Zeolite, method for producing zeolite, resin composition, semiconductor sealing material, method for producing semiconductor sealing material, and electronic device

Abstract

Provided is a zeolite which, when heated to 800°C at a temperature increase rate of 10°C / min and then held for 10 minutes at 800°C in an air atmosphere in thermogravimetric analysis (TGA), the weight loss rate at 800°C is 1% or more based on the weight at 400°C, and in which the total content of uranium and thorium is 200 ppb by mass or less.　The present invention can provide a zeolite which exhibits low moisture absorption, has a low alpha ray amount, and can be advantageously used as a semiconductor sealing material.

Description

Zeolite, method for producing zeolite, resin composition, semiconductor encapsulant, method for producing semiconductor encapsulant, and electronic device

[0001] The present invention relates to a zeolite, a method for producing a zeolite, a resin composition, a semiconductor encapsulant, a method for producing a semiconductor encapsulant, and an electronic device.

[0002] In the field of manufacturing semiconductor devices by mounting semiconductor elements on substrates, there is an increasing demand for high-density mounting of semiconductor elements, and adhesives are used to protect circuit surfaces, etc. Adhesives are used in two ways: as an underfill material between the semiconductor element and the substrate, and as an encapsulant that covers the entire semiconductor element. In this specification, both underfill materials and encapsulants that cover the entire semiconductor element are referred to as "semiconductor encapsulants." Note that the term "semiconductor encapsulant" also encompasses the concept of an encapsulant for the entire electronic device using semiconductors.

[0003] Semiconductor encapsulants are highly filled with inorganic fillers such as silica to improve heat resistance and thermal stability. Semiconductor encapsulants using inorganic fillers such as silica filler are used as encapsulants for electronic components such as large-scale integrated circuits (LSIs). However, silica contains trace amounts of radioactive materials such as uranium, and the alpha rays (hereinafter sometimes referred to as "α rays") emitted from the silica can cause device operation errors (soft errors). For this reason, high-purity silica is required for use as a filler for electronic component encapsulants. For example, a method for producing high-purity silica has been proposed, which involves washing silica gel with acid while ultrasonicating it, followed by rinsing with water (see, for example, Patent Document 1).

[0004] Incidentally, semiconductor encapsulants using inorganic fillers such as silica fillers do not have a sufficiently low thermal expansion coefficient, and there is a demand for a further reduction in the thermal expansion coefficient from the viewpoint of thermal cycle resistance, etc. Zeolite is known as an inorganic filler with a low thermal expansion coefficient (see, for example, Patent Document 2), but the synthesis routes for zeolite are limited, and there have been no examples of zeolite with controlled α-ray emission being used for semiconductor encapsulants.

[0005] Zeolites are also known to be highly hygroscopic, and the presence of water can reduce the dielectric constant and reliability of electronic materials, so zeolites used in this application are required to have low hygroscopicity.

[0006] Japanese Patent Application Laid-Open No. 2-74514 International Publication No. 2023 / 210790

[0007] Under the above circumstances, an object of the present invention is to provide a zeolite that has low moisture absorption and low alpha radiation dose and is suitable for use as a semiconductor encapsulant.

[0008] The present inventors conducted extensive research into the above-mentioned problems and discovered that a specific configuration can provide a zeolite with low moisture absorption and low alpha radiation, thereby solving the above-mentioned problems, and thus completed the present invention. The gist of the present invention is as follows: [1] A zeolite that, when heated to 800°C at a heating rate of 10°C / min in an air atmosphere and held at 800°C for 10 minutes, exhibits a weight loss of 1% or more at 800°C, based on the weight at 400°C, and has a uranium and thorium content of 200 ppb by mass or less, as determined by thermogravimetric analysis (TGA). [2] The zeolite according to [1] above, in which the circularity of the primary particles is 0.850 or more. [3] The zeolite according to [1] or [2] above, in which the CBU has d6r. [4] The zeolite according to any one of [1] to [3] above, in which the zeolite has a structure with an oxygen ring of 8 or less members. [5] The zeolite according to any one of [1] to [4] above, which has a CHA structure. [6] The zeolite according to any one of [1] to [5] above, which has a uranium content of 8 ppb by mass or less. [7] The zeolite according to any one of [1] to [6] above, which has a thorium content of 1 ppb by mass or less. [8] The zeolite according to any one of [1] to [7] above, which has a sodium and potassium content of 2,000 ppm by mass or less in total. [9] The zeolite according to any one of [1] to [8] above, which has a uranium and thorium content of 0.00002 ppb by mass or more in total.

[10] The zeolite according to any one of [1] to [9] above, which has a uranium to thorium content ratio (uranium content / thorium content) of 0.01 or more and 1,000 or less.

[11] Surface alpha dose at 4.0 to 10.0 MeV is 0.0072 count / cm ２

[12] The zeolite according to any one of the above [1] to

[10] , wherein the surface alpha dose at 2.0 to 10.0 MeV is less than 0.0135 count / cm ２

[13] A method for producing the zeolite according to any one of [1] to

[12] above, using as raw materials a silicon atom raw material having a uranium content of less than 10 ppb by mass based on silicon atoms and a thorium content of less than 314 ppb by mass based on silicon atoms, and an aluminum atom raw material having a uranium content of 455 ppb by mass or less based on aluminum atoms and a thorium content of 4 ppb by mass or less based on aluminum atoms.

[14] A resin composition containing the zeolite according to any one of [1] to

[12] above and a resin.

[15] The resin composition according to

[14] above, wherein the resin comprises at least one resin selected from the group consisting of epoxy resins and polyimide resins.

[16] The resin composition according to

[14] above, wherein the resin comprises an epoxy resin.

[17] A semiconductor encapsulant comprising the resin composition according to any one of

[14] to

[16] above.

[18] A method for producing a semiconductor encapsulant, comprising a step of curing the resin composition according to any one of

[14] to

[16] above.

[19] An electronic device comprising the semiconductor encapsulant according to

[17] above.

[0009] According to the present invention, it is possible to provide a zeolite that has low moisture absorption and low alpha radiation, and is suitable for use as a semiconductor encapsulant.

[0010] [Zeolite] The zeolite of the present invention (hereinafter sometimes referred to as "the zeolite") is characterized in that, when heated to 800°C at a heating rate of 10°C / min in an air atmosphere and held at 800°C for 10 minutes, the weight loss rate at 800°C (hereinafter sometimes simply referred to as "weight loss rate") based on the weight at 400°C is 1% or more, as determined by thermogravimetric analysis (TGA). Such zeolites can be obtained, for example, by containing an organic substance, preferably a component derived from an organic structure-directing agent, which is a raw material for zeolite, inside the pores. As a method for producing a zeolite containing an organic substance, preferably a component derived from an organic structure-directing agent, inside the pores, for example, a calcination treatment that is usually performed in the zeolite production process can be omitted or only partially performed. Zeolite containing organic matter, preferably components derived from an organic structure-directing agent, inside its pores is thought to experience a greater weight loss when heat-treated in the high temperature range of 400°C to 800°C, compared to ordinary calcined zeolite, due to the elimination of adsorbed water and organic matter, preferably the organic structure-directing agent, present in the zeolite pores.

[0011] The resin composition of the present invention (hereinafter sometimes referred to as "the resin composition") described below uses a zeolite containing an organic substance, preferably a component derived from an organic structure-directing agent, inside the pores, and thereby exhibits low moisture absorption in the cured product. The mechanism by which the use of the present zeolite exhibits low moisture absorption is presumed to be as follows. Zeolite exhibits adsorption properties for water and other substances because it has a porous structure and contains acid sites that serve as adsorption sites. Furthermore, it is presumed that the presence of an organic substance, preferably a component derived from an organic structure-directing agent, in the pores prevents the zeolite from becoming completely porous, resulting in reduced adsorption properties for water and other substances and reduced moisture absorption. From the above perspectives, the weight loss rate of the present zeolite is 1% or more, preferably 2% or more, and more preferably 3% or more. The weight loss rate may be 5% or more, 10% or more, or 20% or more.

[0012] (Uranium and Thorium Content) The present zeolite is characterized in that the total content of uranium and thorium is 200 mass ppb or less. When the total content of uranium and thorium is 200 mass ppb or less, the amount of α-rays emitted from the zeolite can be reduced. From the above viewpoints, the total content of uranium and thorium is preferably 150 mass ppb or less, more preferably 100 mass ppb or less, even more preferably 50 mass ppb or less, particularly preferably 25 mass ppb or less, and most preferably 10 mass ppb or less. On the other hand, from the viewpoint of reducing the risk of environmental uranium and environmental thorium naturally present in the environment being adsorbed to the surface sites of the zeolite, it is preferable that a certain amount of uranium and thorium is already contained in the zeolite. Specifically, the total content of uranium and thorium contained in the present zeolite is preferably 0.00002 mass ppb or more, more preferably 0.0002 mass ppb or more.

[0013] Furthermore, the uranium content of the present zeolite is preferably 17 ppb by mass or less. A uranium content of 17 ppb by mass or less can sufficiently reduce the alpha dose of the present zeolite. From the above perspectives, the uranium content is more preferably 15 ppb by mass or less, even more preferably 10 ppb by mass or less, and particularly preferably 8 ppb by mass or less. On the other hand, from the viewpoint of reducing the risk of environmental uranium naturally present in the environment being adsorbed to the surface sites of the zeolite, it is preferable that a certain amount of uranium is already contained in the zeolite. Specifically, the uranium content of the present zeolite is preferably 0.00001 ppb by mass or more, and more preferably 0.0001 ppb by mass or more. Methods for adjusting the uranium content of the present zeolite to the above range include, but are not limited to, the use of high-purity raw materials and washing with acid.

[0014] Furthermore, the content of thorium contained in the present zeolite is preferably 200 mass ppb or less. A thorium content of 200 mass ppb or less can sufficiently reduce the alpha dose of the present zeolite. From the above perspectives, the thorium content is more preferably 100 mass ppb or less, even more preferably 50 mass ppb or less, particularly preferably 10 mass ppb or less, even more preferably 5 mass ppb or less, and most preferably 1 mass ppb or less. On the other hand, from the viewpoint of reducing the risk of environmental thorium naturally present in the environment being adsorbed to the surface sites of the zeolite, it is preferable that a certain amount of thorium is already contained in the zeolite. Specifically, the content of thorium contained in the present zeolite is preferably 0.00001 mass ppb or more, and more preferably 0.0001 mass ppb or more. Methods for adjusting the thorium content of the present zeolite to the above range include, but are not limited to, the use of high-purity raw materials and washing with acid.

[0015] Furthermore, the content ratio of uranium to thorium contained in the present zeolite (uranium content / thorium content) is preferably 0.01 or more, more preferably 0.025 or more, and even more preferably 0.1 or more, from the viewpoint of suppressing long-term deterioration due to the short half-life of uranium. Furthermore, from the viewpoint of enhancing the thermal stability of zeolite due to the high stability of thorium, the content ratio (uranium content / thorium content) is preferably 1,000 or less, more preferably 500 or less, even more preferably 300 or less, and particularly preferably 150 or less.

[0016] (α-ray dose) The α-ray dose of the present zeolite is 0.0072 count / cm at the surface at 4.0 to 10.0 MeV. ２ It is preferable that the surface alpha dose at 4.0 to 10.0 MeV is less than 0.0072 count / cm ２ By having a surface α dose of less than 0.005 count / cm at 4.0 to 10.0 MeV, the surface α dose of the present zeolite at 4.0 to 10.0 MeV can be reduced by using the zeolite as a semiconductor encapsulant. ２h or less, more preferably 0.004 count / cm ２ h or less, and more preferably 0.003 count / cm ２ h or less is particularly preferred, and 0.002 count / cm ２ h or less, and 0.001 count / cm ２ The lower the surface α dose of the present zeolite at 4.0 to 10.0 MeV, the better. The lower limit of the surface α dose at 4.0 to 10.0 MeV is not particularly limited, but is, for example, 0.0001 count / cm ２ The α-ray dose of the present zeolite may be 0.0135 counts / cm at a surface α-ray dose of 2.0 to 10.0 MeV. ２ It is preferable that the alpha dose at 2.0 to 10.0 MeV is less than 0.0135 count / cm ２ By having a surface α dose of less than 0.010 counts / cm at 2.0 to 10.0 MeV, the surface α dose of the present zeolite at 2.0 to 10.0 MeV can be reduced by using the present zeolite as a semiconductor encapsulant. ２ h or less, more preferably 0.009 count / cm ２ h or less, and more preferably 0.008 count / cm ２ h or less, especially 0.007 count / cm ２ h or less, especially 0.006 count / cm ２ h or less, especially 0.005 count / cm ２ h or less, especially 0.004 count / cm ２ ・Less than h, 0.003 count / cm ２ h or less is particularly preferred, and 0.002 count / cm ２ h or less, and 0.001 count / cm ２The lower the surface α dose of the present zeolite at 2.0 to 10.0 MeV, the better. The lower limit of the surface α dose at 2.0 to 10.0 MeV is not particularly limited, but is, for example, 0.0001 count / cm ２ The surface alpha doses at 4.0 to 10.0 MeV and 2.0 to 10.0 MeV are measured by the method described in the Examples. Methods for adjusting the surface alpha doses of the present zeolite at 4.0 to 10.0 MeV and 2.0 to 10.0 MeV to fall within the above ranges include, but are not limited to, the use of highly pure raw materials and washing with an acid.

[0017] (Alkali Content) In the present zeolite, it is preferable that the content of alkalis such as alkali metals and alkaline earth metals is low. A low content of alkalis such as alkali metals makes it less likely to cause corrosion of device wiring or deterioration of semiconductor element performance when used as a semiconductor encapsulant. Among alkalis, it is preferable that the content of alkali metals, especially sodium and potassium, is low, and it is preferable that the total content of sodium and potassium is 2,000 ppm by mass or less. When the total content of sodium and potassium is 2,000 ppm by mass or less, it is possible to suppress corrosion of wiring and deterioration of semiconductor element performance when used as a semiconductor encapsulant. From the above viewpoints, it is more preferable that the total content of sodium and potassium is 1,500 ppm by mass or less, even more preferably 1,000 ppm by mass or less, particularly preferably 500 ppm by mass or less, particularly preferably 100 ppm by mass or less, and most preferably 50 ppm by mass or less. In the present invention, it is particularly preferable to reduce the sodium content. The total content of sodium and potassium is preferably 0.11 ppb by mass or more from the viewpoint of promoting zeolite nucleation and controlling the rate of zeolite crystal growth. Specifically, the total content of sodium and potassium contained in the present zeolite is preferably 0.11 ppb by mass or more.

[0018] Furthermore, the sodium content of the present zeolite is preferably 2,000 ppm by mass or less. When the sodium content is 2,000 ppm by mass or less, when used as a semiconductor encapsulant, it is possible to suppress wiring corrosion and deterioration of the performance of semiconductor elements. From the above viewpoints, the sodium content is more preferably 1,500 ppm by mass or less, even more preferably 1,000 ppm by mass or less, and particularly preferably 500 ppm by mass or less, particularly preferably 250 ppm by mass or less, particularly preferably 200 ppm by mass or less, particularly preferably 100 ppm by mass or less, particularly preferably 50 ppm by mass or less, particularly preferably 40 ppm by mass or less, particularly preferably 30 ppm by mass or less, even more preferably 20 ppm by mass or less, and most preferably 15 ppm by mass or less. On the other hand, from the viewpoint of promoting zeolite nucleation, sodium is preferably contained. That is, it is preferable that the zeolite particle contains at least one sodium atom. Therefore, the sodium content contained in the present zeolite is preferably 0.04 mass ppb or more. Furthermore, the potassium content contained in the present zeolite is preferably 180 mass ppm or less. When the potassium content is 180 mass ppm or less, when used as a semiconductor encapsulant, corrosion of wiring and deterioration of the performance of semiconductor elements can be suppressed. From the above viewpoints, the potassium content is more preferably 150 mass ppm or less, even more preferably 100 mass ppm or less, of which 50 mass ppm or less, of which 20 mass ppm or less, of which 10 mass ppm or less is particularly preferred, 5 mass ppm or less is particularly preferred, and 3 mass ppm or less is most preferred. On the other hand, from the viewpoint of controlling the rate of zeolite crystal growth, potassium is preferably contained. That is, it is preferable that the zeolite particles contain one or more potassium atoms. Therefore, the potassium content contained in the present zeolite is preferably 0.07 mass ppb or more.

[0019] Furthermore, the content ratio of sodium to potassium contained in the present zeolite (sodium content / potassium content) is preferably 0.5 or more, more preferably 1 or more, and even more preferably 5 or more, from the viewpoint that sodium has a small ionic radius and promotes densification of the zeolite framework formation. Moreover, the content ratio (sodium content / potassium content) is preferably 10,000 or less, more preferably 5,000 or less, from the viewpoint that potassium has a high ionization tendency and promotes dissolution of the silicon atom raw material and aluminum atom raw material, which are the raw materials for the zeolite. Methods for adjusting the contents of sodium and potassium contained in the present zeolite to fall within the above ranges include, but are not limited to, the use of high-purity raw materials and washing with acid.

[0020] (Zeolite Particle Size) The particle size of the present zeolite refers to the diameter (equivalent circle diameter) of the largest circle having an area equal to the projected area of ​​the particle when observed with a particle image analyzer. The present zeolite may be formed as secondary particles formed by aggregation of multiple zeolite particles. In this case, the particle size of the zeolite is the particle size of the primary particles, i.e., the equivalent circle diameter of the primary particles. From the viewpoint of dispersibility when added to a resin, the particle size of the present zeolite is preferably 0.01 μm or more, more preferably 0.05 μm or more, and even more preferably 0.1 μm or more. On the other hand, from the viewpoint of handling as a filler, the particle size is preferably 200 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less. In particular, when used as an underfill material, the particle size is preferably 0.05 μm or more from the viewpoint of dispersibility when added to a resin, and is preferably 10 μm or less from the viewpoint of gap injection properties. Furthermore, when used as an encapsulant that covers the entire semiconductor element, the particle size is preferably 0.01 μm or more from the viewpoint of dispersibility when added to a resin, and preferably 100 μm or less from the viewpoint of handling as a filler. The particle size of zeolite is determined by randomly selecting 100 or more particles of zeolite (powder, particles in a resin composition described below), measuring their particle sizes, and averaging the results. While 100 particles are sufficient for calculating the average, in the examples and comparative examples, the average value was calculated from 20,000 to 30,000 particles to improve accuracy.

[0021] (Zeolite Structure) Zeolite is a type of zeolite containing silicon or aluminum and oxygen. ４ The zeolite is a compound having a basic unit (T element is an element other than oxygen that constitutes the framework). Specific examples of zeolites include crystalline porous aluminosilicates, crystalline porous aluminophosphates (ALPOs), and crystalline porous silicoaluminophosphates (SAPOs). The zeolite may have any of the above structures, but aluminosilicates are preferred. The zeolite is a TO ４ Zeolite is composed of structural units called Composite Building Units (hereinafter sometimes referred to as "CBUs"), which are composed of several (several to several tens) connected units. As a result, it has regular channels (tubular pores) and cavities. The CBUs and the crystalline structure of zeolites described below can be represented by codes defining the structure of zeolites established by the International Zeolite Association (IZA). The structure of zeolites can be identified using the Zeolite Structure Database 2018 Edition (http: / / www.iza-structure.org / databases / ) based on X-ray diffraction patterns obtained using an X-ray structure analyzer (e.g., a BRUKER D2PHASER tabletop X-ray diffractometer).

[0022] (Zeolite Skeleton) The zeolite skeleton preferably has d6r as the CBU. By having d6r, a resin composition with a low thermal expansion coefficient after curing is easily obtained. Zeolites having d6r as the CBU include AEI, AFT, AFV, AFX, AVL, CHA, EAB, EMT, ERI, FAU, GME, JSR, KFI, LEV, LTL, LTN, MOZ, MSO, MWW, OFF, SAS, SAT, SAV, SBS, SBT, SFW, SSF, SZR, TSC, and zeolites with a -WEN structure. Of these, zeolites with a structure of 8 or less oxygen-membered rings are particularly preferred from the viewpoint that water molecules are less likely to penetrate into the pores. Zeolites having an 8-membered oxygen ring or less structure include zeolites having an AEI, AFT, AFX, CHA, ERI, KFI, SAT, SAV, SFW, and TSC structure. Among these, zeolites having an AEI, AFX, CHA, or ERI structure are more preferred because the structure is stable even when the shape is controlled, and zeolites having a CHA structure are even more preferred. In this specification, a structure having an 8-membered oxygen ring means a structure in which the number of oxygen elements is 8 when the number of oxygen elements is the largest among the pores formed by oxygen and T elements (elements other than oxygen that constitute the framework) that form the zeolite framework. Furthermore, the above-mentioned zeolites may be used alone or in combination of two or more types.

[0023] (Average Thermal Expansion Coefficient of Zeolite) The average thermal expansion coefficient of the present zeolite is preferably low because a small amount of zeolite can easily reduce the average thermal expansion coefficient of the liquid composition described below. A small amount of zeolite is also preferred because the various physical properties of the resin are less likely to change due to the addition of zeolite. A low average thermal expansion coefficient is particularly preferred because it can suppress an increase in the viscosity of the liquid composition described below. Specifically, the average thermal expansion coefficient of zeolite is usually less than 0 ppm / K, preferably −2 ppm / K or less, more preferably −3 ppm / K or less, even more preferably −4 ppm / K or less, and most preferably −5 ppm / K or less.

[0024] On the other hand, considering that the zeolite will be used as a liquid composition containing the zeolite and a resin, as described below, the average thermal expansion coefficient of the zeolite is preferably high so that the difference with the average thermal expansion coefficient of the resin is small and the zeolite and the resin are less likely to separate. Therefore, the average thermal expansion coefficient of the zeolite is usually −1,000 ppm / K or higher, preferably −900 ppm / K or higher, more preferably −800 ppm / K or higher, even more preferably −700 ppm / K or higher, particularly preferably −500 ppm / K or higher, and most preferably −300 ppm / K or higher. In particular, when used as a semiconductor encapsulant, a high average thermal expansion coefficient is preferred. Specifically, the average thermal expansion coefficient is −100 ppm / K or higher, more preferably −50 ppm / K or higher, even more preferably −40 ppm / K or higher, particularly preferably −30 ppm / K or higher, even more preferably −25 ppm / K or higher, and most preferably −20 ppm / K or higher. The average thermal expansion coefficient of zeolite can be measured by calculating the lattice constant using a BRUKER X-ray diffractometer "D8ADVANCE" and X-ray diffraction analysis software "JADE." Here, to eliminate the influence of moisture desorption, the zeolite is usually measured in a dried state. The average thermal expansion coefficient of zeolite is usually measured in the range of 50 to 100°C. That is, it is a numerical value representing the change in lattice constant per degree Celsius from the average lattice constant at 50°C and the average lattice constant at 100°C when the zeolite is heated. Here, the average lattice constant at each temperature is the average value of the lattice constants of the a-axis, b-axis, and c-axis. The average thermal expansion coefficient is measured by gradually increasing the temperature after waiting until the lattice constant stabilizes.

[0025] Resins generally have a large thermal expansion coefficient in the high temperature range. Therefore, it is preferable that the average thermal expansion coefficient of zeolite is low, particularly when the temperature is raised to the high temperature range. Specifically, the average thermal expansion coefficient (high temperature range) in the range of 50 to 350°C is preferably -5 ppm / K or less, more preferably -5.5 ppm / K or less, and even more preferably -6 ppm / K or less. Here, the average thermal expansion coefficient (high temperature range) of zeolite is a numerical value representing the deviation in lattice constant per degree Celsius from the average lattice constant at 50°C and the average lattice constant at 350°C when the zeolite is heated.

[0026] (Zeolite Shape) The present zeolite is preferably spherical. By making the zeolite spherical, an increase in viscosity of a resin composition containing the zeolite can be suppressed. Specifically, the primary particles have the following circularity. Note that "primary particles" refer to unit particles that do not contain crystal grain boundaries inside. Furthermore, "primary particles" can be determined by observation using a particle image analyzer.

[0027] (Circularity of Primary Particles of Zeolite) The circularity of the primary particles of the present zeolite (hereinafter sometimes simply referred to as "circularity") is preferably 0.850 or more, more preferably 0.870 or more, even more preferably 0.890 or more, particularly preferably 0.910 or more, and most preferably 0.920 or more. There is no particular upper limit to the circularity of the primary particles, and it may be 1 or less. In the case of a cube, which is common in ordinary zeolites, the circularity is 0.785. In this specification, "circularity" is defined as "4 x π x area / (circumference)". ２". The area and circumference can be determined by observation using a particle image analyzer. In this application, "circularity" is the average value of 100 or more particles obtained by the particle image analyzer. While 100 particles are sufficient for calculating the average value, in the examples and comparative examples, an average value of 20,000 to 30,000 particles is used to improve accuracy. Methods for adjusting the circularity of the primary particles of this zeolite to fall within the above range include performing a classification treatment after hydrothermal synthesis and adding seed crystals, amino acids, surfactants, or organic structure-directing agents in desired proportions during hydrothermal synthesis.

[0028] (Zeolite Framework Density) The framework density of the present zeolite is not particularly limited as long as it is within a range that does not impair the effects of the present invention. The framework density of the zeolite is preferably low in that structural vibration of the zeolite is likely to occur and the average thermal expansion coefficient is likely to be low. Therefore, the framework density of the zeolite is preferably 17.0 T / 1000 Å. ３ or less, more preferably 16.0T / 1000Å ３ On the other hand, the framework density of the zeolite is preferably high in that the structural stability of the zeolite is likely to be high. The framework density of the zeolite is preferably 12.0T / 1000Å or less. ３ More preferably, 13.0T / 1000Å or more ３ More preferably, 14.0T / 1000Å ３ That's all. When the framework density is within the above range, the zeolite can be used as a stable filler. The framework density indicates the number of T atoms present per unit volume of the zeolite, and is a value determined by the structure of the zeolite. In this specification, the numerical values ​​listed in the IZA Zeolite Structure Database 2017 Edition (http: / / www.iza-structure.org / databases / ) may be used.

[0029] Framework density: 16.0T / 1000Å ３ Larger, 17.0T / 1000Å ３Examples of the following zeolites include zeolites with ERI, LTL, LTN, MOZ, OFF, SAT, SSF, and -WEN structure types, and framework densities of 15.0T / 1000Å and above. ３ Larger, 16.0T / 1000Å ３ Examples of the following zeolites include zeolites of the AEI, AFT, AFV, AFX, AVL, EAB, GME, LEV, MWW, and SFW structure types, with a framework density of 14.0 T / 1000 Å. ３ Larger, 15.0T / 1000Å ３ Examples of the following zeolites include CHA, KFI, SAS, and SAV structure zeolites with a framework density of 14.0 T / 1000 Å. ３ Examples of zeolites in the following ranges include zeolites of the EMT, FAU, JSR, SBS, SBT, and TSC type structures.

[0030] (Zeolite Composition) The composition of the present zeolite is not particularly limited as long as the effects of the present invention are not impaired, but an aluminosilicate containing at least aluminum atoms and silicon atoms in its framework structure is preferred because it is advantageous for application to fillers. One type of zeolite may be used alone, or two or more types may be used in any combination and ratio.

[0031] In addition, when elements such as gallium, iron, boron, titanium, zirconium, tin, zinc, phosphorus, etc. are used instead of silicon or aluminum, the molar ratio of the oxide of the substituted element can be converted into the molar ratio of alumina or silica. Specifically, when gallium is used instead of aluminum, the molar ratio of gallium oxide can be converted into the molar ratio of alumina.

[0032] (Silica / Alumina Molar Ratio (SAR) of Zeolite) The silica / alumina molar ratio (hereinafter referred to as "SAR" or "Si / Al") of the present zeolite is ２ The SAR (Si / Al ratio) of the zeolite is not particularly limited as long as the effect of the present invention is not impaired. ２A high SAR (Si / Al ratio) of zeolite is preferable in that the moisture resistance of the cured product is increased and the amount of counter cations is easily controlled. ２ The SAR (Si / Al ratio) of the zeolite is usually 2 or more, preferably 5 or more, more preferably 10 or more, even more preferably 14 or more, among which 18 or more, among which 20 or more, among which 22 or more, among which 23 or more, among which 23.5 or more, particularly preferably 24 or more, especially more preferably 24.5 or more, and most preferably 25 or more. ２ The SAR (Si / Al ratio) of zeolite is preferably low in terms of easy and inexpensive production. ２ The SAR (Si / Al ratio) is usually 2,000 or less, preferably 1,000 or less, more preferably 500 or less, even more preferably 100 or less, particularly 50 or less, particularly 47.5 or less, particularly 45 or less, particularly 42.5 or less, particularly 40 or less, particularly 39 or less, particularly 38 or less, particularly preferably 37 or less, especially more preferably 36 or less, and most preferably 35 or less. ２ When the SAR (Si / Al ratio) of the zeolite is within the above range, it is easy to control the amount of counter cations, and the production cost of the zeolite is low. ２ The SAR (Si / Al ratio) of the zeolite can be adjusted by the type and ratio of the silicon-containing compound and aluminum-containing compound used as raw materials, the type and amount of the structure-directing agent, the use of seed crystals, and synthesis conditions such as temperature and time. ２ The ratio can be determined by the method described below.

[0033] (Counter cation of zeolite) The counter cation of the present zeolite is not particularly limited as long as the effects of the present invention are not impaired. The counter cation of the zeolite is usually a component derived from the organic structure-directing agent, a proton, an alkali metal ion, or an alkaline earth metal ion. Preferably, it is a component derived from the organic structure-directing agent, a proton, or an alkali metal ion, more preferably a component derived from the organic structure-directing agent, a proton, a Li ion, a Na ion, or a K ion, and even more preferably a component derived from the organic structure-directing agent. In the case of alkali metal ions or alkaline earth metal ions, the smaller their size, the more likely the zeolite will exhibit an average thermal expansion coefficient of less than 0 ppm / K, which is preferable. In the case of components derived from the organic structure-directing agent, they are more flexible than alkali metal ions or alkaline earth metal ions, and therefore the zeolite will more likely exhibit an average thermal expansion coefficient of less than 0 ppm / K, which is preferable. That is, the zeolite is preferably a component type derived from an organic structure-directing agent (hereinafter, sometimes referred to as "as-made type"), a proton type, or an alkali metal type, more preferably an as-made type, a proton type, a Li type, a Na type, or a K type, and even more preferably an as-made type.

[0034] (Crystallinity of Zeolite) The crystallinity of the present zeolite is not particularly limited as long as the effects of the present invention are not impaired. The reason for this is that it is presumed that the Composite Building Unit (CBU) is a factor that has a greater influence on the average thermal expansion coefficient of the cured product than the structure specified by the IZA code. The crystallinity of zeolite can be determined by comparing a certain X-ray diffraction peak determined using an X-ray diffractometer (e.g., a BRUKER D2PHASER tabletop X-ray diffractometer) with the X-ray diffraction peak of a reference zeolite. A specific calculation example is the crystallinity of LTA zeolite in Scientific Reports 2016, 6, Article number: 29210.

[0035] (Surface Treatment of Zeolite) The present zeolite may be subjected to a surface treatment such as silylation treatment or fluorination treatment, as long as the effects of the present invention are not impaired. The surface treatment may be a physical treatment or a chemical treatment.

[0036] [Method for Producing Zeolite] Known methods can be applied to the method for producing zeolite. For example, when producing CHA-type zeolite, production can be performed with reference to the method described in JP 2009-097856 A. More specifically, an aluminum atom raw material, a silica atom raw material, an organic structure-directing agent, and the like are mixed to prepare an aqueous gel. The mixing order is usually such that the aluminum atom raw material is mixed with water, and then the silica atom raw material and the organic structure-directing agent are mixed therewith. Next, the prepared aqueous gel is subjected to hydrothermal synthesis, and the product is separated. Adhering components derived from the raw materials are removed by methods such as washing with water and drying, to obtain the zeolite.

[0037] The particularly preferred zeolite described above can be produced by the following method (hereinafter, sometimes referred to as "the present production method"). The present production method includes a step of hydrothermally synthesizing a raw material composition containing a silicon atom raw material, an aluminum atom raw material, an organic structure-directing agent, and water. Furthermore, as described above, the present production method may not perform the commonly performed calcination treatment, or may perform partial calcination as long as the zeolite after the calcination treatment achieves the aforementioned weight loss rate of 1% or more. If partial calcination is performed, the calcination conditions described below are preferred. In the present production method, partial calcination can be performed as described above, but it is preferable not to perform the calcination treatment. In other words, the present zeolite is preferably uncalcined (uncalcined). By not performing the calcination treatment, it is easier to achieve a weight loss rate of 1% or more, and ultimately, it is possible to easily produce a zeolite for obtaining a low moisture absorption resin composition. If necessary, a desired zeolite (hereinafter, sometimes referred to as "seed zeolite") may be used.

[0038] (Silicon Atom Source) It is important to use a silicon atom source having a uranium content of less than 10 ppb by mass based on silicon atoms and a thorium content of less than 314 ppb by mass based on silicon atoms as the silicon atom source for use in the present invention. In particular, uranium and thorium in the silicon atom source often remain in the zeolite produced, so it is important to reduce the uranium and thorium contents in the silicon atom source. By reducing the uranium and thorium contents in the silicon atom source, the uranium and thorium contents in the zeolite produced can be reduced. The uranium and thorium contents in the silicon atom source were measured using the method described in the Examples. Methods for reducing the uranium and thorium contents in the silicon atom source include, for example, heating the silicon atom source in the presence of a halogen.

[0039] Furthermore, it is preferable that the silicon atom raw material has a low content of alkali metals such as sodium and potassium. Specifically, it is preferable to use a silicon atom raw material such that the zeolite to be produced satisfies the above-mentioned sodium and potassium contents. Methods for reducing the sodium and potassium contents in the silicon atom raw material include, for example, washing with pure water and ion exchange.

[0040] The silicon atom source used in this production method is not particularly limited as long as it satisfies the above-mentioned uranium and thorium contents, and various known substances can be used. For example, colloidal silica, amorphous silica, trimethylethoxysilane, tetraethyl orthosilicate, aluminosilicate gel, and zeolite can be used. These silicon atom sources may be crystalline or amorphous as long as they satisfy the above-mentioned uranium and thorium contents, but amorphous is preferable from the viewpoint of high reactivity. Furthermore, recycled materials can also be used as the silicon atom source, such as used zeolite and used silica. The silicon atom source may be any material that satisfies the above-mentioned uranium and thorium contents as a whole, and one type may be used alone, or two or more types may be used in any combination and ratio.

[0041] (Aluminum atom raw material) The aluminum atom raw material is preferably an aluminum atom raw material having a uranium content of 455 mass ppb or less based on aluminum atoms and a thorium content of 4 mass ppb or less based on aluminum atoms. Since the uranium and thorium in the aluminum atom raw material remain in the produced zeolite, they do not have as much of an effect as the silicon atom raw material, but it is also important to reduce the uranium and thorium contents in the aluminum atom raw material. There are no particular limitations on the method for reducing the uranium and thorium contents in the aluminum atom raw material, but for example, thorough washing after production is recommended.

[0042] Furthermore, it is preferable that the aluminum atom raw material has a small content of alkali metals such as sodium and potassium. Specifically, it is preferable to use an aluminum atom raw material that satisfies the above-mentioned sodium and potassium contents in the present zeolite to be produced. Methods for reducing the sodium and potassium contents in the aluminum atom raw material include, for example, washing with pure water and ion exchange.

[0043] The aluminum atom source used in this production method is not particularly limited as long as it satisfies the above-mentioned uranium and thorium contents, and various known substances can be used. For example, amorphous aluminum hydroxide, pseudoboehmite, boehmite, bayerite, gibbsite, diaspore, aluminum sulfate, aluminum nitrate, aluminum lactate, aluminum isopropoxide, and zeolite can be used. Any aluminum atom source can be used as long as it satisfies the above-mentioned uranium and thorium contents. However, amorphous aluminum hydroxide, pseudoboehmite, boehmite, bayerite, gibbsite, and diaspore are preferred, with amorphous aluminum hydroxide being particularly preferred, from the viewpoints of low amounts of undesirable anions and high solubility in alkaline solutions. The aluminum atom source may be any material that satisfies the above-mentioned uranium and thorium contents as a whole, and one type may be used alone, or two or more types may be used in any combination and ratio.

[0044] (Organic Substance) As described above, the present zeolite contains an organic substance inside the pores. The organic substance is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include amines, amino acids, fatty acids, surfactants, polymers, and organic structure-directing agents. Examples of amines include trimethylamine, adamantylamine, and morpholine. Examples of amino acids include lysine, arginine, and ornithine. Examples of fatty acids include oleic acid and stearic acid. Surfactants that do not contain alkali metals such as sodium and potassium are preferred, and examples include polymers such as polyethylene glycol and polyethyleneimine. Examples of organic structure-directing agents include those described below. Among these, organic structure-directing agents are preferred because they fill the space within the zeolite framework, thereby inhibiting the diffusion of water vapor into the pores and reducing hygroscopicity. In other words, the present zeolite preferably contains a component derived from the organic structure-directing agent as the organic substance. When using an organic substance, one type may be used alone, or two or more types may be used in any combination and ratio.

[0045] (Organic Structure-Directing Agent) As the organic structure-directing agent, various known substances such as tetramethylammonium hydroxide (TMAOH), tetraethylammonium hydroxide (TEAOH), tetrapropylammonium hydroxide (TPAOH), and N,N,N-trimethyl-1-adamantylammonium hydroxide (TMadaOH) can be used. Of these, N,N,N-trimethyl-1-adamantylammonium hydroxide (TMadaOH) is preferred from the viewpoints of easily retaining organic substances within the pores of the zeolite at temperatures ranging from room temperature to 200°C and reducing the hygroscopicity of the zeolite. These may be used alone, or two or more may be used in any combination and ratio. The amount of the organic structure-directing agent used is, in terms of a molar ratio relative to the silicon (Si) contained in the raw material composition, usually 0.01 or more, preferably 0.02 or more, more preferably 0.03 or more, particularly preferably 0.04 or more, and most preferably 0.05 or more. On the other hand, it is usually not more than 1, preferably not more than 0.6, more preferably not more than 0.55, even more preferably not more than 0.5, particularly preferably not more than 0.45, and most preferably not more than 0.4. By using it within this range, it is thought that high-purity spherical zeolite with few by-products can be easily grown.

[0046] (Water) When a seed zeolite described below is used, the amount of water used is, from the viewpoint of facilitating crystal formation, typically 5 or more, preferably 7 or more, more preferably 9 or more, and even more preferably 10 or more, in terms of the molar ratio to silicon (Si) contained in the raw material composition other than the seed zeolite. Setting the amount of water within this range is preferred because crystals are easily formed. Furthermore, when zeolite is hydrothermally synthesized under conditions in which the amount of water is increased and the raw material concentration is diluted, zeolite with large particle sizes is likely to be obtained. Furthermore, from the viewpoint of easily achieving the effect of reducing costs for waste liquid treatment, the molar ratio to silicon (Si) is typically 50 or less, preferably 45 or less, more preferably 40 or less, even more preferably 35 or less, particularly preferably 30 or less, and most preferably 25 or less.

[0047] (Seed Zeolite) In the present zeolite production method, a seed zeolite may be used. When a seed zeolite is used, one type may be used alone, or two or more types may be used in any combination and ratio.

[0048] (Mixing of Raw Materials (Preparation of Pre-Reaction Raw Material Composition)) The raw material composition can usually be obtained by mixing a silicon atom raw material, an aluminum atom raw material, an organic structure-directing agent, and water, and then adding a seed zeolite, if used. In addition to the above-mentioned components, in the production of zeolite, components such as an acid component that promotes the reaction and a metal stabilizer such as a polyamine may be added in any step as needed. Furthermore, when mixing the raw materials, heating may be performed in order to obtain a zeolite with higher crystallinity. The heating temperature is usually 150°C or less, preferably 120°C or less, and more preferably 100°C or less. The heating temperature may be constant during heating, or may be changed stepwise or continuously. The heating time is not particularly limited, but is usually 1 minute or more, preferably 5 minutes or more, and more preferably 10 minutes or more, and on the other hand, is usually 24 hours or less, preferably 12 hours or less, and more preferably 8 hours or less.

[0049] (Aging) The raw material composition prepared as described above may be hydrothermally synthesized immediately after preparation. However, to obtain a zeolite with higher crystallinity, it is preferable to age the raw material for a certain period of time under predetermined temperature conditions. Particularly when scaling up the reaction, it is preferable to age the raw material while stirring it for a certain period of time, as this improves agitation and makes it easier to make the raw material more uniform. The temperature during aging is usually 100°C or lower, preferably 95°C or lower, and more preferably 90°C or lower. While the lower limit is not particularly limited, the temperature during aging is usually 0°C or higher, preferably 10°C or higher. The aging temperature may be constant during aging, or may be changed stepwise or continuously. The aging time is not particularly limited, but is usually 2 hours or longer, preferably 3 hours or longer, and more preferably 5 hours or longer. On the other hand, it is usually 30 days or shorter, preferably 10 days or shorter, and more preferably 4 days or shorter.

[0050] (Hydrothermal Synthesis) Next, the obtained raw material composition is subjected to hydrothermal synthesis. Hydrothermal synthesis is typically carried out by placing the raw material composition prepared as described above or an aqueous gel obtained by aging the raw material composition in a pressure-resistant container and maintaining a predetermined temperature under self-generated pressure or under a gas pressure to an extent that does not inhibit crystallization, while stirring, rotating or shaking the container, or while standing still. The reaction temperature during hydrothermal synthesis is typically 120°C or higher, preferably 130°C or higher, more preferably 140°C or higher, and even more preferably 150°C or higher, in order to increase the reaction rate. On the other hand, it is typically 230°C or lower, preferably 220°C or lower, more preferably 200°C or lower, and even more preferably 190°C or lower. The reaction time is not particularly limited, but is typically 2 hours or higher, preferably 3 hours or higher, and more preferably 5 hours or higher. On the other hand, it is typically 30 days or lower, preferably 10 days or lower, more preferably 7 days or lower, and even more preferably 5 days or lower. The reaction temperature may be constant during the reaction, or may be changed stepwise or continuously.

[0051] (Drying step) After hydrothermal synthesis, the zeolite is separated from the composition after hydrothermal synthesis (hydrothermal synthesis reaction liquid). The separation method is not particularly limited, but is usually separated by filtration, decantation, direct drying, or the like after washing with water. Even when separated by filtration or decantation, it is usually dried thereafter. The drying conditions are not particularly limited, and for example, the drying temperature is preferably 50°C or higher and 200°C or lower, and more preferably 70°C or higher and 150°C or lower. The drying atmosphere is not particularly limited, but may be performed in air or in an inert gas atmosphere such as nitrogen or argon.

[0052] (Caustic Treatment) The dried zeolite may be calcined to remove the organic structure-directing agent and other components used during production in any proportion, provided that the pores contain organic matter, preferably components derived from the organic structure-directing agent. By using a zeolite containing organic matter, preferably components derived from the organic structure-directing agent, in the resin composition, a resin composition that provides a cured product with a low CTE and low moisture absorption can be provided. When calcining is performed, the calcination temperature is typically 200°C to 1,000°C. Calcining at 200°C or higher can remove the organic structure-directing agent and other components, while calcining at 1,000°C or lower does not impair the physical properties of the zeolite. From the above perspectives, the calcination temperature is preferably 300°C or higher, more preferably 350°C or higher, even more preferably 400°C or higher, and preferably 900°C or lower, more preferably 800°C or lower, and even more preferably 700°C or lower. The calcination atmosphere is not particularly limited, and may be performed in air or an inert gas atmosphere such as nitrogen or argon. The calcination method is not particularly limited, and a muffle furnace, kiln, fluidized bed calcination furnace, etc. can be used, but a method of calcining by passing the above-mentioned gas is preferred. The gas flow rate is not particularly limited, but the amount of gas flow per 1 g of powder is preferably in the range of 0.1 ml / min to 100 ml / min, and more preferably 5 ml / min to 20 ml / min.

[0053] [Resin Composition] The resin composition contains zeolite and a resin. The resin composition may be liquid at room temperature. When the resin composition is liquid at room temperature (hereinafter, sometimes referred to as a "liquid composition"), it can be used as a liquid semiconductor encapsulant and is suitable as a semiconductor encapsulant. Each constituent element will be described in detail below, but when it is assumed that the resin composition is liquid at room temperature, the term "resin composition" will be read as a liquid composition. In this specification, "liquid at room temperature" means that the resin composition has fluidity between 10°C and 35°C.

[0054] (Zeolite Content) From the viewpoint of reducing the thermal expansion coefficient of the resin composition, the content of the zeolite in the resin composition is preferably 40% by mass or more, more preferably 45% by mass or more, and even more preferably 50% by mass or more, relative to the total amount of the resin composition. On the other hand, from the viewpoint of suppressing an increase in the viscosity of the resin composition, the content of the zeolite in the resin composition is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, relative to the total amount of the resin composition.

[0055] (Inorganic Filler Other Than Zeolite) The resin composition may contain an inorganic filler other than the zeolite (hereinafter, sometimes referred to as "other inorganic filler"). The other inorganic filler is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include at least one type selected from the group consisting of metals, carbon, metal carbides, metal oxides, and metal nitrides. Examples of metals include silver, copper, aluminum, gold, nickel, iron, and titanium. Examples of carbon include carbon black, carbon fiber, graphite, fullerenes, and diamond. Examples of metal carbides include silicon carbide, titanium carbide, and tungsten carbide. Examples of metal oxides include magnesium oxide, aluminum oxide (alumina), silicon oxides such as silica, calcium oxide, zinc oxide, yttrium oxide, zirconium oxide, cerium oxide, ytterbium oxide, and sialon (ceramics composed of silicon, aluminum, oxygen, and nitrogen). Examples of metal nitrides include boron nitride, aluminum nitride, and silicon nitride. Among these inorganic fillers, silica is preferred from the viewpoint of being able to lower the viscosity of the resin composition. Note that even in this silica, it is preferred that the total content of uranium and thorium is 200 pbb by mass or less.

[0056] The average particle size of the other inorganic filler is not particularly limited as long as it is within a range that achieves the effects of the present invention, but is preferably in the range of 0.1 μm to 20 μm. If it is equal to or greater than the lower limit, the viscosity of the resin composition can be reduced, and if it is equal to or less than the upper limit, handling as a filler becomes easy. From the above viewpoints, the average particle size of the other inorganic filler is more preferably in the range of 0.2 μm to 10 μm, and even more preferably in the range of 0.5 μm to 5 μm.

[0057] The content of the present zeolite in the total inorganic filler is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, from the viewpoint of fully exhibiting the effect of the present zeolite, i.e., the low CTE.

[0058] (Total Amount of Inorganic Filler) The total content of all inorganic fillers (total inorganic fillers) contained in the present resin composition is preferably high in order to facilitate the expression of the filler's effect. On the other hand, when the present resin composition is liquid at room temperature, it is preferably low in order to ensure high fluidity and easy filling into narrow spaces. Specifically, the total content of all inorganic fillers is preferably 40% by mass or more, more preferably 45% by mass or more, and even more preferably 50% by mass or more, relative to the total amount of the composition. On the other hand, it is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0059] (Resin) The resin in the present resin composition is not particularly limited as long as the effects of the present invention are exhibited, and examples thereof include thermosetting resins, thermoplastic resins, etc. Among these, when considering a semiconductor encapsulation material, it is preferable to contain a thermosetting resin.

[0060] <Thermosetting Resin> The resin composition preferably contains a thermosetting resin. The thermosetting resin is not particularly limited, and examples thereof include epoxy resins, polyimide resins, maleimide resins, polyamide resins, phenolic resins, vinyl ester resins, unsaturated polyester resins, and melamine resins. Among these thermosetting resins, in the present invention, it is preferable to contain at least one selected from the group consisting of epoxy resins and polyimide resins, and it is more preferable to contain an epoxy resin.

[0061] <<Epoxy Resin>> As the epoxy resin that can be used in the present invention, it is preferable to use an epoxy compound having an aromatic ring, such as a bisphenol A skeleton, a bisphenol F skeleton, or a biphenyl skeleton, because the thermal expansion coefficient after curing tends to be low. Specific examples include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, biphenyl epoxy resins, naphthalene ring-containing epoxy resins, epoxy resins having a dicyclopentadiene skeleton, phenol novolac resins, cresol novolac epoxy resins, triphenylmethane epoxy resins, aminophenol epoxy resins, aliphatic epoxy resins, and copolymer epoxy resins of aliphatic epoxy resins and aromatic epoxy resins. Among these, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, biphenyl epoxy resins, and naphthalene ring-containing epoxy resins are preferred, and bisphenol A epoxy resins, bisphenol F epoxy resins, naphthalene ring-containing epoxy resins, aminophenol epoxy resins, and biphenyl epoxy resins are more preferred.

[0062] Furthermore, it is preferable to use a polyfunctional epoxy resin in the resin composition, since the glass transition temperature after heat curing is likely to be high. As the polyfunctional epoxy resin, various phenols such as phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, dicyclopentadiene phenol resin, phenol aralkyl resin, naphthol novolac resin, biphenyl novolac resin, terpene phenol resin, heavy oil modified phenol resin, and various phenolic compounds such as polyhydric phenol resins obtained by condensation reaction of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, and epoxy resins produced from epihalohydrin are preferred.

[0063] From the viewpoint of fluidity, the viscosity of the epoxy resin at 23°C is preferably 5 Pa·s or less, and more preferably 0.1 to 3 Pa·s. The method for measuring the viscosity of epoxy resins is specified in JIS K7233 (1986), and the single cylinder rotational viscometer method is suitable. The viscosity of the epoxy resin used in the present invention at 23°C may be measured using a B-type rotational viscometer ("LVDV-1 Pri", manufactured by Brookfield, spindle: S62), which is one of the single cylinder rotational viscometer methods.

[0064] From the viewpoint of viscosity control, the epoxy resin preferably has an epoxy equivalent of 50 g / equivalent or more and 500 g / equivalent or less, more preferably 90 g / equivalent or more and 150 g / equivalent or less. A high epoxy equivalent is preferable in terms of excellent heat resistance. On the other hand, a low epoxy equivalent is preferable in terms of the fact that a lower melting point and lower viscosity of the epoxy resin improve the filling properties of the resin composition and tend to improve bonding properties due to filling. One type of epoxy resin may be used alone, or two or more types may be mixed in any combination and ratio. When mixed, the epoxy equivalent is the equivalent of the mixture.

[0065] The content of the epoxy resin in the resin composition is preferably low, since this relatively increases the content of inorganic fillers such as zeolite and makes it easier to reduce the thermal expansion coefficient. On the other hand, a high content is preferable, since it makes it easier to maintain the excellent physical properties of the epoxy resin. As described above, from the viewpoint of achieving both the maintenance of the excellent physical properties of the resin and the heat resistance (resistance to thermal expansion) of the cured resin composition, specifically, the content is preferably 5% by mass or more, and more preferably 10% by mass or more, relative to the total amount of the resin composition. On the other hand, the content is preferably 50% by mass or less, more preferably 35% by mass or less, and even more preferably 20% by mass or less.

[0066] <<Polyimide Resin>> The polyimide resin used in the present invention is preferably a polyimide obtained from a tetracarboxylic dianhydride and a diamine, particularly an aromatic polyimide obtained from an aromatic tetracarboxylic dianhydride and an aromatic diamine, because the resulting resin composite tends to have a low coefficient of thermal expansion and exhibits excellent properties such as heat resistance, mechanical strength, electrical properties, and solvent resistance. More specifically, a polyimide powder obtained by spraying a polyimide precursor solution onto a polyimide resin powder obtained by polymerizing and imidizing an aromatic tetracarboxylic acid component and p-phenylenediamine to form a granule is preferably used, and the polyimide powder is then composited with a filler to form a resin composite. The polyimide powder is granulated by bonding the polyimide powder particles together with the polyimide precursor, and the polyimide precursor acts as a binder in the resulting aggregate. As the polyimide precursor, for example, polyamic acid is used, and as the polyimide precursor solution used as a raw material, a polyamic acid is used which is produced by reacting a tetracarboxylic dianhydride with a diamine in the presence of a basic compound having a pKa of 7.5 or more, using water and / or an alcohol-based solvent as a reaction solvent.

[0067] (Dispersant) The resin composition may contain a dispersant to enhance the dispersibility of inorganic fillers such as the zeolite. The dispersant contained in the liquid composition containing a resin and a filler is added mainly to a liquid composition containing a resin and a filler with a large polarity difference to improve the interface state between the two and enhance compatibility. This can produce effects such as reducing viscosity, improving filler dispersibility, and preventing filler aggregation and sedimentation.

[0068] Examples of dispersants include acrylic dispersants and polymeric dispersants. Here, "polymeric dispersant" refers to a dispersant with a weight-average molecular weight of 1,000 or more. Polymeric dispersants are preferred. The main chain structure of the polymeric dispersant is not particularly limited, but examples include polyurethane, polyacrylic, polyester, polyamide, polyimide, and polyurea skeletons. From the perspective of storage stability, polyurethane, polyacrylic, and polyester skeletons are preferred. The structure of the polymeric dispersant is also not particularly limited, but examples include random structures, block structures, comb structures, and star structures. Similarly, from the perspective of storage stability, block structures and comb structures are preferred. Solvent-free dispersants, particularly solvent-free polymeric dispersants, are preferred. The absence of a solvent in the dispersant can prevent volatilization of the dispersant and the generation of voids when the composition is heated and cured. Commercially available dispersants can be used. The following dispersants are commercially available, and among these, a dispersant having at least one functional group selected from the group consisting of an amino group and an amine salt may be used.

[0069] Commercially available polymeric dispersants include the DISPERBYK series of wetting dispersants 101, 102, 103, 106, 108, 109, 110, 111, 112, 116, 130, 140, 142, 145, 161, 162, 163, 164, 166, 167, 168, 170, 171, 174, 108, 182, 183, 184, 185, 2000, 2001, 2008, 2020, 2050, 2070, 2096, 2150, 2152, and 2155 available from BYK-Chemie, and the EFKA series 4008 available from BASF Japan. 4009, 4010, 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4340, 4400, 4401, 4402, 4403, 4406, 4800, 5010, 5044, 5054, 5055, 5063, 5064, 5065, 5066, 5070, 5244, and 3000, 5000, 11200, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000SC, and 24 000GR, 26000, 28000, 31845, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 36000, 36600, 37500, 38500, 39000, 53095, 54000, 55000, 56000, 71000, DISPARLON series 1210, 1220, 1831, 1850, 1860, 2100, 2150, 2200, 7004, KS-260, KS-273N, KS-860, KS-873N, PW-36, DN-900 commercially available from Kusumoto Chemical Co., Ltd. DA-234, DA-325, DA-375, DA-550, DA-1200, DA-1401, DA-7301, PB-711, PB-821, PB-822, PN-411, PA-111 of the Ajisper series commercially available from Ajinomoto Co., Inc., 104A, 104C, 104E, 104H, 104S, 104BC, 104DPM, 104PA, 104PG-50, 420, 440, DF110D, DF110L, DF37, DF58, DF75, DF210, CT111, CT121 of the Surfynol series commercially available from Air Products Co., Ltd.Examples of such compounds include CT131, CT136, GA, TG, TGE, STG and E1004 of the Olfin series commercially available from Nissin Chemical Industry Co., Ltd., 70, 2120, and 2190 of the SN Sparse series manufactured by San Nopco Ltd., the Adekacol and Adekatol series commercially available from ADEKA Corporation, and the Sannonik series, Naroacty CL series, Emulmin series, Newpol PE series, Ionet M series, Ionet D series, Ionet S series, Ionet T series, and Sunseparator 100 commercially available from Sanyo Chemical Industries, Ltd.

[0070] The content of the dispersant is preferably high, for example, in order to easily uniformly disperse the inorganic filler in the liquid composition. On the other hand, the content of the dispersant is preferably low, in order to prevent an increase in the thermal expansion coefficient due to phase separation between the inorganic filler and the resin such as the epoxy resin. Therefore, in order to easily fill the liquid composition into a narrow space and to easily achieve a low thermal expansion coefficient after curing, the content of the dispersant is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 0.1% by mass or more and 25% by mass or less, relative to the total amount of the composition.

[0071] (Curing Agent) The resin composition preferably further contains a curing agent. The curing agent refers to a substance that contributes to the crosslinking reaction between crosslinking groups of a resin, particularly preferably an epoxy resin. The curing agent is not particularly limited, and those generally known as resin curing agents, particularly preferably epoxy resin curing agents, can be used. Examples include phenol-based curing agents, amine-based curing agents such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, acid anhydride-based curing agents, amide-based curing agents, tertiary amines, imidazole and its derivatives, organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan-based curing agents, isocyanate-based curing agents, blocked isocyanate-based curing agents, and dicyandiamine compounds. From the viewpoints of imparting fluidity and fast curing, acid anhydride-based curing agents are preferred as the curing agent.

[0072] Specific examples of phenolic curing agents include bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 1,4-bis(4-hydroxyphenoxy)benzene, 1,3-bis(4-hydroxyphenoxy)benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolac, bisphenol A novolac, o-cresol novolac, m-cresol novolac, p-cresol novolac, xylenol novolac, poly-p-hydroxystyrene, hydroquinone, resorcinol, catechol, t-butylcatechol, t-butylhydroquinone, fluoroglycinol, pyrogallol, t-butylpyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, Examples include 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allylated products or polyallylated products of the above dihydroxynaphthalenes, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, and allylated pyrogallol.

[0073] Specific examples of amine-based curing agents include aliphatic amines such as ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra(hydroxyethyl)ethylenediamine, etc. Specific examples of polyether amines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propylamine), polyoxypropylene diamine, polyoxypropylene triamines, etc. Examples of alicyclic amines include isophoronediamine, methacenediamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, and norbornenediamine. Examples of aromatic amines include tetrachloro-p-xylylenediamine, m-xylylenediamine, p-xylylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethylphenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl)ethylamine, diaminodiethyldimethyldiphenylmethane, and α,α'-bis(4-aminophenyl)-p-diisopropylbenzene.

[0074] Specific examples of acid anhydride curing agents include dodecenyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyloctadecanedioic) anhydride, poly(phenylhexadecanedioic) anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhimic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic anhydride. Examples of the acid anhydride include ethylene glycol bistrimellitate dianhydride, HET acid anhydride, Nadic acid anhydride, methyl Nadic acid anhydride, hydrogenated Nadic acid, hydrogenated methyl Nadic acid, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid anhydride, 3,4-dimethyl-6-(2-methyl-1-propenyl)-4-cyclohexene-1,2-dicarboxylic acid anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride, and 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride.

[0075] Examples of amide-based curing agents include dicyandiamide and polyamide resins. Examples of tertiary amines include 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol. Examples of imidazole and its derivatives include 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole, 2-ethyl-4(5)-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, and 2,4-diamino-6-[2'-methylimidazole]. Examples include 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of the above imidazoles with epoxy resins or polymer-encapsulated imidazole.

[0076] Examples of organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, etc., examples of phosphonium salts include tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, tetrabutylphosphonium tetrabutylborate, etc., and examples of tetraphenylboron salts include 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate, etc. One of these curing agents may be used alone, or two or more may be mixed in any combination and ratio.

[0077] When the present resin composition contains a curing agent, the content of the curing agent is preferably such that the equivalent ratio of the epoxy groups in the epoxy resin to the functional groups in the curing agent (functional groups in the curing agent / epoxy groups in the epoxy resin) is in the range of 0.8 to 2.0, and more preferably in the range of 0.8 to 1.5, when the curing agent is a phenolic curing agent, an amine curing agent, or an acid anhydride curing agent, because this makes it less likely to be affected by residual unreacted epoxy groups or functional groups of the curing agent.

[0078] When the curing agent is an amide-based curing agent, a tertiary amine, imidazole and its derivatives, organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan-based curing agents, isocyanate-based curing agents, blocked isocyanate-based curing agents, etc., it is preferably used in an amount of 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, per 100 parts by mass of the epoxy resin. On the other hand, it is preferably used in an amount of 20 parts by mass or less, more preferably 15 parts by mass or less. In the case of a dicyandiamine compound, it is preferably used in an amount of 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, per 100 parts by mass of the epoxy resin. On the other hand, it is preferably used in an amount of 10 parts by mass or less, more preferably 6 parts by mass or less.

[0079] (Reactive Diluent) When the resin composition is in a liquid state, the resin composition may contain a reactive diluent. The reactive diluent is not particularly limited as long as it contains at least one type of monofunctional epoxy compound. Monofunctional epoxy compounds are epoxy compounds having one epoxy group and have traditionally been used as reactive diluents to adjust the viscosity of epoxy resin compositions. Monofunctional epoxy compounds are broadly classified into aliphatic monofunctional epoxy compounds and aromatic monofunctional epoxy compounds, and aromatic monofunctional epoxy compounds are preferred from the viewpoint of viscosity.

[0080] (Other Additives) In addition to the above, the present resin composition may appropriately contain other additives selected from coupling agents, ultraviolet inhibitors, antioxidants, plasticizers, flame retardants, colorants, flow improvers, antifoaming agents, ion trapping agents, etc.

[0081] Furthermore, when the present resin composition is liquid, the present resin composition is preferably solvent-free. By using a solvent-free system, it is possible to prevent the solvent from volatilizing and generating voids when the liquid composition is heat-cured. Note that the term "solvent" refers to a volatile component, and in this specification, this term encompasses water and organic solvents. A solvent-free liquid composition is one that does not substantially contain a solvent. For example, the solvent content is preferably less than 3% by mass, more preferably less than 1% by mass, and even more preferably 0% by mass, relative to the total amount of the liquid composition.

[0082] (Method for producing the present resin composition) The present resin composition can be obtained by mixing and kneading a zeolite, a resin, and optionally an inorganic filler other than zeolite, a curing agent, a dispersant, a reactive diluent, and other additive components using a vacuum mixer, mixing roll, planetary mixer, etc., and degassing as necessary. The order in which these components are mixed is arbitrary, as long as there are no particular problems, such as the generation of reactions or precipitates. Two or more of the constituent components may be mixed in advance, and then the remaining components may be mixed, or all of the components may be mixed at once.

[0083] (Physical Properties of the Resin Composition) <Average Coefficient of Thermal Expansion (CTE)> When the resin composition is cured to a gel fraction of 80% or more, the average coefficient of thermal expansion (CTE) of the cured product at 25 to 100°C is preferably 0 ppm / K or more, more preferably 2 ppm / K or more, even more preferably 4 ppm / K or more, and particularly preferably 10 ppm / K or more. On the other hand, it is preferably 100 ppm / K or less, more preferably 50 ppm / K or less, and even more preferably 30 ppm / K or less. Because such a resin composition has a low average coefficient of thermal expansion at temperatures below the glass transition temperature, it is useful as a material requiring various heat resistance properties, and is particularly effective for application to electronic devices.

[0084] The average thermal expansion coefficient may be measured by thermomechanical analysis of a cured product obtained by curing a resin composition to a gel fraction of 80% or more. Specific measurement conditions are as described in the Examples.

[0085] <Viscosity> When the present resin composition is used as a liquid composition, it is preferably a composition that has fluidity at room temperature (23°C). The viscosity of the present resin composition is preferably low in order to make it easy to fill even narrow spaces with the composition. On the other hand, it is preferably high in order to make it less likely to drip when filling the composition. The viscosity of the present resin composition at 23°C is preferably 0.1 Pa·s or more, more preferably 1 Pa·s or more, even more preferably 3 Pa·s or more, and particularly preferably 5 Pa·s or more. On the other hand, it is preferably 250 Pa·s or less, more preferably 150 Pa·s or less, even more preferably 50 Pa·s or less, and particularly preferably 20 Pa·s or less.

[0086] The viscosity at 23° C. may be measured using a B-type rotational viscometer, which is one of the single cylinder rotational viscometer methods. The B-type rotational viscometer may be, for example, the one described in the Examples.

[0087] <Water Absorption> When the resin composition is cured to a gel fraction of 80% or more, the cured product preferably has a water absorption of 5% or less. If the water absorption is 5% or less, problems caused by moisture absorption are unlikely to occur, even when the resin composition is used as part of an electronic component such as an underfill material. From the above perspective, the lower the water absorption, the better, more preferably 4% or less, even more preferably 3% or less, and particularly preferably 2% or less. The water absorption can be measured by the method described in the examples.

[0088] (Applications) The resin composition can be used, for example, in catalyst modules, molecular sieve membrane modules, optical components, moisture-absorbing materials, food products, building materials, and components and packaging materials for electronic devices, among which electronic devices are preferred. Electronic devices include devices that have two or more electrodes and control the current flowing between the electrodes or the voltage generated therefrom using electricity, light, magnetism, or chemicals, or devices that generate light, an electric field, or a magnetic field using an applied voltage or current. Specific examples include resistors, rectifiers (diodes), switching elements (transistors, thyristors), amplifier elements (transistors), memory elements, chemical sensors, and devices that combine or integrate these elements. Other examples include photodiodes or phototransistors that generate photocurrent, electroluminescent elements that emit light when an electric field is applied, and optical elements such as photoelectric conversion elements or solar cells that generate electromotive force when exposed to light. The electronic device is preferably a semiconductor device. The semiconductor device preferably has at least a semiconductor substrate, and examples include devices in which a semiconductor chip is mounted on a substrate and devices in which semiconductor chips and semiconductor substrates are stacked in multiple layers. That is, an electronic device including the semiconductor encapsulant of the present invention is also within the scope of the present invention.

[0089] [Semiconductor encapsulant] The semiconductor encapsulant of the present invention can encapsulate and protect a variety of objects, such as electronic devices that use semiconductors, and a semiconductor encapsulant comprising the resin composition of the present invention is also within the scope of the present invention. More specifically, there are embodiments in which the liquid semiconductor encapsulant is used as an underfill material, and embodiments in which the liquid semiconductor encapsulant is used as an encapsulant that covers the entire semiconductor element.

[0090] (Liquid semiconductor encapsulant) When the resin composition is in a liquid state, it is preferably used as a liquid semiconductor encapsulant, and in this case, the liquid composition is cured to form a semiconductor encapsulant. Note that a method for producing a semiconductor encapsulant including a step of curing the resin composition is also within the scope of the present invention. The liquid semiconductor encapsulant can be used as an underfill material as described below, and can also be used as an encapsulant that covers the entire semiconductor element.

[0091] <Underfill Material> When the above-described liquid semiconductor encapsulant is used as an underfill material, it can be suitably used in the following manner. The liquid semiconductor encapsulant may be used as a semiconductor encapsulant that fills gaps formed in components by filling the gaps and then curing. A method for manufacturing a semiconductor encapsulant that includes a step of filling the gaps with a resin composition and then curing the resin composition is also within the scope of the present invention. The liquid semiconductor encapsulant may also be used as a semiconductor encapsulant that fills gaps between components, for example, by applying the liquid semiconductor encapsulant to various components, overlaying another component on the liquid semiconductor encapsulant, and then appropriately curing the liquid semiconductor encapsulant. In this case, the liquid semiconductor encapsulant may be appropriately cured to a B-stage before overlaying the other component. Among these, the present resin composition, particularly a liquid composition in which the present resin composition is in a liquid form, is preferably used for applications in which the resin composition is filled into gaps and cured. That is, it is preferable to produce a semiconductor encapsulant by filling the gaps with the resin composition and then curing the resin composition.

[0092] The resin composition is preferably used as a liquid semiconductor encapsulant, and particularly preferably as an underfill material. The underfill material is preferably used in the manufacture of electrical devices, particularly semiconductor devices, and is preferably used to fill gaps formed between a substrate and a semiconductor chip, between substrates, or between semiconductor chips. Known substrates can be used as the substrate, and substrates made of organic materials such as epoxy resin substrates and phenolic resin substrates are preferably used. The semiconductor chip is preferably formed from a semiconductor substrate such as a silicon substrate. The resin composition has a low thermal expansion coefficient when cured, and its use as an underfill material reduces the difference with the thermal expansion coefficient of the semiconductor substrate, thereby improving thermal cycle resistance, etc.

[0093] The underfill material is preferably used as a semiconductor encapsulant that fills the gap between a substrate and a semiconductor chip in a laminate having a semiconductor chip mounted on a substrate, and then hardens by heating to seal the gap between the substrate and the chip. In this case, the semiconductor chip may be bonded to the surface of the substrate on which a wiring pattern is formed via bumps, for example, by reflow or the like, before the underfill material is filled.

[0094] The underfill material may be used in the manufacture of semiconductor devices using a pre-apply method. Specifically, the underfill material is filled between the bumps on the surface of a semiconductor chip on which a plurality of bumps are formed, forming an underfill layer. The filled underfill material may be B-staged as necessary. The semiconductor chip on which the underfill layer is formed may then be placed on the surface of the substrate with the underfill layer facing the substrate. The underfill layer is then cured by heating and pressurizing, etc., to form a semiconductor encapsulant, and the semiconductor chip may be bonded via the bumps to the surface of the substrate on which a wiring pattern is formed.

[0095] In the pre-apply method, an underfill material may be applied to the surface of a substrate on which a wiring pattern has been formed to form an underfill layer. The applied underfill layer may be B-staged as necessary. The semiconductor chip on which the bumps have been formed may then be placed on the substrate on which the underfill layer has been formed, with the bump-formed surface facing the surface of the substrate on which the underfill layer has been formed. The underfill layer is then cured by heating and pressurizing, etc., to form a semiconductor encapsulant, and the semiconductor chip may be bonded to the surface of the substrate on which the wiring pattern has been formed via the bumps.

[0096] In the above description, the underfill material is used as a semiconductor encapsulant that fills the gap between the substrate and the semiconductor chip, but the use of the underfill material is not particularly limited, and it may be used to fill the gap between semiconductor chips, or as a semiconductor encapsulant that fills the gap between substrates, etc. Furthermore, the substrate is not limited to a substrate made of an organic material, and may be a semiconductor substrate, etc.

[0097] <Encapsulant> The liquid semiconductor encapsulant can also be used as an encapsulant that covers the entire semiconductor element. By covering an organic electronic element, such as an electronic device, with the semiconductor encapsulant, it is possible to effectively block oxygen and moisture from entering from the outside, thereby improving the lifespan of the electronic device. This is particularly effective for protecting objects including elements that are sensitive to moisture or humidity. When the liquid semiconductor encapsulant is used as an encapsulant that covers the entire semiconductor element, it can be produced using a mold. That is, a mold encapsulation method can be used in which a semiconductor chip or wire bonding is placed in a mold cavity, a liquid semiconductor encapsulant or a molten semiconductor encapsulant (resin) is poured into it, and then the resin is cured and the product is removed. This method allows for relatively easy production of an encapsulant that covers the entire semiconductor element.

[0098] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to the following examples and comparative examples as long as it does not deviate from the gist of the present invention.

[0099] (Evaluation of Physical Properties) The evaluation of physical properties was carried out as follows.

[0100] (α-rays) The α-rays of zeolite were measured using the following procedure. 5 g of zeolite was dispersed in 25 ml of ethyl alcohol, and the entire sample was transferred onto a 13 cm square sample stage so that the surface was uniform, and then allowed to dry naturally. The naturally dried sample was vacuum-dried together with the sample stage to completely remove the dispersion medium. After vacuum drying, the sample stage was set in a trace α-ray energy distribution measuring device (device name: KS-1000, manufactured by Hitachi, Ltd.), and measurements were carried out for 200 hours. Of the results obtained, the surface α-rays were measured at 2.0 to 10.0 MeV, which is the measurement range of the device, and at 4.0 to 10.0 MeV, which is the range of α-ray existence energies for natural nuclides with a decay chain. Note that the lower limit of measurement under these measurement conditions was 0.0064 counts / cm for the surface α-rays at 2.0 to 10.0 MeV. ２ h, surface alpha dose at 4.0-10.0 MeV is 0.0039 count / cm ２ (Evaluation criteria) A (good): The surface alpha dose at 2.0 to 10.0 MeV and the surface alpha dose at 4.0 to 10.0 MeV are both below the lower limit of measurement. B (fair): The surface alpha dose at 2.0 to 10.0 MeV is 0.0064 count / cm ２ h or more and the surface alpha dose at 4.0 to 10.0 MeV is less than the lower limit of measurement C (bad); the surface alpha dose at 2.0 to 10.0 MeV is 0.0064 count / cm ２ ・The surface alpha dose at 4.0 to 10.0 MeV is 0.0039 count / cm ２ ・More than h

[0101] (SAR(Si / Al ２ SAR (Si / Al ratio) of zeolite ２ The SiO ratio was measured by the following procedure: Approximately 500 mg of zeolite was covered with a polypropylene film, which was then placed in a fluorescent X-ray analyzer (apparatus name: Supermini 200, manufactured by Rigaku) ​​for measurement. ２ Concentration and Al ２ O ３ The SAR (Si / Al) was calculated from the obtained concentration values. ２ The ratio was calculated.

[0102] (Weight Loss Rate) The weight loss rate of zeolite was measured by the following procedure. Approximately 5 mg of zeolite was placed in a platinum cup and placed in a thermal analyzer (apparatus name: TGA Q5000IR, manufactured by TA Instruments). The temperature was increased from room temperature to 800°C at a rate of 10°C / min in an air atmosphere and held at 800°C for 10 minutes. The weight loss rate was determined as the weight loss rate at 800°C relative to the weight at 400°C. Specifically, it was calculated by the formula "weight loss rate of zeolite = 100 × {(weight at 400°C) - (weight held at 800°C for 10 minutes)} / (weight at 400°C)."

[0103] (Circularity of Primary Particles) The circularity of primary particles of zeolite was measured by the following procedure. Particles were observed using a particle image analyzer (device name: MORPHOLOGI 4, manufactured by Spectris). The area and circumference of 20,000 to 30,000 particles detected were determined, and the formula "Circularity = 4 x π x Area / (Circumference)" was used. ２ The average value of the obtained circularity values ​​of each particle was calculated, and this was taken as the circularity of the primary particles of the zeolite.

[0104] (Circle-equivalent diameter of primary particles) The circle-equivalent diameter of primary particles of zeolite was measured by the following procedure. Particles were observed using a particle image analyzer (device name: MORPHOLOGI 4, manufactured by Spectris). The area of ​​20,000 to 30,000 particles detected was calculated, and the circle-equivalent diameter was calculated as follows: "Circle-equivalent diameter = 2 × (area / π)" ０．５ The average of the obtained circle-equivalent diameters of each particle was calculated, and this was taken as the circle-equivalent diameter of the primary particles of the zeolite.

[0105] (Elemental Analysis of Uranium and Thorium) The amounts of uranium and thorium contained in the zeolite and the raw materials, amorphous silica and aluminum hydroxide, were measured by the following procedure. Each substance was dissolved in acid, and the amounts of uranium and thorium in the solution were measured using a high-resolution inductively coupled plasma mass spectrometer (instrument name: ELEMENT XR, manufactured by Thermo Fisher Scientific). The lower detection limit of the instrument was 0.1 ppb by mass.

[0106] (Elemental analysis of sodium and potassium) The amounts of sodium and potassium contained in the zeolite and the raw materials, amorphous silica and aluminum hydroxide, were measured by the following procedure. Each substance was dissolved in acid, and then the amounts of sodium and potassium in the solution were measured using an inductively coupled plasma optical emission spectrometer (device name: iCAP7600Duo, manufactured by Thermo Fisher Scientific). The detection limit of the device was 1 ppm by mass.

[0107] (Average Coefficient of Thermal Expansion (CTE)) The average coefficient of thermal expansion of the cured product when the resin composition was cured to a gel fraction of 80% or more was measured by thermomechanical analysis using a method in accordance with JIS K7197 (2012). It was measured by a compression method using a thermomechanical analyzer (model: TMA SS7100, manufactured by SII NanoTechnology, Inc.). Specifically, when the resin composition was cured to a gel fraction of 80% or more, the cured product was cut into a size of φ6 mm x 10 mm, and the temperature was increased from 20°C to 200°C at a rate of 5°C / min using a thermomechanical analyzer by a compression method. The temperature change in the change in the sample length from 25 to 100°C was measured, and the slope of the tangent was taken as the average coefficient of thermal expansion (CTE).

[0108] (Viscosity) The viscosity of the resin composition at 23°C was measured using a Brookfield type rotational viscometer. When the viscosity was 0.1 to 100 Pa s, an "LVDV-1 Pri" manufactured by Brookfield, with spindles S64 and S63, was used as the Brookfield type rotational viscometer, and when the viscosity exceeded 100 Pa s, an "HBDV-E" manufactured by Brookfield, with spindle S-07, was used. The value measured at 5 rpm was used as the representative viscosity value for each sample.

[0109] (Water absorption rate) When the resin composition was cured to a gel fraction of 80% or more, the cured product was kept in a drying oven at 125°C for 3 hours, and then kept in a constant temperature and humidity chamber adjusted to 85°C and 85% humidity for 3 hours, after which the weight change rate (%) was evaluated.

[0110] Production Example 1 To a vessel were sequentially added water, N,N,N-trimethyl-1-adamantylammonium hydroxide (TMadaOH) manufactured by Seichem Corporation as an organic structure directing agent (SDA), Kyoward 200S manufactured by Kyowa Chemical Industry Co., Ltd. as an aluminum atom source, which has a uranium content of 454.9 ppb by mass based on aluminum atoms and a thorium content of 3.8 ppb by mass based on aluminum atoms, and amorphous silica as a silicon atom source, which has a uranium content of less than 0.3 ppb by mass based on silicon atoms and a thorium content of less than 0.3 ppb by mass based on silicon atoms. The composition and molar ratio of the resulting mixture were as follows: SiO ２ :Al ２ O ３ :TMadaOH:H ２ The ratio of SiO to CHA-type zeolite was 1.0:0.0294:0.176:18. ２ After adding 5% by mass of the zeolite to the powder and mixing well, the resulting mixture was placed in a pressure vessel and subjected to hydrothermal synthesis in an oven at 150°C for 48 hours. After suction filtration and washing, the mixture was dried to obtain CHA-type zeolite. The primary particles of the resulting zeolite had a circularity of 0.922. The primary particles of the resulting zeolite also had an equivalent circle diameter of 4.00 µm. When the obtained powder was subjected to XRD analysis, it was confirmed to be CHA-type zeolite. The SAR (Si / Al ２ The weight loss ratio of the obtained zeolite was determined by the above method and was 23.6%. The amounts of uranium and thorium contained in the obtained zeolite were determined by the above method and were found to be 7.8 mass ppb, and the amount of thorium was less than 0.1 mass ppb, which is the lower limit of detection. The amounts of sodium and potassium contained in the obtained zeolite were determined by the above method and were found to be 34 mass ppm and 1 mass ppm, respectively. The α dose of the obtained zeolite was determined by the above method and was found to be 0.0064 counts / cm, which is the lower limit of detection, within the measurement range of the apparatus, 2.0 to 10.0 MeV. ２h, and the surface alpha dose in the range of 4.0 to 10.0 MeV, which is the range of alpha ray energy in natural nuclides with decay chains, is also the lower detection limit of 0.0039 count / cm ２ Therefore, the evaluation result of the alpha dose was A.

[0111] Production Example 2 To a vessel were sequentially added water, N,N,N-trimethyl-1-adamantylammonium hydroxide (TMadaOH) manufactured by Seichem Corporation as an organic structure directing agent (SDA), and "Aluminumsol-10A" manufactured by Kawaken Fine Chemicals Co., Ltd. as an aluminum atom source, which has a uranium content of less than 1.9 ppb by mass based on aluminum atoms and a thorium content of 22.7 ppb by mass based on aluminum atoms. The mixture was heated at 80°C for 3 hours while stirring thoroughly. Thereafter, amorphous silica was added as a silicon atom source, which has a uranium content of less than 0.3 ppb by mass based on silicon atoms and a thorium content of less than 0.3 ppb by mass based on silicon atoms. The composition and molar ratio of the resulting mixture were as follows: SiO ２ :Al ２ O ３ :TMadaOH:H ２ The ratio of SiO to CHA-type zeolite was 1.0:0.0294:0.176:18. ２ After adding 5% by mass of the zeolite to the powder and mixing well, the resulting mixture was placed in a pressure vessel and subjected to hydrothermal synthesis in an oven at 150°C for 48 hours. After suction filtration and washing, the mixture was dried to obtain CHA-type zeolite. The primary particles of the resulting zeolite had a circularity of 0.934. The primary particles of the resulting zeolite also had a circular equivalent diameter of 4.61 µm. When the obtained powder was subjected to XRD analysis, it was confirmed to be CHA-type zeolite. The SAR (Si / Al ２The weight loss ratio of the obtained zeolite was determined by the above method and was found to be 23.7%. The amounts of uranium and thorium contained in the obtained zeolite were determined by the above method and found to be 0.4 mass ppb, and the amount of thorium was less than the detection limit of 0.1 mass ppb. The amounts of sodium and potassium contained in the obtained zeolite were determined by the above method and found to be 11 mass ppm, and the amount of potassium was less than the detection limit of 1 mass ppm. The α dose of the obtained zeolite was determined by the above method and found to be 0.0064 counts / cm, which is the detection limit for the surface α dose in the measurement range of the instrument, 2.0 to 10.0 MeV. ２ h, and the surface alpha dose in the range of 4.0 to 10.0 MeV, which is the range of alpha ray energy in natural nuclides with decay chains, is also the lower detection limit of 0.0039 count / cm ２ Therefore, the evaluation result of the alpha dose was A.

[0112] Production Example 3 To a vessel were sequentially placed water, N,N,N-trimethyl-1-adamantylammonium hydroxide (TMadaOH) manufactured by Seichem Corporation as an organic structure directing agent (SDA), "amorphous aluminum hydroxide" manufactured by Asada Chemical Industry Co., Ltd. as an aluminum atom source having a uranium content of 480.1 ppb by mass based on aluminum atoms and a thorium content of 9.6 ppb by mass based on aluminum atoms, "Snowtex N-40" manufactured by Nissan Chemical Industries Co., Ltd. as a silicon atom source having a uranium content of 10.1 ppb by mass based on silicon atoms and a thorium content of 314.7 ppb by mass based on silicon atoms, and amorphous silica having a uranium content of less than 0.3 ppb by mass based on silicon atoms and a thorium content of less than 0.3 ppb by mass based on silicon atoms. At this time, the ratio of Snowtex N-40 to amorphous silica is SiO derived from Snowtex N-40. ２ Concentration: 25%, SiO derived from amorphous silica ２ The concentration was adjusted to 75%. The composition and molar ratio of the resulting mixture was: SiO ２ :Al ２ O ３ :TMadaOH:H ２The ratio of SiO to CHA-type zeolite was 1.0:0.0294:0.19:25. ２ After adding 5% by mass of the zeolite to the powder and mixing well, the resulting mixture was placed in a pressure vessel and subjected to hydrothermal synthesis in an oven at 150°C for 48 hours. After suction filtration and washing, the mixture was dried to obtain CHA-type zeolite. The primary particles of the resulting zeolite had a circularity of 0.950. The primary particles of the resulting zeolite also had an equivalent circle diameter of 2.14 µm. When the obtained powder was subjected to XRD analysis, it was confirmed to be CHA-type zeolite. The SAR (Si / Al ２ The weight loss ratio of the obtained zeolite was determined by the above method and was 22.2%. The amounts of uranium and thorium contained in the obtained zeolite were determined by the above method and were found to be 11 mass ppb and 27 mass ppb, respectively. The amounts of sodium and potassium contained in the obtained zeolite were determined by the above method and were found to be 244 mass ppm and 2 mass ppm, respectively. The α dose of the obtained zeolite was determined by the above method and was found to be 0.0064 counts / cm, which is the lower limit of detection, at the surface α dose in the measurement range of the apparatus, 2.0 to 10.0 MeV. ２ h, and the surface alpha dose in the range of 4.0 to 10.0 MeV, which is the range of alpha ray energy in natural nuclides with decay chains, is also the lower detection limit of 0.0039 count / cm ２ Therefore, the evaluation result of the alpha dose was A.

[0113] Production Example 4 To a vessel were sequentially placed water, N,N,N-trimethyl-1-adamantylammonium hydroxide (TMadaOH) manufactured by Seichem Corporation as an organic structure directing agent (SDA), sodium oleate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. as a surfactant, "Kyoward 200S" manufactured by Kyowa Chemical Industry Co., Ltd. as an aluminum atom source having a uranium content of 454.9 ppb by mass based on aluminum atoms and a thorium content of 3.8 ppb by mass based on aluminum atoms, "Snowtex N-40" manufactured by Nissan Chemical Industries, Ltd. as a silicon atom source having a uranium content of 10.1 ppb by mass based on silicon atoms and a thorium content of 314.7 ppb by mass based on silicon atoms, and amorphous silica having a uranium content of less than 0.3 ppb by mass based on silicon atoms and a thorium content of less than 0.3 ppb by mass based on silicon atoms. At this time, the ratio of Snowtex N-40 to amorphous silica is SiO derived from Snowtex N-40. ２ Concentration: 75%, SiO derived from amorphous silica ２ The concentration was adjusted to 25%. The composition and molar ratio of the resulting mixture was: SiO ２ :Al ２ O ３ :TMadaOH:H ２ The ratio of O to surfactant was 1.0:0.025:0.3:25:0.02. Then, CHA-type zeolite was added as a seed crystal to SiO ２ After adding 5% by mass of the zeolite to the powder and mixing well, the resulting mixture was placed in a pressure vessel and subjected to hydrothermal synthesis in an oven at 150°C for 48 hours. After suction filtration and washing, the mixture was dried to obtain CHA-type zeolite. The primary particles of the resulting zeolite had a circularity of 0.947. The primary particles of the resulting zeolite also had an equivalent circle diameter of 1.86 µm. When the obtained powder was subjected to XRD analysis, it was confirmed to be CHA-type zeolite. The SAR (Si / Al ２The weight loss ratio of the obtained zeolite was determined by the above method and was 22.8%. The amounts of uranium and thorium contained in the obtained zeolite were determined by the above method and were found to be 12 mass ppb and 88 mass ppb, respectively. The amounts of sodium and potassium contained in the obtained zeolite were determined by the above method and were found to be 2110 mass ppm and 208 mass ppm, respectively. The α dose of the obtained zeolite was determined by the above method and was found to be 0.0068 count / cm at the surface in the measurement range of the instrument, 2.0 to 10.0 MeV. ２ h, and the surface alpha dose in the range of 4.0 to 10.0 MeV, which is the range of alpha ray existence energy in natural nuclides with decay chains, is the lower limit of detection, 0.0039 count / cm ２ Therefore, the evaluation result of the alpha dose was B.

[0114] Comparative Production Example 1 To a vessel were sequentially added water, N,N,N-trimethyl-1-adamantylammonium hydroxide (TMadaOH) manufactured by Seichem Corporation as an organic structure directing agent (SDA; Structure Directing Agent), sodium oleate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. as a surfactant, "Kyoward 200S" manufactured by Kyowa Chemical Industry Co., Ltd. as an aluminum atom source having a uranium content of 454.9 ppb by mass based on aluminum atoms and a thorium content of 3.8 ppb by mass based on aluminum atoms, and "Snowtex N-40" manufactured by Nissan Chemical Industries, Ltd. as a silicon atom source having a uranium content of 10.1 ppb by mass based on silicon atoms and a thorium content of 314.7 ppb by mass based on silicon atoms. The composition and molar ratio of the resulting mixture were as follows: SiO ２ :Al ２ O ３ :TMadaOH:H ２ The ratio of O to surfactant was 1.0:0.025:0.3:25:0.02. Then, CHA-type zeolite was added as a seed crystal to SiO ２After adding 5% by mass of the zeolite to the powder and mixing well, the resulting mixture was placed in a pressure vessel and subjected to hydrothermal synthesis in an oven at 150°C for 48 hours. After suction filtration and washing, the mixture was dried to obtain CHA-type zeolite. The primary particles of the resulting zeolite had a circularity of 0.936. The primary particles of the resulting zeolite also had a circular equivalent diameter of 1.90 µm. When the obtained powder was subjected to XRD analysis, it was confirmed to be CHA-type zeolite. The SAR (Si / Al ２ The weight loss ratio of the obtained zeolite was determined by the above method and was 22.6%. The amounts of uranium and thorium contained in the obtained zeolite were determined by the above method and were found to be 18 mass ppb and 207 mass ppb, respectively. The amounts of sodium and potassium contained in the obtained zeolite were determined by the above method and were found to be 2120 mass ppm and 184 mass ppm, respectively. The α dose of the obtained zeolite was determined by the above method and was found to be 0.0135 count / cm at the surface in the measurement range of 2.0 to 10.0 MeV. ２ h, and the surface alpha dose in the range of 4.0 to 10.0 MeV, which is the range of alpha ray existence energy in natural nuclides with decay chains, is 0.0072 count / cm ２ Therefore, the evaluation result of the alpha dose was C.

[0115] Comparative Production Example 2 A zeolite was produced in the same manner as in Comparative Production Example 1. The produced zeolite was calcined at 600°C for 6 hours in an air stream to obtain a calcined zeolite. The weight loss rate of the obtained zeolite was determined by the above-mentioned method and was found to be 0.4%.

[0116] Next, examples of the resin composition of the present invention will be described. <Components> The components used in preparing the resin composition are as follows.

[0117] <Epoxy Resin> (A) p-Aminophenol Type Epoxy Resin; Mitsubishi Chemical Corporation, Product Name: "jER630", Epoxy Equivalent: 97 g / equivalent <Curing Agent> (B) Acid Anhydride Curing Agent; Acid Anhydride (Main Component: Hydrogenated Methyl Nadic Anhydride): New Japan Chemical Co., Ltd., Product Name: "RIKACID HNA-100" (Acid Anhydride Equivalent: 174-184) (C) Imidazole Curing Agent; Shikoku Chemicals Corporation, Product Name: "2E4MZ-CN" <Filler> (D) Zeolite Filler 1; The zeolite produced in Production Example 1 described above was used. (E) Zeolite Filler 2; The zeolite produced in Production Example 2 described above was used. (F) Zeolite Filler 3; The zeolite produced in Production Example 3 described above was used. (G) Zeolite Filler 4; The zeolite produced in Production Example 4 described above was used. (H) Zeolite filler 5: The zeolite produced in the above-mentioned Comparative Production Example 1 was used. (I) Zeolite filler 6: The zeolite produced in the above-mentioned Comparative Production Example 2 was used. <Additives> (J) Additive: Wetting and dispersing agent, product name "DISPERBYK-2152" (amino group-containing ultramolecular weight polyester, comb type, solvent-free), manufactured by BYK Japan.

[0118] Example 1 The filler, resin, curing agent, and additives shown in Table 1 were blended in the amounts shown in Table 1. The mixture was then mixed at 1,500 rpm for 5 minutes using a vacuum mixer (EME Corporation, "V-mini 300") to prepare a resin composition (liquid composition). The viscosity of this liquid composition was evaluated using the method described above. The results are shown in Table 1. Next, this liquid composition was poured into a mold and heated at 80°C for 2 hours, then heated at 120°C for 2 hours to cure to a gel fraction of 80% or more, and then demolded to obtain a cured product. The CTE and water absorption of this cured product were evaluated using the evaluation methods described above. The results are shown in Table 1.

[0119] Examples 2 to 4 and Comparative Examples 1 and 2 In Example 1, the zeolite filler was replaced with one shown in Table 1, and resin compositions (liquid compositions) and cured products were obtained in the same manner as in Example 1. The results of evaluation in the same manner as in Example 1 are shown in Table 1.

[0120]

[0121] The zeolite fillers used in Examples 1 to 4 had low amounts of uranium and thorium, and the alpha dose was rated as good, with an A or B rating. In particular, the zeolite fillers used in Examples 1 to 3 had extremely low amounts of uranium and thorium, and the alpha dose of the cured products was rated as A (both the surface alpha dose at 2.0 to 10.0 MeV and the surface alpha dose at 4.0 to 10.0 MeV were below the lower measurement limit). Therefore, it is expected that electronic devices using the cured products prepared in Examples 1 to 4 as semiconductor encapsulants will be less likely to experience operational errors (soft errors). In particular, it is expected that electronic devices using the cured products prepared in Examples 1 to 3 as semiconductor encapsulants will be extremely unlikely to experience operational errors (soft errors). Furthermore, the water absorption of the cured products prepared in Examples 1 to 4 was lower than that of the cured product prepared in Comparative Example 2. This is presumed to be due to the fact that the zeolite fillers used in Examples 1 to 4 contain components derived from the organic structure-directing agent and have low water adsorption. Furthermore, the zeolites of Examples 1 to 3 have lower sodium and potassium contents than the zeolite of Comparative Example 1, and it is expected that the reliability of devices will be improved when used as semiconductor encapsulants. In particular, the zeolites of Examples 1 and 2 have extremely lower sodium and potassium contents than the zeolite of Comparative Example 1, and it is expected that the reliability of devices will be improved when used as semiconductor encapsulants. In other words, the zeolites of the present invention have low moisture absorption and low alpha radiation levels, and are suitable for use as semiconductor encapsulants.

[0122] According to the present invention, it is possible to provide a zeolite that has low moisture absorption and low alpha radiation. By sealing electronic devices such as electronic devices with a semiconductor encapsulant containing the zeolite, it is possible to suppress the deterioration of the dielectric constant and reliability of the electronic materials due to the presence of water, and to suppress malfunctions caused by alpha rays.

Claims

1. A zeolite that, when heated to 800°C at a rate of 10°C / min in an air atmosphere and held at 800°C for 10 minutes, exhibits a weight loss of 1% or more at 800°C, based on the weight at 400°C, as determined by thermogravimetric analysis (TGA), and has a uranium and thorium content of 200 ppb by mass or less in total.

2. The zeolite according to claim 1, wherein the circularity of the primary particles is 0.850 or more.

3. The zeolite of claim 1 having d6r as CBU.

4. The zeolite according to claim 1, which has an oxygen ring structure of 8 or less members.

5. The zeolite of claim 1, which has a CHA structure.

6. The zeolite according to claim 1, having a uranium content of 8 ppb by mass or less.

7. The zeolite according to claim 1, having a thorium content of 1 ppb by mass or less.

8. The zeolite according to claim 1, wherein the total content of sodium and potassium is 2,000 mass ppm or less.

9. The zeolite according to claim 1, wherein the total content of uranium and thorium is 0.00002 ppb by mass or more.

10. The zeolite according to claim 1, wherein the uranium to thorium content ratio (uranium content / thorium content) is 0.01 or more and 1,000 or less.

11. Surface alpha dose at 4.0 to 10.0 MeV is 0.0072 count / cm ２ 2. The zeolite of claim 1, wherein the zeolite has a viscosity of less than 1000 sq m.

12. Surface alpha dose at 2.0 to 10.0 MeV is 0.0135 count / cm ２ 2. The zeolite of claim 1, wherein the zeolite has a viscosity of less than 1000 sq m.

13. A method for producing a zeolite according to any one of claims 1 to 12, using as raw materials a silicon atom raw material having a uranium content of less than 10 ppb by mass on a silicon atom basis and a thorium content of less than 314 ppb by mass on a silicon atom basis, and an aluminum atom raw material having a uranium content of 455 ppb by mass or less on an aluminum atom basis and a thorium content of 4 ppb by mass or less on an aluminum atom basis.

14. A resin composition comprising the zeolite according to any one of claims 1 to 12 and a resin.

15. The resin composition according to claim 14, wherein the resin comprises at least one resin selected from the group consisting of epoxy resins and polyimide resins.

16. The resin composition of claim 14, wherein the resin comprises an epoxy resin.

17. A semiconductor encapsulant comprising the resin composition according to claim 14.

18. A method for producing a semiconductor encapsulant, comprising a step of curing the resin composition according to claim 14.

19. An electronic device comprising the semiconductor encapsulant of claim 17.

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