a release film, if necessary) is attached to the upper mold. Then, the upper mold and the lower mold are clamped so that the resin composition placed on the lower mold contacts the substrate 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 so that good sealing is achieved. For example, the temperature of the mold 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, and preferably 50 MPa or lower, more preferably 30 MPa or lower, and particularly preferably 20 MPa or lower. The cure time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 3 minutes or more, and 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. Usually, the mold is removed after the formation of the resin composition layer. The mold may be removed before or after the resin composition layer is thermally cured.

[0154] After forming the resin composition layer on the substrate, the resin composition layer is thermally cured (post-cured) to form a cured layer. The thermal 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 the resin composition layer is thermally cured, the resin composition layer may be subjected to a preheating treatment at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of usually 50° C. or more and less than 120° C. (preferably 60° C. or more and 110° C. or less, more preferably 70° C. or more and 100° C. or less) for usually 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

[0156] In the manner described above, a circuit board having a cured layer formed of a cured product of the resin composition of the present invention can be produced. The method for producing a circuit board may further include any optional step.

[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 this semiconductor chip package include the following.

[0158] The semiconductor chip package according to the first example includes the above-mentioned circuit board 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 may be any conditions that allow conductive connection between the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board. For example, the conditions used in flip-chip mounting of the semiconductor chip may be used. Also, 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 bonding a semiconductor chip to a circuit board. The bonding conditions are that the bonding temperature is usually 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 the bonding time is usually in the range of 1 second to 60 seconds (preferably in the range of 5 seconds to 30 seconds).

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

[0162] After the semiconductor chip is bonded to the circuit board, the semiconductor chip may be filled with a molded underfill material, which may be the resin composition described above.

[0163] The 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 usually functions as an encapsulation layer. An example of the semiconductor chip package according to the second example is a fan-out type WLP.

[0164] Fig. 1 is a cross-sectional view showing a schematic configuration of a fan-out type WLP as an example of a semiconductor chip package according to the present embodiment. A semiconductor chip package 100 as a fan-out type WLP includes, for example, a semiconductor chip 110, a sealing layer 120 formed so as to cover the periphery of the semiconductor chip 110, a rewiring formation layer 130 as an insulating layer provided on the surface of the semiconductor chip 110 opposite to the sealing layer 120, a rewiring layer 140 as a conductor layer, a solder resist layer 150, and a bump 160, as shown in Fig. 1.

[0165] The method for manufacturing such a semiconductor chip package includes: (A) a step of laminating a temporary fixing film on a substrate; (B) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (C) forming an encapsulation layer on the semiconductor chip; (D) peeling the substrate and the temporary fixing film from the semiconductor chip; (E) a step of forming a rewiring formation layer on the surface from which the substrate and the temporary fixing film of the semiconductor chip have been peeled off; (F) forming a rewiring layer as a conductor layer on the rewiring formation layer; and (G) forming a solder resist layer on the rewiring layer; The method for manufacturing the semiconductor chip package further comprises: (H) A process of dicing and separating multiple semiconductor chip packages into individual semiconductor chip packages. may also include

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

[0167] Examples of the substrate include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel (SPCC); substrates such as FR-4 substrates in which glass fibers are impregnated with epoxy resin or the like and then heat-cured; and substrates made of bismaleimide triazine resins such as BT resin.

[0168] The temporary fixing film may be made of any material that can be peeled off from the semiconductor chip and can temporarily fix the semiconductor chip. Commercially available products include "Riva Alpha" manufactured by Nitto Denko Corporation.

[0169] (Process (B)) Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. The temporary fixing of the semiconductor chip can be performed using, for example, a device such as a flip chip bonder or a die bonder. The layout and number of the semiconductor chips can be appropriately set depending on 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 temporarily fixed by arranging them in a matrix shape of multiple rows and multiple columns.

[0170] (Process (C)) Step (C) is a step of forming an encapsulating layer on a semiconductor chip. The encapsulating layer can be formed by a cured product of the resin composition of the present invention. The encapsulating layer is usually formed by a method including a step of forming a resin composition layer on a semiconductor chip and a step of thermally curing the resin composition layer to form a cured product layer as the encapsulating layer. The formation of the resin composition layer on the semiconductor chip can be performed by the same method as the method of 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 the semiconductor chip, the resin composition layer is thermally cured to obtain an encapsulation layer that covers the semiconductor chip. This encapsulates the semiconductor chip with the cured product of the resin composition of the present invention. The thermal curing conditions of the resin composition layer may be the same as the thermal curing conditions of the resin composition layer in the manufacturing method of the circuit board. Furthermore, before thermally curing the resin composition layer, a preheating treatment may be performed on the resin composition layer at a temperature lower than the curing temperature. The treatment conditions of this preheating treatment may be the same as the preheating treatment in the manufacturing method of the circuit board.

[0172] (Process (D)) Step (D) is a step of peeling off the substrate and the temporary fixing film from the semiconductor chip. It is desirable to adopt an appropriate peeling method according to the material of the temporary fixing film. For example, the peeling method may be a method of heating, foaming or expanding the temporary fixing film to peel it off. In addition, for example, the peeling method may be a method of irradiating the temporary fixing film with ultraviolet light through the substrate to reduce the adhesive strength of the temporary fixing film to peel it off.

[0173] In the method of peeling off the temporary fixing film by heating, foaming or expanding it, the heating conditions are usually 100° C. to 250° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. In the method of peeling off the temporary fixing film by reducing the adhesive strength of the temporary fixing film by irradiating it with ultraviolet light, the irradiation amount of ultraviolet light is usually 10 mJ / cm 2 ~1000mJ / cm 2 It is.

[0174] When the base material and the temporary fixing film are peeled off from the semiconductor chip as described above, the surface of the encapsulation layer is exposed. The manufacturing method of the semiconductor chip package may include polishing the exposed surface of the encapsulation layer. The polishing can improve the smoothness of the surface of the encapsulation layer. The polishing method can be the same as that described in the manufacturing method of the circuit board.

[0175] (Process (E)) Step (E) is a step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off. Usually, this rewiring formation layer is formed on the semiconductor chip and the sealing layer.

[0176] The material of the rewiring formation layer may be any material having insulating properties. When the sealing layer is formed from the cured product of the resin composition of the present invention, the rewiring formation layer formed on the sealing layer may be formed from a photosensitive resin composition.

[0177] After forming the rewiring formation layer, a via hole is usually formed in the rewiring formation layer in order to connect the semiconductor chip and the rewiring layer to each other. When the rewiring formation layer is formed of a photosensitive resin composition, the method of forming the via hole usually includes exposing the surface of the rewiring formation layer through a mask. Examples of the active energy ray include ultraviolet light, visible light, electron beams, and X-rays, and ultraviolet light is particularly preferred. Examples of the exposure method include a contact exposure method in which a mask is attached to the rewiring formation layer and exposed to light, and a non-contact exposure method in which a mask is not attached to the rewiring formation layer and exposed to light using parallel light.

[0178] The exposure can form a latent image in the redistribution layer, and then development can be performed to remove a part of the redistribution layer to form a via hole as an opening portion penetrating the redistribution layer. The development can be performed by either wet development or dry development. Examples of the development method include a dip method, a paddle method, a spray method, a brushing method, and a scraping method, and the paddle method is preferable from the viewpoint of resolution.

[0179] The shape of the via hole is not particularly limited, but is generally circular (approximately 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 opening of the via hole on the surface of the rewiring formation layer.

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

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

[0182] In step (G), bumping processing may be performed to form bumps, if necessary. The bumping processing can be performed by a method such as solder balls or solder plating. In addition, the formation of via holes in the bumping processing can be performed in the same manner as in step (E).

[0183] (Process (H)) The method for manufacturing a semiconductor chip package may include a step (H) in addition to the steps (A) to (G). The step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them. The method for 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 FIG. 1, in which the rewiring formation layer 130 or the solder resist layer 150 is formed from a cured product of the resin composition of the present invention.

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

[0186] The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by 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 8 parts of hardener ba (anhydride hardener "MH-700" manufactured by New Japan Chemical Co., Ltd., anhydride group equivalent: 164 g / eq.) as component (B), 2 parts of epoxy resin aa (liquid epoxy resin "ZX1059" manufactured by Nippon Steel Chemical & Material Co., Ltd., 1:1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq.) as component (A), Epoxy resin ab (alicyclic epoxy resin "Celloxide 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 curing accelerator "2MA-OK-PW" manufactured by Shikoku Chemical Industry Co., Ltd.) 0.4 parts, component (A) 2 parts of epoxy resin ad (ADEKA's glycidylamine type epoxy resin "EP3950L", epoxy equivalent: 95 g / eq.) as component (A), 2 parts of epoxy resin ae (ADEKA's dicyclopentadiene dimethanol type epoxy resin "EP-4088S", epoxy equivalent: 170 g / eq.) as component (A), 3 parts of reactive component e2a (Shin-Nakamura Chemical Co., Ltd.'s compound having a methacryloyl group and a polyethylene oxide structure "M-130G") as component (E-2), 0.1 parts of radical polymerization initiator (NOF Corp.'s "Perhexyl (registered trademark) O", 10-hour half-life temperature T10: 69.9°C) as component (F), 0.1 parts of inorganic filler ca (Silica surface-treated with surface treatment agent "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.) as component (C), true density: 2.6 g / cm 3 , average particle size: 1.5μm, specific surface area: 2.78m 2 A resin composition was prepared by uniformly dispersing 90 parts of silica (also referred to as "silica A") and 0.2 parts of a silane coupling agent e1a ("KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.) as the component (E-1) using a mixer. The prepared resin composition was in a paste form. Hereinafter, the resin composition thus prepared, which contains at least the components (A), (B) and (C), is also referred to as "resin paste A".

[0188] The amount of solvent contained in the prepared resin paste A of Example 1 was 0 mass% (i.e., none) relative to 100 mass% of the non-volatile components of the resin composition. The viscosity of the resin paste A of Example 1 was measured at 25°C using an E-type viscometer and was 80 Pa s. The viscosity measured in this manner is shown in Table 1.

[0189] (2) Measurement and evaluation of the cured product Then, the cured product of Resin Paste A was subjected to the measurements and evaluations described below.

[0190] [Example 2] In Example 1, instead of blending 2 parts each of epoxy resin aa ("ZX1059"), epoxy resin ab ("Celloxide 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") ("Celloxide 2021P"), 2 parts of epoxy resin ac ("HP4032D"), Two parts of epoxy resin af (Nagase ChemteX Corporation's polyether-containing epoxy resin "EX-992L", epoxy equivalent: 680 g / eq.), two parts of epoxy resin ag (Osaka Gas Chemicals's fluorene structure-containing epoxy resin "EG-280", epoxy equivalent: 460 g / eq.), and two parts of epoxy resin ah (ADEKA Corporation's glycidylamine type epoxy resin "EP-3980S", epoxy equivalent: 115 g / eq.) were mixed. In Example 1, the amount of the 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 blending 3 parts of reactive component e2a ("M-130G") as component (E-2), 3 parts of reactive component e2b (bifunctional methacrylate "BPE-1300N" manufactured by Shin-Nakamura Chemical Co., Ltd.) were blended.

[0191] Resin paste A was prepared in the same manner as in Example 1 except for the above. The amount of solvent contained in the prepared resin paste A of Example 2 was 0 mass% (i.e., none) relative to 100 mass% of the non-volatile components of the resin composition. Then, using resin paste A, the cured product 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 ("Celloxide 2021P"), epoxy resin ac ("HP4032D"), epoxy resin ad ("EP3950L") and epoxy resin ae ("EP-4088S") used as component (A) were changed from 2 parts each to 3 parts each. In addition, in Example 1, instead of mixing 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 mixed. Furthermore, in Example 1, instead of mixing 0.4 parts of the curing accelerator da ("2MA-OK-PW") as component (D), 0.4 parts of the curing accelerator db (imidazole-based curing accelerator "2E4MZ" manufactured by Shikoku Chemical Industries, Ltd.) were mixed.

[0193] Resin paste A was prepared in the same manner as in Example 1 except for the above. The amount of solvent contained in the prepared resin paste A of Example 3 was 0 mass% (i.e., none) relative to 100 mass% of the non-volatile components of the resin composition. Then, using resin paste A, the cured product was measured and evaluated in the same manner as in Example 1.

[0194] [Example 4] In Example 1, instead of mixing 2 parts each of epoxy resin aa ("ZX1059"), epoxy resin ab ("Celloxide 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 mixed. In Example 1, instead of blending 90 parts of inorganic filler ca ("silica A") as component (C), inorganic filler cb (silica surface-treated with a surface treatment agent "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd., true density: 2.6 g / cm 3 , average particle size: 4μm, specific surface area: 3.01m 2 / g; also called "Silica B") was blended in 130 parts. Furthermore, in Example 1, the amount of the silane coupling agent e1a ("KBM403") blended as the component (E-1) was changed from 0.2 parts to 0.1 parts. Furthermore, the components (E-2) and (F) used in Example 1 were not blended.

[0195] Resin paste A was prepared in the same manner as in Example 1 except for the above. The amount of solvent contained in the prepared resin paste A of Example 4 was 0 mass% (i.e., none) relative to 100 mass% of the non-volatile components of the resin composition. Then, using resin paste A, the cured product was measured and evaluated in the same manner as in Example 1.

[0196] [Example 5] In Example 4, instead of mixing 3 parts of epoxy resin aa ("ZX1059"), 2 parts of epoxy resin ac ("HP4032D"), and 1 part of epoxy resin ai ("JP-100") as component (A), 3 parts of epoxy resin aa ("ZX1059"), 1 part of epoxy resin ac ("HP4032D"), and 1 part of epoxy resin ai ("EG-280") were mixed. In addition, in Example 4, instead of blending 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 blended. That is, in Example 5, multiple types of silane coupling agents were blended. Further, in Example 4, as the component (E-2), reactive component e2c (polyoxyalkylene-modified silicone resin "KF-6012" manufactured by Shin-Etsu Silicone Co., Ltd., viscosity (25 ° C.): 1500 mm 2 / s) was blended in 1 part. In addition, in Example 4, the blending amount of the radical polymerization initiator as the component (F) was changed from 0.1 parts to 0 parts. That is, in Example 5, the component (F) was not blended.

[0197] Resin paste A was prepared in the same manner as in Example 4, except for the above. The amount of solvent contained in the prepared resin paste A of Example 5 was 0 mass% (i.e., none) relative to 100 mass% of the non-volatile components of the resin composition. Then, using resin paste A, the cured product was measured and evaluated in the same manner as in Example 1.

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

[0199] Resin paste A was prepared in the same manner as in Example 5, except for the above. The amount of solvent contained in the prepared resin paste A of Example 6 was 0 mass% (i.e., none) relative to 100 mass% of the non-volatile components of the resin composition. Then, using resin paste A, the cured product was measured and evaluated in the same manner as in Example 1.

[0200] [Example 7] In Example 5, instead of mixing 3 parts of epoxy resin aa ("ZX1059"), 1 part of epoxy resin ac ("HP4032D"), and 1 part of epoxy resin ag ("EG-280") as the component (A), 3 parts of epoxy resin aa ("ZX1059"), 1 part of epoxy resin ac ("HP4032D"), and 1 part of epoxy resin ad ("EP3950L") were mixed. In Example 5, instead of blending one part of reactive component e2c ("KF-6012") as component (E-2), one part of reactive component e2e (also called "polyether polyol A") was blended. The reactive component e2e was obtained by synthesizing it as follows.

[0201] <Synthesis of reactive component e2e ("Polyether polyol A")> In a reaction vessel, 22.6 g of ε-caprolactone monomer (Daicel Corporation, "Placcel M"), 10 g of polypropylene glycol (Fujifilm Wako Pure Chemical Industries, Ltd., "Polypropylene glycol, diol type, 3,000"), and 1.62 g of tin(II) 2-ethylhexanoate (Fujifilm Wako Pure Chemical Industries, Ltd.) were charged, and the mixture was heated to 130°C under a nitrogen atmosphere and stirred for about 16 hours to react. The product after the reaction was dissolved in chloroform, and the product was reprecipitated with methanol and then dried. As a result, a polyester polyol having an aliphatic skeleton and terminated with a hydroxyl group was obtained as the reactive component e2e ("polyether polyol A"). The reactive component e2e ("polyether polyol A") had an Mn of 9000 from GPC analysis.

[0202] Resin paste A was prepared in the same manner as in Example 5, except for the above. The amount of solvent contained in the prepared resin paste A of Example 7 was 0 mass% (i.e., none) relative to 100 mass% of the non-volatile components of the resin composition. Then, using resin paste A, the cured product 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 ("Celloxide 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 ("Celloxide 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. In Example 3, instead of blending 90 parts of the inorganic filler ca ("silica A") as the component (C), 130 parts of the inorganic filler cb ("silica B") was blended. Furthermore, in Example 3, the amount of the silane coupling agent e1a ("KBM403") blended as the component (E-1) was changed from 0.2 parts to 0.3 parts. In addition, in Example 3, instead of blending 3 parts of reactive component e2a ("M-130G") as component (E-2), 2 parts of reactive component e2e ("Polyether polyol A") were blended, and the blending amount of radical polymerization initiator as component (F) was changed from 0.1 part to 0 part. That is, in Example 8, component (F) was not blended.

[0204] Resin paste A was prepared in the same manner as in Example 3 except for the above. The amount of solvent contained in the prepared resin paste A of Example 8 was 0 mass% (i.e., none) relative to 100 mass% of the non-volatile components of the resin composition. Then, using resin paste A, the cured product 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 ("Celloxide 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 ("Celloxide 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. In Example 8, instead of blending 3 parts of curing agent bb ("Kayahard AA") as component (B), 3 parts of curing agent bc ("2,2-diallyl bisphenol A" manufactured by Sigma-Aldrich) were blended. Furthermore, in Example 8, the amount of inorganic filler cb ("silica B") blended as component (C) was changed from 130 parts to 100 parts. In Example 8, instead of blending 2 parts of reactive component e2e ("Polyether polyol A") as the component (E-2), 2 parts of reactive component e2c ("KF-6012") was blended.

[0206] Resin paste A was prepared in the same manner as in Example 8, except for the above. The amount of solvent contained in the prepared resin paste A of Example 9 was 0 mass% (i.e., none) relative to 100 mass% of the non-volatile components of the resin composition. Then, using resin paste A, the cured product was measured and evaluated in the same manner as in Example 1.

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

[0208] Resin paste A was prepared in the same manner as in Example 4, except for the above. The amount of solvent contained in the prepared resin paste A of Example 10 was 0 mass% (i.e., none) relative to 100 mass% of the non-volatile components of the resin composition. Then, using resin paste A, the cured product was measured and evaluated in the same manner as in Example 1.

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

[0210] Resin paste A was prepared in the same manner as in Example 4, except for the above. The amount of solvent contained in the prepared resin paste A of Comparative Example 1 was 0 mass% (i.e., none) relative to 100 mass% of the non-volatile components of the resin composition. Then, using resin paste A, the cured product 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 the component (E-3).

[0212] Resin paste A was prepared in the same manner as in Comparative Example 1, except for the above. The amount of solvent contained in the prepared resin paste A of Comparative Example 2 was 0 mass% (i.e., none) relative to 100 mass% of the non-volatile components of the resin composition. Then, using resin paste A, the cured product was measured and evaluated in the same manner as in Example 1.

[0213] [Comparative Example 3] In Comparative Example 2, instead of blending 130 parts of inorganic filler ca ("silica A") as component (C), 120 parts of inorganic filler ca ("silica A") and inorganic filler cc (alumina surface-treated with the surface treatment agent "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd. and classified to a maximum particle size of 5 μm or less, true density: 3.98 g / cm 3 , maximum particle size: 5μm, average particle size: 1.0μm, specific surface area: 3.98m 2 / g; also called "alumina A") was blended at 30 parts. In addition, in Comparative Example 2, the blending amount of the non-reactive additive e3a ("B-2000") as the 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 above. The amount of solvent contained in the prepared resin paste A of Comparative Example 3 was 0 mass% (i.e., none) relative to 100 mass% of the non-volatile components of the resin composition. Then, using resin paste A, the cured product was measured and evaluated in the same manner as in Example 1.

[0215] <Measurement and evaluation of the cured product> Cured products of the resin pastes A obtained in Examples 1 to 10 and Comparative Examples 1 to 3 were obtained as follows, and were measured and evaluated.

[0216] <Porosity measurement> (1) Preparation of hardened material The resin pastes A obtained in Examples 1 to 10 and Comparative Examples 1 to 3 were cured according to a curing method including the following (1-1) compression molding step and (1-2) post-cure step in this order, thereby obtaining cured products with a degree of cure of 95% or more.

[0217] (1-1) Compression molding process The compression molding process employed was a process in which a resin composition was placed so as to be bonded to a silicon wafer, and then compression molded under conditions of a pressure of 15 tons, a temperature of 130°C, and a time of 10 minutes to obtain a compression molded body of the resin composition bonded to the silicon wafer and having a thickness of 300 μm.

[0218] Specifically, in the compression molding step, the above-mentioned standardized compression molding step was adopted, and the following steps (c1) to (c4) were carried out in this order. (c1) A step of placing a silicon wafer and a resin composition in a mold to which a release film is attached (c2) A step of closing the mold within 90 seconds after placing the resin composition to bond the silicon wafer and the resin composition. (c3) A process of reducing the pressure inside the mold to a pressure reduction level within the range of 0 to 0.7 torr (c4) A process of compression molding under conditions of a pressure of 15 tons, a temperature of 130°C, and a time of 10 minutes to obtain a compression molded body of the resin composition having a thickness of 300 μm bonded to the silicon wafer.

[0219] In step (c1), a compression molding machine (Apic Yamada's compression molding machine "WCM-300") was used, which was configured to include a pair of separable dies. In this step, the inside of the die was heated to 130°C (mold temperature), which is the temperature used in step (c4). A silicon wafer (thickness: 775 μm, diameter: 12 inches) was used after being subjected to a release treatment. The silicon wafer was fixed to the surface of the die located vertically below out of the pair of dies. A release film was attached to the die facing the silicon wafer out of the pair of dies. AGC's "Aflex (registered trademark) 50N 390NT" (mirror finish) was used as the release film.

[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 out and placed at the center of the silicon wafer. The amount of resin paste A used was sufficient to cover the entire silicon wafer surface and to form a resin composition layer with a thickness of 300 μm.

[0221] In step (c4), the thickness of the compression molded body obtained was set to 300 μm. As the compression molding machine, a compression molding machine was used in which the pressure in the mold reaches 15 tons from an applied pressure of 0 tons within 60 seconds. The 10 minutes was defined as the elapsed time after the pressure reached 15 tons. The compression molded body (with silicon wafer) obtained in this manner is also referred to as "compression molded body C" hereinafter.

[0222] The compression molded body C (compression molded body before post-cure process) of Example 1 obtained through the same process as the compression molding process was removed from the mold together with the silicon wafer, and the degree of cure of the compression molded body was immediately measured by differential scanning calorimetry using a differential scanning calorimeter (Hitachi High-Tech Science Corporation "DSC7020"), which was 85%. In addition, the porosity of the compression molded body C (porosity before post-cure) was measured, which was 0.005%. The porosity was measured in the same manner as the porosity of the cured product D described later.

[0223] (1-2) Post-cure process The post-cure step involved heating the compression molded product of the resin composition obtained under nitrogen atmosphere at 150° C. for 1 hour to obtain a cured product.

[0224] Specifically, in the post-cure step, the above-mentioned standardized post-cure step was adopted, and the following steps (p1) to (p2) were carried out in this order. (p1) a step of placing the compression molded resin composition removed from the mold in an oven set at a temperature of 150° C. and 1 atmospheric pressure in a nitrogen atmosphere and waiting for one hour to obtain a cured product; and (p2) A process of removing the cured product from the oven within 120 seconds after step (p1) and allowing it to cool in a room temperature and normal pressure environment.

[0225] In step (p1), Yamato Scientific Co., Ltd.'s "DN6101" oven was used. Prior to step (p1), the oven was set to a nitrogen atmosphere, a temperature of 150°C, and 1 atm. Prior to step (p1), the compression molded body to be put into the oven was the one (compression molded body C) that was taken out of the mold used in step (c4) together with the silicon wafer. The thickness of the resin composition layer of the compression molded body C of Example 1 that was put into the oven was 305 μm.

[0226] In step (p2), the cured product removed from the oven was allowed to cool indoors. The indoor pressure was normal (about 1 atm), the temperature was room temperature (about 23°C), and the humidity was 50%. After 6 hours, it was confirmed that the surface temperature of the cured product had reached 23°C.

[0227] It was confirmed that the thickness of the resin composition layer in the cured product obtained from the resin paste A of Example 1 obtained through the step (p2) was less than ±5% of the thickness of 305 μm before post-cure and was within the range of 300 μm ±5 μm. In addition, the degree of cure of the resin composition layer in the cured product was measured by differential scanning calorimetry using a differential scanning calorimeter (Hitachi High-Tech Science Corporation "DSC7020"), and was 100%. It was also confirmed that the cure shrinkage of the resin composition layer in the cured products of other Examples and Comparative Examples was less than ±5% of the thickness of 300 μm before post-cure and the degree of cure was 95% or more. Hereinafter, the cured product (with silicon wafer) obtained in this manner is also referred to as "cured product D".

[0228] (2) Measurement of porosity of hardened material (2-1) Determining the observation area The following procedure was carried out to obtain an SEM cross-sectional image of cured material D. The SEM used was an SEM attached to the FIB-SEM hybrid system "SMI3050SE" manufactured by SII NanoTechnology (now Hitachi High-Technologies Corporation). First, the cured product D was cut into 1 cm squares with the silicon wafer still attached. After that, the longitudinal cross section of each cut piece was cut using the FIB attached to the FIB-SEM hybrid system. When cutting the cross section, the FIB was focused at a position of 30 μm in width and 30 μm in depth. The obtained cross section was then observed at a magnification of 27,000 times using an SEM, and a region in 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 observed 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 cut surface of the silicon wafer or the cut surface of the resin composition layer, and the in-plane direction refers to the direction parallel to the surface of the silicon wafer or the surface on which the resin composition layer is formed. The observation region of 1000 pixels × 1000 pixels corresponds to an area of ​​approximately 9 μm × 9 μm. The observation area defined as described above was captured as a SEM cross-sectional image.

[0229] (2-2) Image analysis of void regions Next, the SEM cross-sectional image obtained in (2-1) above was 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 software "ImageJ" was "1.51j8". The latest version of the analysis software "ImageJ" is available on the Internet. First, the analysis software was started and the SEM cross-sectional image was displayed. FIG. 2 is a photograph of the SEM cross-sectional image of the cured product D of Example 8 displayed by the analysis software (more specifically, the SEM cross-sectional image of the cured product D of Example 8, which was the subject of the third porosity measurement). Next, the outline of each void region in the displayed image was surrounded using the command "Freehand selection" of the analysis software. Next, the surrounded outline and the inner area defined by the outline were cut out using "cut" included in the command "Edit" so that the void region was identified. The same operation was performed for all void regions recognized in the SEM cross-sectional image. Then, the contrast of the identified void region (black region) was adjusted using "Threshold" of "Adjust" included in the command "Image" so that only the void region was black. Next, the inside of the identified void region was colored red using the command "Red". FIG. 3 shows a photograph showing the void region colored red in the SEM cross-sectional image of FIG. 2. Then, using the "Measure" command included in the "Analyze" command, the total area (number of pixels) of the area colored red (void area) was obtained.

[0230] (2-3) Calculation of void ratio Then, the total area (number of pixels) of the void region obtained in (2-2) above was divided by the number of pixels in the observation region (1000 pixels x 1000 pixels), and the divided value was multiplied by 100 to calculate the porosity (%).

[0231] (2-4) Calculation of the average value The above steps (2-1) to (2-3) were repeated 50 times. In other words, the observation area was changed by exposing the cross section 50 times (number of observations N = 50), and the porosity was calculated. The sum of the obtained porosities was then divided by 50 to calculate the average value. By increasing the number of observations in this way, it is expected that chance (uneven distribution of components on the observation surface) and arbitrariness (missed counts) can be eliminated. The average calculated porosity values ​​are shown in Table 1.

[0232] However, the SEM cross-sectional images for which the porosity should be calculated were selected as follows, and the porosity was not calculated for SEM cross-sectional images that did not satisfy the following requirements. First, the volume percentage (%) of the inorganic filler contained in the resin paste A prepared in each example and comparative example was calculated based on its blending amount and true density. On the other hand, the area percentage (%) was calculated as a value obtained by dividing the number of pixels of the inorganic filler region in the SEM cross-sectional image obtained in the above (2-1) by the number of pixels of the observation region (1000 pixels x 1000 pixels) and multiplying the result by 100 in the same manner as in the above (2-2). Then, the obtained volume percentage (%) and area percentage (%) of the inorganic filler were compared, and the SEM cross-sectional images that satisfied the requirement that the value of the area percentage (%) was within ±3 of the value of the volume percentage (%) were selected as the objects for calculating the porosity.

[0233] <Warpage evaluation> The resin compositions prepared in the examples and comparative examples were compression molded on a 12-inch silicon wafer using a compression molding device (mold temperature: 130°C, pressure: 6MPa, cure time: 10 minutes) to form a resin composition layer with a thickness of 300 μm. The resin composition layer was then heated at 180°C for 90 minutes to thermally cure. This resulted in a sample substrate including a silicon wafer and a cured layer of the resin composition. The amount of warping of the sample substrate at 25°C was measured using a shadow moire measuring device ("ThermoireAXP" manufactured by Akorometrix). The measurement was performed in accordance with JEITA EDX-7311-24, a standard of the Japan Electronics and Information Technology Industries Association. Specifically, a virtual plane calculated by the least squares method of all data on the substrate surface in the measurement area was used as a reference plane, and the difference between the minimum and maximum values ​​in the vertical direction from the reference plane was calculated as the amount of warping, and the amount of warping was evaluated according to the following criteria. ○: Warpage is less than 2000μm (2mm). ×: Warpage is 2 mm or more. The measured amount of warpage and the evaluation results of the low warpage property are shown in Table 1.

[0234] <Evaluation of long-term reliability> 1. Preparation of cured material for evaluation The resin compositions prepared in the Examples and Comparative Examples were compression molded onto a release-treated 12-inch silicon wafer using a compression molding device (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes) to form a resin composition layer with a thickness of 300 μm. The resin composition layer was peeled off from the silicon wafer and heated at 180°C for 90 minutes to thermally cure the resin composition layer, thereby obtaining a cured product A for evaluation.

[0235] 2. Evaluation of long-term reliability The long-term reliability was evaluated by subjecting the cured material A for evaluation to an HTS test, measuring the strength at break before and after the HTS (High Thermal Storage) test, and calculating the degree of change (%) in the strength at break.

[0236] (1) HTS Testing The cured product for evaluation A was subjected to an HTS test. In the HTS test, the cured product for evaluation A was held at 150° C. for 1000 hours. In this way, a cured product for evaluation after the HTS test was obtained.

[0237] (2) Measurement of breaking strength before and after HTS testing The cured product for evaluation before the HTS test was cut into a dumbbell-shaped No. 1 shape in plan view to obtain five test pieces. Similarly, the cured product for evaluation after the HTS test was cut into a dumbbell-shaped No. 1 shape in plan view to obtain five test pieces. A tensile test was performed on each of the test pieces using an Orientec tensile tester "RTC-1250A" at 23°C and a test speed of 5mm / min, and the tensile strength at break (also simply referred to as "strength at break") was obtained from the stress-strain curve. The measurement was performed in accordance with JIS K7127:1999. The average value of the strength at break of the five test pieces was taken as the tensile strength at break σ0 before the HTS test. The average value of the strength at break of the five test pieces was taken as the tensile strength at break σ1 after the HTS test. The change in tensile strength at break (%) before and after the HTS test was calculated based on the following formula. Degree of change (%) = {(σ1-σ0) / σ0} x 100 Based on the calculated degree of change (%), the long-term reliability was evaluated according to the following criteria.

[0238] Long-term reliability criteria: ○: 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) ×: The absolute value of the degree of change (%) is 10% or more (the degree of change is large, and long-term reliability is poor) The measured breaking strengths and the degree of change are shown in Table 1.

[0239] <Evaluation of dielectric properties> The resin compositions prepared in the Examples and Comparative Examples were compression molded on a release-treated 12-inch silicon wafer using a compression molding device (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes) to form a resin composition layer with a thickness of 300 μm. The resin composition was then peeled off from the release-treated silicon wafer and heated at 150°C for 90 minutes to thermally cure the resin composition to prepare a sample. The dielectric constant and dielectric loss tangent at 60 GHz were measured by the Fabry-Perot method. Measurements were performed on three test pieces, and the average value was calculated. The average values ​​of the measured dielectric constant and dielectric tangent are shown in Table 1.

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

[0241] [Table 1] [Explanation of symbols]

[0242] 100 Semiconductor chip package 110 Semiconductor Chip 120 Sealing layer 130 Rewiring formation layer 140 Redistribution layer 150 Solder resist layer 160 Bump

Claims

1. A resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, When the resin composition is cured by a curing method including the following compression molding step and post-cure step, the resulting cured product exhibits a porosity in the range of 0.002% to 2% and a strength at break of 55 MPa or more but less than 110 MPa; Here, the porosity is the area ratio (%) of void regions in an SEM cross-sectional image of a cured resin composition. <Compression molding process> A process of placing the resin composition so that it is bonded to the silicon wafer, and then compression molding it under conditions of a pressure of 15 tons, a temperature of 130°C, and a time of 10 minutes to obtain a compression molded body of the resin composition bonded to the silicon wafer and having a thickness of 300 μm. <Post-cure process> A step of heating the compression molded body of the obtained resin composition under nitrogen atmosphere at a temperature of 150°C for 1 hour to obtain a cured product.

2. A resin composition as described in claim 1, wherein the porosity is obtained by calculating the area ratio (%) of the void area obtained as a void image to the observation area having a thickness dimension of 1000 pixels and an in-plane dimension of 1000 pixels in an SEM cross-sectional image at a magnification of 27,000 times.

3. A resin composition described in claim 1 or 2, wherein the porosity is the arithmetic mean value of the area percentage (%) of void regions obtained from 50 SEM cross-sectional images of the cured product.

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

5. The post-cure process comprises the following steps (p1) to (p2): (p1) a step of placing the compression-molded resin composition removed from the mold in an oven set at a temperature of 150°C and 1 atmosphere under a nitrogen atmosphere, and waiting for one hour to obtain a cured product; and (p2) A step of removing the cured product from the oven within 120 seconds after step (p1) and allowing it to cool in an environment at room temperature and normal pressure. The resin composition according to any one of claims 1 to 4, comprising in this order:

6. A resin composition described in any one of claims 1 to 5, wherein the resin porosity, which indicates the area ratio of the void area in the resin component area obtained by excluding the void area within the area defined by the outer shape area of ​​the inorganic filler (C) from the void area obtained as a void image by image analysis, to the observation area, is within the range of 0.002% to 2%.

7. A resin composition described in any one of claims 1 to 6, wherein component (A) is 0.5 mass% or more and 45 mass% or less, when the non-volatile components in the resin composition are 100 mass%.

8. A resin composition described in any one of claims 1 to 7, wherein component (C) is 30 mass% or more when the non-volatile components in the resin composition are 100 mass%.

9. A resin composition described in any one of claims 1 to 8, wherein component (A) includes (A-1) a liquid epoxy resin.

10. A resin composition described in any one of claims 1 to 9, which contains (E-1) a silane coupling agent, and the silane coupling agent is of a single type.

11. A resin composition described in any one of claims 1 to 9, which contains (E-1) a silane coupling agent and which contains multiple types of silane coupling agents.

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

13. A resin composition described in any one of claims 1 to 12, wherein the solvent content is 3 mass% or less when the non-volatile components in the resin composition are 100 mass%.

14. A resin composition described in any one of claims 1 to 13, having a viscosity at 25°C measured using an E-type viscometer within the range of 1 Pa·s to 1000 Pa·s.

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

6.

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

03.

17. A resin composition described in any one of claims 1 to 16, wherein the degree of cure of the cured product is 95% or more.

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

19. A resin composition described in any one of claims 1 to 18, which is for use in a rewiring formation layer.

20. A resin paste formed containing the resin composition described in any one of claims 1 to 19.

21. A cured product of the resin composition described in any one of claims 1 to 19 or the resin paste described in claim 20.

22. A cured product obtained by curing a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler 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 strength at break of 55 MPa or more and less than 110 MPa, wherein the porosity is the area ratio (%) of the void region in an SEM cross-sectional image of the cured product. <Compression molding process> A process of placing the resin composition so that it is bonded to the silicon wafer, and then compression molding it under conditions of a pressure of 15 tons, a temperature of 130°C, and a time of 10 minutes to obtain a compression molded body of the resin composition bonded to the silicon wafer and having a thickness of 300 μm. <Post-cure process> A step of heating the compression molded body of the obtained resin composition under nitrogen atmosphere at a temperature of 150°C for 1 hour to obtain a cured product.

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

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

25. The semiconductor chip package of claim 23 or 24, which is a fan-out type package.

26. A semiconductor device comprising the semiconductor chip package according to claim 23.

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