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

Abstract

To provide a zeolite having a low sodium content and suitable for use as a semiconductor sealing material.SOLUTION: A content of sodium is less than 100 ppm by mass.SELECTED DRAWING: None

Description

[Technical Field]

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

[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 in order to improve heat resistance and thermal stability. However, 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 (for example, Patent Document 1), but alkalis such as sodium hydroxide are generally added during the synthesis of zeolite, and there is a concern that residual alkalis may cause corrosion of device wiring or a decrease in the performance of semiconductor elements. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2023 / 210790 Summary of the Invention [Problem to be solved by the invention]

[0005] Under the above circumstances, an object of the present invention is to provide a zeolite that has a low sodium content and is suitable for use as a semiconductor encapsulant. [Means for solving the problem]

[0006] As a result of intensive research into the above-mentioned problems, the present inventors have found that a zeolite with a low sodium content can be obtained by synthesizing it using specific raw materials, thereby solving the above-mentioned problems, and have completed the present invention. The gist of the present invention is as follows. [1] Zeolite having a sodium content of less than 100 ppm by mass. [2] The zeolite according to [1] above, having a potassium content of 180 mass ppm or less. [3] The zeolite according to [2] above, having a total content of sodium and potassium of 280 mass ppm or less. [4] The zeolite according to [2] or [3] above, wherein the ratio of sodium to potassium contained in the zeolite (sodium content / potassium content) is 0.5 or more and 10,000 or less. [5] The zeolite according to any one of the above [1] to [4], wherein 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, based on the weight at 400°C, is 1% or more, as determined by thermogravimetric analysis (TGA). [6] The zeolite according to any one of the above [1] to [5], which is an as-made type. [7] The zeolite according to any one of the above [1] to [6], having an SAR (Si / Al2 ratio) of 14 or more and 50 or less. [8] The zeolite according to any one of the above [1] to [7], wherein the circularity of the primary particles is 0.850 or more. [9] The zeolite according to any one of the above [1] to [8], which has d6r as CBU.

[10] The zeolite according to any one of the above [1] to [9], which has an oxygen ring structure of 8 or less members.

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

[10] , which has a CHA type structure.

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

[11] , wherein the total content of uranium and thorium is 200 mass ppb or less.

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

[12] and a resin.

[14] The resin composition according to

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

[15] The resin composition according to

[13] or

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

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

[13] to

[15] above.

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

[13] to

[16] above.

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

[16] above. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a zeolite that has a low sodium content and is suitable for use as a semiconductor encapsulant. DETAILED DESCRIPTION OF THE INVENTION

[0008] [Zeolite] The zeolite of the present invention (hereinafter sometimes referred to as "the zeolite") is characterized by having a sodium content of less than 100 ppm by mass. A sodium content of less than 100 ppm by mass makes it less likely to cause corrosion of device wiring or performance degradation of semiconductor elements when used as a semiconductor encapsulant. From the above perspectives, the sodium content of the zeolite of the present invention is more preferably 80 ppm by mass or less, even more preferably 60 ppm by mass or less, particularly preferably 50 ppm by mass or less, even more preferably 40 ppm by mass or less, and most preferably 35 ppm by mass or less. On the other hand, from the viewpoint of promoting nucleation of zeolite, sodium is preferably contained. That is, it is preferable that the zeolite particle contains at least one sodium atom. Therefore, the sodium content in the present zeolite is preferably 0.04 mass ppb or more. The sodium content in the zeolite can be measured by the method described in the Examples. Methods for adjusting the sodium content of the present zeolite to fall within the above range include, but are not limited to, using a highly pure raw material and washing with an acid.

[0009] Furthermore, the potassium content of the present zeolite is preferably 180 ppm by mass or less. When the potassium content is 180 ppm by mass or less, like sodium, when used as a semiconductor encapsulant, corrosion of device wiring and deterioration of semiconductor element performance are less likely to occur. From the above viewpoints, the potassium content of the present zeolite is more preferably 150 ppm by mass or less, even more preferably 100 ppm by mass or less, particularly preferably 50 ppm by mass or less, even more preferably 10 ppm by mass or less, and most preferably 5 ppm by mass or less. 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 particle contains at least one potassium atom. Therefore, the potassium content in the present zeolite is preferably 0.07 mass ppb or more. The potassium content in the zeolite can be measured using the same method as the method for measuring the sodium content described above. Methods for adjusting the potassium content of the present zeolite to fall within the above range include, but are not limited to, using a highly pure raw material and washing with an acid.

[0010] Furthermore, the total content of sodium and potassium in the present zeolite is preferably 280 ppm by mass or less. When the total content of sodium and potassium is 280 ppm by mass or less, when the present zeolite is used as a semiconductor encapsulant, corrosion of device wiring and deterioration of semiconductor element performance are less likely to occur. From the above viewpoints, the total content of sodium and potassium contained in the present zeolite is more preferably 200 ppm by mass or less, even more preferably 150 ppm by mass or less, particularly preferably 100 ppm by mass or less, even more preferably 75 ppm by mass or less, and 50 ppm by mass or less, and most preferably 35 ppm by mass or less. 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.

[0011] 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 of promoting densification of the zeolite framework formation due to the small ionic radius of sodium. Moreover, the content ratio (sodium content / potassium content) is preferably 10,000 or less, more preferably 5,000 or less, from the viewpoint of promoting dissolution of the silicon atom raw material and aluminum atom raw material, which are the raw materials for the zeolite, due to the high ionization tendency of potassium.

[0012] Furthermore, as described above, the present zeolite preferably has a low content of sodium and potassium, but it is also preferable that the content of alkalis such as alkali metals and alkaline earth metals other than sodium and potassium is low. A low alkali content can suppress wiring corrosion and deterioration in the performance of semiconductor elements when used as a semiconductor encapsulant.

[0013] Furthermore, the uranium and thorium contents of the present zeolite are also preferably low, and specifically, the total amount of uranium and thorium is preferably 200 mass ppb or less. When the total content is 200 mass ppb or less, α rays generated from the present zeolite can be suppressed, and malfunctions caused by α rays can be suppressed. From the above viewpoints, the total content of uranium and thorium is more preferably 150 mass ppb or less, even more preferably 100 mass ppb or less, particularly preferably 50 mass ppb or less, even more 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.

[0014] Furthermore, the uranium content of the present zeolite is preferably 17 mass ppb or less. A uranium content of 17 mass ppb or less can sufficiently reduce the alpha dose of the present zeolite. From the above perspectives, the uranium content is more preferably 15 mass ppb or less, even more preferably 10 mass ppb or less, and particularly preferably 8 mass ppb 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 mass ppb or more, and more preferably 0.0001 mass ppb or more. Methods for adjusting the uranium content in the present zeolite to fall within the above range include, but are not limited to, using a highly pure raw material and washing with an acid.

[0015] 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 thorium content 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 in the present zeolite to fall within the above range include, but are not limited to, using a highly pure raw material and washing with an acid.

[0016] The present zeolite preferably exhibits a weight loss rate at 800°C (hereinafter sometimes simply referred to as "weight loss rate") of 1% or more 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, based on the weight at 400°C, as determined by thermogravimetric analysis (TGA). Such a zeolite 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 may 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 lose a larger amount of weight 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.

[0017] 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, so that the cured product exhibits low moisture absorption. The mechanism by which the use of such a zeolite exhibits low moisture absorption is presumed to be as follows. Zeolites exhibit adsorption properties for water and other substances because they have a porous structure and acid sites that serve as adsorption sites. It is believed that the presence of organic substances, preferably components derived from organic structure-directing agents, within the pores prevents the zeolite from becoming completely porous, reducing its adsorption properties for water and other substances and its hygroscopicity. From this perspective, thermogravimetric analysis (TGA) of this zeolite shows that when the temperature is increased from 400°C to 800°C at a rate of 10°C / min and then held at 800°C for 10 minutes, the weight loss is preferably 1% or more, more preferably 2% or more, and even more preferably 3% or more. The weight loss may be 5% or more, 10% or more, or 20% or more.

[0018] (Zeolite particle size) The particle size of the present zeolite means the diameter of the largest circle (equivalent circle diameter) 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 particle, i.e., the equivalent circle diameter of the primary particle. 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 from the viewpoint of suppressing dispersibility when added to a resin, while it is preferably 200 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less from the viewpoint of uniformity when added to a resin. In particular, when used in an underfill material, the particle size is preferably 0.05 μm or more from the viewpoint of dispersibility when added to a resin, and preferably 10 μm or less from the viewpoint of gap injection properties. When used in an encapsulant that covers an 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 zeolite particles (powder, particles in a resin composition described later), measuring their particle sizes, and averaging the results. Although 100 particles are sufficient for calculating the average, in the examples and comparative examples, the average value of 20,000 to 30,000 particles was used to improve accuracy.

[0019] (Zeolite structure) Zeolite is a compound that contains silicon or aluminum and oxygen and has a TO4 unit (T element is an element other than oxygen that constitutes the framework) as a basic unit. Specific examples of zeolite 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. Zeolite is made up of structural units called Composite Building Units (hereinafter sometimes referred to as "CBUs"), which are made up of several (several to several tens) TO4 units connected together, and therefore has regular channels (tubular pores) and cavities (hollow spaces). The crystal structure of this CBU and zeolite, which will be described later, can be expressed using the code that specifies the structure of zeolites established by the International Zeolite Association (IZA). The structure of a zeolite can be identified using the Zeolite Structure Database 2018 Edition (http: / / www.iza-structure.org / databases / ) based on the X-ray diffraction pattern obtained using an X-ray structure analyzer (for example, the BRUKER D2PHASER tabletop X-ray diffractometer).

[0020] (Zeolite framework) The skeleton of the present zeolite preferably has d6r as the CBU, which makes it easier to obtain a resin composition with a low thermal expansion coefficient after curing. Examples of zeolites having d6r as 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. Among these, zeolites having an 8-membered oxygen ring or less structure are particularly preferred from the viewpoint of making it difficult for water molecules to penetrate into the pores. Zeolites having an 8-membered oxygen ring or less structure include zeolites with AEI, AFT, AFX, CHA, ERI, KFI, SAT, SAV, SFW, and TSC structure. Among these, zeolites with AEI, AFX, CHA, and ERI structure are more preferred, and zeolites with CHA structure are even more preferred, because the structure is stable even after shape control. 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 composed of oxygen and T elements (elements other than oxygen that constitute the framework) that form the zeolite framework. The above zeolites may be used alone or in combination of two or more kinds.

[0021] (Average thermal expansion coefficient of zeolite) The average thermal expansion coefficient of the present zeolite is preferably low because a small amount of the zeolite can easily reduce the average thermal expansion coefficient of the liquid composition described below. Furthermore, 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. In particular, a low average thermal expansion coefficient is preferred because it can suppress an increase in the viscosity of the liquid composition described below. Specifically, the average thermal expansion coefficient of the 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.

[0022] On the other hand, considering that the zeolite is used as a resin 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 difficult to separate. Therefore, the average thermal expansion coefficient of the zeolite is usually -1,000 ppm / K or more, preferably -900 ppm / K or more, more preferably -800 ppm / K or more, even more preferably -700 ppm / K or more, particularly preferably -500 ppm / K or more, and most preferably -300 ppm / K or more. In particular, when used as a semiconductor encapsulant, the average thermal expansion coefficient is preferably high, specifically -100 ppm / K or more, more preferably -50 ppm / K or more, even more preferably -40 ppm / K or more, particularly preferably -30 ppm / K or more, especially preferably -25 ppm / K or more, and most preferably -20 ppm / K or more. 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." In order 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 to the average lattice constant at 100°C when the temperature of the zeolite is raised. 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 raising the temperature after waiting until the lattice constant has stabilized.

[0023] 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, especially when the temperature is raised to a 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.

[0024] (Zeolite shape) The present zeolite is preferably spherical. By making the shape of the zeolite spherical, an increase in viscosity of a resin composition containing the zeolite can be suppressed. Specifically, it is preferable that the primary particles have the following circularity. The term "primary particle" refers to a unit particle that does not contain a crystal grain boundary inside. The "primary particle" can be determined by observation using a particle image analyzer.

[0025] (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. The circularity of cubic zeolites, which are common in ordinary zeolites, 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 the present application, "circularity" is the average value of 100 or more particles obtained using the particle image analyzer. Although 100 particles are sufficient for calculating the average value, in the examples and comparative examples, the average value is calculated from 20,000 to 30,000 particles to improve accuracy. Methods for adjusting the circularity of the primary particles of the present zeolite to fall within the above range include carrying out a classification treatment after hydrothermal synthesis, and adding seed crystals, amino acids, surfactants, and organic structure-directing agents in any proportion during hydrothermal synthesis.

[0026] (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 Less than 16.0T / 1000Å, more preferably 16.0T / 1000Å 3 The following is the result. On the other hand, a high framework density of the zeolite is preferable in that the structural stability of the zeolite is likely to be high. The framework density of the zeolite is preferably 12.0T / 1000Å. 3 More preferably, 13.0T / 1000Å or more 3 More preferably, 14.0T / 1000Å 3 When the framework density is within the above range, the zeolite can be used as a stable filler. The framework density refers to the number of T atoms present per unit volume of zeolite, and is a value determined by the structure of the zeolite. In this specification, the values ​​listed in the IZA Zeolite Structure Database 2017 Edition (http: / / www.iza-structure.org / databases / ) may be used.

[0027] Framework density: 16.0T / 1000Å 3 Larger, 17.0T / 1000Å 3 Examples of the following zeolites include zeolites with ERI, LTL, LTN, MOZ, OFF, SAT, SSF and -WEN structure types. Framework density: 15.0T / 1000Å 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. Framework density: 14.0T / 1000Å 3 Larger, 15.0T / 1000Å 3 Examples of the following zeolites include zeolites of the CHA, KFI, SAS and SAV structure types. Framework density: 14.0T / 1000Å 3 Examples of zeolites within the following ranges include zeolites of the EMT, FAU, JSR, SBS, SBT, and TSC structure types.

[0028] (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.

[0029] 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.

[0030] (Silica / Alumina Molar Ratio (SAR) of Zeolite) The silica / alumina molar ratio (hereinafter sometimes referred to as "SAR" or "Si / Al2 ratio") of the present zeolite is not particularly limited as long as the effects of the present invention are not impaired. A high SAR (Si / Al2 ratio) of the zeolite is preferable in that it increases the moisture resistance of the cured product and makes it easier to control the amount of countercations. Therefore, the SAR (Si / Al2 ratio) of the zeolite is usually 2 or more, preferably 5 or more, more preferably 10 or more, even more preferably 14 or more, particularly 18 or more, particularly 20 or more, particularly 22 or more, particularly 23 or more, particularly 23.5 or more, particularly preferably 24 or more, even more preferably 24.5 or more, and most preferably 25 or more. On the other hand, a low SAR (Si / Al2 ratio) of the zeolite is preferable in terms of easy and inexpensive production. Therefore, the SAR (Si / Al2 ratio) of the zeolite 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 preferably 36 or less, and most preferably 35 or less. When the SAR (Si / Al2 ratio) is within the above range, the amount of counter cations is easily controlled, and the production cost of the zeolite is low. The SAR (Si / Al2 ratio) of 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 structure-directing agent, the use of seed crystals, and synthesis conditions such as temperature and time. The SAR (Si / Al2 ratio) of zeolite can be determined by the method described in the Examples.

[0031] (Zeolite counter cation) 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, the counter cation 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, the more flexible they are compared to alkali metal ions or alkaline earth metal ions, and the more likely the zeolite will 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.

[0032] (Zeolite crystallinity) The crystallinity of the present zeolite is not particularly limited as long as the effects of the present invention are not impaired. This is because the Composite Building Unit (CBU) is presumed to be a factor that has a greater impact on the average thermal expansion coefficient of the cured product than the structure specified by the IZA code. The crystallinity of the zeolite can be determined by comparing a certain X-ray diffraction peak determined using an X-ray diffractometer (e.g., a BRUKER D2PHASER benchtop 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.

[0033] (Zeolite surface treatment) 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.

[0034] [Zeolite manufacturing method] Known methods can be applied to the production of zeolite. For example, when producing CHA-type zeolite, it can be produced with reference to the method described in JP-A-2009-097856. More specifically, an aluminum atom source, a silica atom source, an organic structure-directing agent, and the like are mixed to prepare an aqueous gel. The mixing order is usually as follows: the aluminum atom source is mixed with water, and then the silica atom source and the organic structure-directing agent are mixed with this. The prepared aqueous gel is then 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 a zeolite.

[0035] The particularly preferred zeolite described above can be produced by the following method (hereinafter sometimes referred to as "the present production method"). This 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, in this production method, as described above, the calcination treatment that is usually performed may not be performed, or partial calcination may be performed as long as the zeolite after the calcination treatment achieves the aforementioned weight loss rate of 1% or more. When 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. That is, it is preferable that the present zeolite is not calcined (uncalcined). By not performing the calcination treatment, it is easy to achieve a weight loss rate of 1% or more, and therefore it is possible to easily produce a zeolite for obtaining a resin composition with low moisture absorption. If necessary, a desired zeolite (hereinafter, sometimes referred to as "seed zeolite") may be used.

[0036] (silicon atom raw material) The silicon atom source used in this production method is not particularly limited as long as it is a source that satisfies the above-mentioned sodium content of the present zeolite. It is preferable to use a silicon atom source that satisfies the above-mentioned potassium content, uranium content, and thorium content of the present zeolite, and various known substances can be used as the silicon atom source. 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 are sources that satisfy the above-mentioned sodium content of the present zeolite, but amorphous is preferred from the viewpoint of high reactivity. Methods for reducing the sodium and potassium content in the silicon atom raw material include, for example, washing with pure water and ion exchange. Furthermore, as a method for reducing the uranium and thorium contents in the silicon atom raw material, for example, there is a method for heating the silicon atom raw material in the presence of a halogen. Furthermore, recycled materials can also be used as silicon atom raw materials, such as used zeolite and used silica. The silicon atom raw materials may be any raw materials that, as a whole, satisfy the above-mentioned sodium content of the present zeolite, and one type may be used alone, or two or more types may be used in any combination and ratio.

[0037] (Aluminum atom source) The aluminum atom source used in this production method is not particularly limited as long as it satisfies the sodium content of the zeolite. It is preferable to use an aluminum atom source that satisfies the potassium, uranium, and thorium contents of the zeolite. Various known aluminum atom sources 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 uranium and thorium contents. However, amorphous aluminum hydroxide, pseudoboehmite, boehmite, bayerite, gibbsite, and diaspore are preferred, with amorphous aluminum hydroxide being particularly preferred, due to their low content of undesirable anions and high solubility in alkaline solutions. Methods for reducing the sodium and potassium content in the aluminum atom raw material include, for example, washing with pure water and ion exchange. The method for reducing the uranium and thorium content in the aluminum atom raw material is not particularly limited, but may be, for example, by thoroughly washing the aluminum atom raw material after production. The aluminum atom source may be any source that, as a whole, satisfies the sodium content of the present zeolite, and one type may be used alone, or two or more types may be used in any combination and ratio.

[0038] (organic matter) As described above, the present zeolite preferably 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, including 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.

[0039] (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. Among these, N,N,N-trimethyl-1-adamantylammonium hydroxide (TMAdaOH) is preferred from the viewpoint of its ability to easily retain organic substances within the pores of the zeolite at temperatures ranging from room temperature to 200°C and to reduce the hygroscopicity of the zeolite. These agents may be used alone or in any combination and ratio of two or more. The amount of organic structure-directing agent used is, in terms of molar ratio to 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 1 or less, preferably 0.6 or less, more preferably 0.55 or less, even more preferably 0.5 or less, particularly preferably 0.45 or less, and most preferably 0.4 or less. By using within this range, it is believed that high-purity spherical zeolite with few by-products can be easily grown.

[0040] (water) When using a seed zeolite (described later), the amount of water used is preferably in a molar ratio to silicon (Si) contained in the raw material composition other than the seed zeolite of typically 5 or more, preferably 7 or more, more preferably 9 or more, and even more preferably 10 or more, from the viewpoint of facilitating crystal formation. Setting the amount of water within this range is preferred because it facilitates crystal formation. 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 size tends to be obtained. Furthermore, in terms of facilitating cost reduction in waste liquid treatment, the molar ratio to silicon (Si) is preferably 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.

[0041] (Seed zeolite) In the present zeolite production method, seed zeolite may be used. When seed zeolite is used, one type may be used alone, or two or more types may be used in any combination and ratio.

[0042] (Mixing of Raw Materials (Preparation of Pre-Reaction Raw Material Composition)) The raw material composition can usually be obtained by mixing the silicon atom raw material, the aluminum atom raw material, the organic structure-directing agent, and water, and then adding seed zeolite, if used. In the production of zeolite, in addition to the above-mentioned components, components such as an acid component that accelerates the reaction and a metal stabilizer such as polyamine may be added at any step as needed. Furthermore, when mixing the raw materials, heating may be performed in order to obtain a zeolite with higher crystallinity. The temperature during heating 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 is usually 24 hours or less, preferably 12 hours or less, and more preferably 8 hours or less.

[0043] (Aging) The raw material composition prepared as described above may be hydrothermally synthesized immediately after preparation, but to obtain a zeolite with higher crystallinity, it is preferable to age the raw material for a certain period of time under specified 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 less, preferably 95°C or less, and more preferably 90°C or less. 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 more, preferably 3 hours or more, and more preferably 5 hours or more. It is also usually 30 days or less, preferably 10 days or less, and more preferably 4 days or less.

[0044] (hydrothermal synthesis) Next, the obtained raw material composition is subjected to hydrothermal synthesis. Hydrothermal synthesis is usually 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 gas pressure to an extent that does not inhibit crystallization, while stirring, rotating or shaking the container, or leaving it stationary. The reaction temperature during hydrothermal synthesis is usually 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 usually 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 usually 2 hours or higher, preferably 3 hours or higher, and more preferably 5 hours or higher. On the other hand, it is usually 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.

[0045] (drying process) After hydrothermal synthesis, the zeolite is separated from the composition (hydrothermal synthesis reaction liquid) after hydrothermal synthesis. The separation method is not particularly limited, but it is usually separated by washing with water, followed by filtration, decantation, direct drying, or the like. 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, and the drying may be performed in air or in an inert gas atmosphere such as nitrogen or argon.

[0046] (Firing) The dried zeolite may be subjected to calcination or the like to remove an arbitrary proportion of the organic structure-directing agent and the like used during production, as long as the pores contain an organic substance, preferably a component derived from the organic structure-directing agent. By using a zeolite containing an organic substance, preferably a component derived from the organic structure-directing agent, in the pores of the present resin composition, it is possible to provide a resin composition that gives a cured product with a low CTE and low moisture absorption. When calcination is performed, the calcination temperature is usually 200°C to 1,000°C. By calcining at 200°C or higher, the organic structure-directing agent and the like can be removed, while at 1,000°C or lower, the physical properties of the zeolite are not impaired. From the above viewpoints, the calcination temperature is preferably 300°C or higher, more preferably 350°C or higher, and even more preferably 400°C or higher, and is preferably 900°C or lower, more preferably 800°C or lower, and even more preferably 700°C or lower. The atmosphere for firing is not particularly limited, and the firing may be carried out in air or in 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 preferable. 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, calcination is performed under a gas flow of 5 ml / min to 20 ml / min.

[0047] [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 resin composition will be read as a liquid composition. In this specification, "liquid at room temperature" means having fluidity between 10°C and 35°C.

[0048] (Zeolite content) The content of the present zeolite in the present 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, based on the total amount of the resin composition, from the viewpoint of reducing the thermal expansion coefficient of the resin composition. On the other hand, the content of the present zeolite in the present 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, based on the total amount of the resin composition, from the viewpoint of suppressing an increase in the viscosity of the resin composition.

[0049] (Inorganic fillers 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, fullerene, 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 reduce the viscosity of the resin composition. Note that even in this silica, the sodium content is preferably 1,000 ppm by mass or less, more preferably 500 ppm by mass or less, and even more preferably 100 ppm by mass or less.

[0050] 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.

[0051] 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, in order to fully exhibit the effect of the present zeolite, i.e., low CTE.

[0052] (Total inorganic filler amount) The total content of all inorganic fillers (total inorganic fillers) contained in the present resin composition is preferably high in order to facilitate the development of their filler effects. 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 ease of filling 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, based on 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.

[0053] (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 semiconductor encapsulation, it is preferable to include a thermosetting resin.

[0054] <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, the present invention preferably contains at least one selected from the group consisting of epoxy resins and polyimide resins, and more preferably contains an epoxy resin.

[0055] <<Epoxy resin>> The epoxy resins that can be used in the present invention are preferably epoxy compounds having an aromatic ring, such as a bisphenol A skeleton, a bisphenol F skeleton, or a biphenyl skeleton, because they tend to have a low thermal expansion coefficient after curing. 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.

[0056] Furthermore, the resin composition is preferably made of a polyfunctional epoxy resin, since it tends to have a high glass transition temperature after heat curing. Examples of polyfunctional epoxy resins include glycidyl ether polyfunctional epoxy resins such as 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, and heavy oil-modified phenol resin, and epoxy resins produced from various phenolic compounds, such as polyhydric phenol resins obtained by condensation reaction of various phenols with various aldehydes, such as hydroxybenzaldehyde, crotonaldehyde, and glyoxal, and epihalohydrin.

[0057] From the viewpoint of fluidity, the epoxy resin preferably has a viscosity of 5 Pa·s or less at 23°C, 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 can be measured using a B-type rotational viscometer ("LVDV-1 Pri", Brookfield, spindle: S62), which is one of the single cylinder rotational viscometer methods.

[0058] 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 the lower melting point of the epoxy resin and the lower viscosity improve the filling properties of the resin composition and tend to enhance bonding properties due to filling. The epoxy resin may be used alone or in any combination and ratio of two or more kinds, but in the case of a mixture, the epoxy equivalent weight is the equivalent weight of the mixture.

[0059] The content of the epoxy resin in the resin composition is preferably low, since this increases the content of inorganic fillers such as zeolite relatively 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.

[0060] <<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 thermal expansion coefficient of the resin composite is likely to be low and the resin composite has excellent properties such as heat resistance, mechanical strength, electrical properties, and solvent resistance. More specifically, it is preferable to use a polyimide powder obtained by granulating a polyimide resin powder obtained by polymerizing and imidizing an aromatic tetracarboxylic acid component and p-phenylenediamine, followed by spraying a polyimide precursor solution on the polyimide resin powder, and then combine the polyimide powder with a filler to form a resin composite material. 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 aggregates. The polyimide precursor may be, for example, a polyamic acid. The polyimide precursor solution used as a raw material is a polyamic acid produced by reacting a tetracarboxylic dianhydride with a diamine in the presence of a basic compound with a pKa of 7.5 or higher, using water and / or an alcohol-based solvent as a reaction solvent.

[0061] (dispersant) The present resin composition may contain a dispersant to enhance the dispersibility of inorganic fillers such as the present zeolite. The dispersant contained in the liquid composition containing a resin and a filler is primarily added to a liquid composition containing a resin and a filler with a large polarity difference to improve the interface between the two and enhance compatibility. This can produce effects such as reducing viscosity, improving filler dispersibility, and preventing filler aggregation and sedimentation.

[0062] 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. The dispersant is preferably a polymeric dispersant. The main chain skeleton of the polymeric dispersant is not particularly limited, but examples include a polyurethane skeleton, a polyacrylic skeleton, a polyester skeleton, a polyamide skeleton, a polyimide skeleton, and a polyurea skeleton. In terms of storage stability, a polyurethane skeleton, a polyacrylic skeleton, and a polyester skeleton are preferred. The structure of the polymeric dispersant is also not particularly limited, but examples include a random structure, a block structure, a comb structure, and a star structure. Similarly, in terms of storage stability, a block structure or a comb structure is preferred. Furthermore, the dispersant is preferably a solvent-free dispersant, particularly a solvent-free polymer dispersant, which can prevent voids from being generated due to the dispersant volatilizing when the composition is heat-cured. Commercially available dispersants can be used as the dispersant. Examples of commercially available dispersants include the following dispersants, 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.

[0063] Commercially available polymeric dispersants include 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 of the DISPERBYK wetting and dispersing agent series available from BYK-Chemie, and 4008 of the EFKA series 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, 1210, 1220, 1831, 1850, 1860, 2100, 2150, 2200, 7004, KS-260, KS-273N, KS-860, KS-873N, PW-36, DN-900, and the DISPARLON series commercially available from Kusumoto Chemicals 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 a surfactant include CT131, CT136, GA, TG, TGE, STG and E1004 from the Olfin series commercially available from Nissin Chemical Industry Co., Ltd., 70, 2120, and 2190 from 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.

[0064] 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 make it easy to fill the liquid composition into a narrow space and to 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.

[0065] (hardening agent) The resin composition preferably further contains a curing agent, which is a substance that contributes to a 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, polyetheramines, 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.

[0066] 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.

[0067] 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, and tetra(hydroxyethyl)ethylenediamine. Examples of polyetheramines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propylamine), polyoxypropylene diamine, polyoxypropylene triamines, and the like. 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.

[0068] 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 acid anhydride, 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 anhydride, 3,4-dimethyl-6-(2-methyl-1-propenyl)-4-cyclohexene-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, and 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride.

[0069] 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, 2,4-diamino-6-[2'-methylimidazole], 1-benzyl-2-methylimidazole, 1-benzyl ... 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 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.

[0070] Examples of organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine. Examples of phosphonium salts include tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, and tetrabutylphosphonium tetrabutylborate. Examples of tetraphenylboron salts include 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate. These curing agents may be used singly or in any combination and ratio of two or more.

[0071] When the 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 is unlikely to be affected by residual unreacted epoxy groups or functional groups of the curing agent.

[0072] When the curing agent is an amide curing agent, a tertiary amine, imidazole and its derivatives, organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan curing agents, isocyanate curing agents, or blocked isocyanate curing agents, it is preferably used in an amount of 0.1 part by mass or more, more preferably 0.5 parts by mass or more, per 100 parts by mass of the epoxy resin, while 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 part by mass or more, more preferably 0.5 part by mass or more, relative to 100 parts by mass of the epoxy resin, and is preferably used in an amount of 10 parts by mass or less, more preferably 6 parts by mass or less.

[0073] (reactive diluent) When the resin composition is liquid, 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.

[0074] (Other additives) In addition to the above, the present resin composition may appropriately contain other additives selected from a coupling agent, an ultraviolet inhibitor, an antioxidant, a plasticizer, a flame retardant, a colorant, a flow improver, an antifoaming agent, an ion trapping agent, and the like.

[0075] 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. 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, and 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.

[0076] (Method of producing the present resin composition) The resin composition can be obtained by mixing and kneading the zeolite and resin, and optionally an inorganic filler other than the zeolite, a curing agent, a dispersant, a reactive diluent, and other additives 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 occurrence 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.

[0077] (Physical properties of the present 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, while it is preferably 100 ppm / K or less, more preferably 50 ppm / K or less, and even more preferably 30 ppm / K or less. Such a resin composition has a low average coefficient of thermal expansion at temperatures equal to or lower than the glass transition temperature, and is therefore useful as a material that requires various heat resistance properties, and is particularly effective for application to electronic devices.

[0078] 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.

[0079] <Viscosity> When used as a liquid composition, the resin composition is preferably a composition that has fluidity at room temperature (23°C). The viscosity of the resin composition is preferably low so that the composition can be easily filled into narrow spaces. On the other hand, a high viscosity is preferable so that dripping and the like are less likely to occur when the composition is filled. The viscosity of the 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.

[0080] 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.

[0081] <Water absorption rate> The resin composition preferably has a water absorption rate of 5% or less when cured to a gel fraction of 80% or more. If the water absorption rate 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 viewpoints, the lower the water absorption rate, the better, more preferably 4% or less, even more preferably 3% or less, and particularly preferably 2% or less. The water absorption rate can be measured by the method described in the Examples.

[0082] (Application) The resin composition can be used, for example, in catalyst modules, molecular sieve membrane modules, optical components, moisture-absorbing components, foods, building materials, and components and packaging materials for electronic devices, and is particularly preferably used in electronic devices. An electronic device is a device that has two or more electrodes and controls the current flowing between the electrodes or the voltage generated therebetween using electricity, light, magnetism, or chemicals, or that generates 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, etc., or 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, electronic devices comprising the semiconductor encapsulant of the present invention are also within the scope of the present invention.

[0083] [Semiconductor encapsulation material] The semiconductor encapsulant of the present invention can encapsulate and protect a variety of objects, such as electronic devices that use semiconductors, and semiconductor encapsulants comprising the resin composition of the present invention are 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.

[0084] (liquid semiconductor encapsulant) When the resin composition is in a liquid form, it is preferably used as a liquid semiconductor encapsulant, and in this case, the liquid composition is cured to form the semiconductor encapsulant. Note that a method for producing a semiconductor encapsulant, which includes 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.

[0085] <Underfill material> When the 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 and then hardens to fill the gaps. Note that a method for producing a semiconductor encapsulant that includes a step of filling the gaps with a resin composition and then hardening the resin composition is also within the scope of the present invention. Furthermore, the liquid semiconductor encapsulant may 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 state, is preferably used for filling gaps and curing them, i.e., it is preferable to produce a semiconductor encapsulant by filling the present resin composition into gaps and then curing it.

[0086] 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, for example, between a substrate and a semiconductor chip, or between substrates or between semiconductor chips. Any known substrate can be used as the substrate, and it is preferable to use a substrate made of an organic material such as an epoxy resin substrate or a phenolic resin substrate. Furthermore, it is preferable to form the semiconductor chip from a semiconductor substrate such as a silicon substrate. The resin composition has a low coefficient of thermal expansion when cured, and when used as an underfill material, the difference in coefficient of thermal expansion between it and semiconductor substrates and other components is reduced, improving thermal cycle resistance and other properties.

[0087] 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.

[0088] The underfill material may be used in the manufacture of semiconductor devices using a pre-application method. Specifically, the underfill material is filled between the bumps on the surface of a semiconductor chip on which multiple 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.

[0089] 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.

[0090] 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.

[0091] <Sealing material> The liquid semiconductor encapsulant can also be used as an encapsulant that covers the entire semiconductor element. By covering organic electronic elements such as electronic devices with a semiconductor encapsulant, it is possible to effectively block oxygen, moisture, etc. from entering from the outside, thereby improving the life of the electronic devices, etc. It is particularly effective in 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 the cavity, and the resin is then hardened to remove the product. This method makes it possible to relatively easily manufacture an encapsulant that covers the entire semiconductor element. [Example]

[0092] 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.

[0093] (Physical property evaluation) The physical properties were evaluated as follows.

[0094] (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 using the following procedure. Each material was dissolved in acid, and the amounts of sodium and potassium in the solution were measured using an inductively coupled plasma optical emission spectrometer (instrument name: iCAP7600Duo, manufactured by Thermo Fisher Scientific). The detection limit of the instrument was 1 ppm by mass.

[0095] (Weight reduction rate) The weight loss rate of zeolite was measured using the following procedure. Approximately 5 mg of zeolite was placed in a platinum cup and placed in a thermal analyzer (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 using the formula "weight loss rate of zeolite = 100 × {(weight at 400°C) - (weight held at 800°C for 10 minutes)} / (weight at 400°C)".

[0096] (Circularity of primary particles) The circularity of the primary particles of zeolite was measured by the following procedure. The particles were observed using a particle image analyzer (MORPHOLOGI 4, manufactured by Spectris). The area and circumference of 20,000 to 30,000 particles detected were calculated, and the circularity was calculated as follows: "Circularity = 4 x π x area / (circumference)" 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.

[0097] (circle equivalent diameter of primary particles) The circularity of the primary particles of zeolite was measured by the following procedure. The particles were observed using a particle image analyzer (MORPHOLOGI 4, manufactured by Spectris). The area of ​​20,000 to 30,000 particles detected was calculated, and the circularity was calculated as "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.

[0098] (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 using the following procedure. Each material 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 detection limit of the instrument was 0.1 ppb by mass.

[0099] (SAR (Si / Al2 ratio)) The SAR (Si / Al2 ratio) of zeolite was measured using the following procedure. Approximately 500 mg of zeolite was covered with a polypropylene film and placed in an X-ray fluorescence analyzer (Supermini200, manufactured by Rigaku) ​​for measurement to determine the SiO2 and Al2O3 concentrations in the zeolite. The SAR (Si / Al2 ratio) was calculated from the obtained concentration values.

[0100] (Average coefficient of thermal expansion (CTE)) The average thermal expansion coefficient of the cured resin composition when cured to a gel fraction of 80% or more was measured by thermomechanical analysis according to JIS K7197 (2012). Measurements were performed using a thermomechanical analyzer (TMA SS7100, manufactured by SII NanoTechnology) using the compression method. 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 × 10 mm, and measured using a thermomechanical analyzer by the compression method, with the temperature rising from 20°C to 200°C at a rate of 5°C / min. The change in the sample length with temperature from 25 to 100°C was measured, and the slope of the tangent was taken as the average coefficient of thermal expansion (CTE).

[0101] (viscosity) The viscosity of the resin composition at 23°C was measured using a Brookfield "LVDV-1 Pri" rotational viscometer with spindles S64 and S63 when the viscosity was 0.1 to 100 Pa·s, and a Brookfield "HBDV-E" rotational viscometer with spindle S-07 when the viscosity exceeded 100 Pa·s. The value measured at 5 rpm was used as the representative viscosity value for each sample.

[0102] (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. The weight change rate (%) after this was evaluated.

[0103] Manufacturing Example 1 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), Kyoward 200S manufactured by Kyowa Chemical Industry Co., Ltd. as an aluminum atom source having a sodium content of 833 ppm by mass based on aluminum atoms, and amorphous silica as a silicon atom source having a sodium content of 3 ppm by mass based on silicon atoms. The composition and molar ratio of the resulting mixture was SiO2:Al2O3:TMAdaOH:H2O = 1.0:0.0294:0.176:18. After adding 5% by mass of CHA-type zeolite as seed crystals relative to SiO2 and mixing thoroughly, 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 circularity of the primary particles of the obtained zeolite was 0.922. The equivalent circle diameter of the primary particles of the obtained zeolite was 4.00 μm. XRD analysis of the obtained powder confirmed that it was a CHA-type zeolite. The SAR (Si / Al2 ratio) of the obtained zeolite was 31.3. The weight loss rate of the obtained zeolite was determined using the above method and was 23.6%. The amounts of uranium and thorium contained in the obtained zeolite were determined using the above method and were found to be 7.8 mass ppb and less than the detection limit of 0.1 mass ppb, respectively. The amounts of sodium and potassium contained in the obtained zeolite were determined using the above method and were found to be 34 mass ppm and 1 mass ppm, respectively.

[0104] Manufacturing Example 2 To the 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, with a sodium content of less than 9 ppm by mass based on aluminum atoms. The mixture was heated to 80°C for 3 hours with thorough stirring. Then, amorphous silica with a sodium content of 3 ppm by mass based on silicon atoms was added as a silicon atom source. The composition and molar ratio of the resulting mixture was SiO2:Al2O3:TMAdaOH:H2O = 1.0:0.0294:0.176:18. After adding 5% by mass of CHA-type zeolite as seed crystals relative to SiO2 and mixing thoroughly, 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 circularity of the primary particles of the obtained zeolite was 0.934. The equivalent circle diameter of the primary particles of the obtained zeolite was 4.61 μm. XRD analysis of the obtained powder confirmed that it was a CHA-type zeolite. The SAR (Si / Al2 ratio) of the obtained zeolite was 27.9. The weight loss rate of the obtained zeolite was determined using the above method and was 23.7%. The amounts of uranium and thorium contained in the obtained zeolite were determined using the above method and found to be 0.4 mass ppb and less than the detection limit of 0.1 mass ppb, respectively. The amounts of sodium and potassium contained in the obtained zeolite were determined using the above method and found to be 11 mass ppm and less than the detection limit of 1 mass ppm, respectively.

[0105] Manufacturing Example 3 To a container were sequentially added 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 sodium content of 833 ppm by mass based on aluminum atoms, and "Snowtex N-40" manufactured by Nissan Chemical Industries, Ltd. as a silicon atom source having a sodium content of 4492 ppm by mass based on silicon atoms. The composition and molar ratio of the resulting mixture was SiO2:Al2O3:TMAdaOH:HO:surfactant = 1.0:0.025:0.3:25:0.02. Then, 5% by mass of CHA-type zeolite was added as seed crystals relative to SiO2 and mixed 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 circularity of the primary particles of the obtained zeolite was 0.936. The equivalent circle diameter of the primary particles of the obtained zeolite was 1.90 μm. XRD analysis of the obtained powder confirmed that it was a CHA-type zeolite. The SAR (Si / Al2 ratio) of the obtained zeolite was 34.3. The weight loss rate 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 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 2120 mass ppm and 184 mass ppm, respectively.

[0106] Production Example 4 The following substances were sequentially added to a vessel: water, N,N,N-trimethyl-1-adamantylammonium hydroxide (TMAdaOH) manufactured by Seichem Co., Ltd. as an organic structure directing agent (SDA), "amorphous aluminum hydroxide" manufactured by Asada Chemical Industry Co., Ltd. as an aluminum atom source, with a sodium content of 796 ppm by mass based on the aluminum atom, "Snowtex N-40" manufactured by Nissan Chemical Co., Ltd. as a silicon atom source, with a sodium content of 4492 ppm by mass based on the silicon atom, and amorphous silica with a sodium content of 3 ppm by mass based on the silicon atom. The ratio of Snowtex N-40 to amorphous silica was adjusted so that the SiO2 concentration derived from Snowtex N-40 was 25% and the SiO2 concentration derived from amorphous silica was 75%. The composition and molar ratio of the resulting mixture was SiO2:Al2O3:TMAdaOH:H2O = 1.0:0.0294:0.19:25. After adding 5% by mass of CHA-type zeolite as seed crystals relative to SiO2 and mixing thoroughly, 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 circularity of the primary particles of the obtained zeolite was 0.950. The equivalent circle diameter of the primary particles of the obtained zeolite was 2.14 μm. XRD analysis of the obtained powder confirmed that it was a CHA-type zeolite. The SAR (Si / Al2 ratio) of the obtained zeolite was 32.4. The weight loss rate 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 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 244 mass ppm and 2 mass ppm, respectively.

[0107] Manufacturing Example 5 A container was charged with water, N,N,N-trimethyl-1-adamantylammonium hydroxide (TMAdaOH) as an organic structure-directing agent (SDA; structure-directing agent) manufactured by Seichem Co., Ltd., sodium oleate as a surfactant manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Kyoward 200S as an aluminum atom source with a sodium content of 833 ppm by mass based on aluminum atoms, Snowtex N-40 as a silicon atom source manufactured by Nissan Chemical Industries, Ltd. with a sodium content of 4492 ppm by mass based on silicon atoms, and amorphous silica with a sodium content of 3 ppm by mass based on silicon atoms. The ratio of Snowtex N-40 to amorphous silica was adjusted so that the SiO2 concentration derived from Snowtex N-40 was 75% and the SiO2 concentration derived from amorphous silica was 25%. The composition and molar ratio of the resulting mixture was SiO2:Al2O3:TMAdaOH:HO:surfactant = 1.0:0.025:0.3:25:0.02. Then, 5% by mass of CHA-type zeolite was added as seed crystals relative to SiO2 and mixed 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 circularity of the primary particles of the obtained zeolite was 0.947. The equivalent circle diameter of the primary particles of the obtained zeolite was 1.86 μm. XRD analysis of the obtained powder confirmed that it was a CHA-type zeolite. The SAR (Si / Al2 ratio) of the obtained zeolite was 32.8. The weight loss rate 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 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 2110 mass ppm and 208 mass ppm, respectively.

[0108] Manufacturing Example 6 Zeolite was produced in the same manner as in Production Example 3. 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 method and was found to be 0.4%.

[0109] Next, examples of the resin composition of the present invention will be described. <Composition ingredients> The components used in preparing the resin composition are as follows:

[0110] <Epoxy resin> (A) p-Aminophenol type epoxy resin; manufactured by Mitsubishi Chemical Corporation, product name "jER630", epoxy equivalent: 97 g / equivalent <Curing agent> (B) Acid anhydride hardener: Acid anhydride (main component: hydrogenated methyl nadic acid anhydride): manufactured by New Japan Chemical Co., Ltd., product name "Rikacid HNA-100" (acid anhydride equivalent: 174-184) (C) Imidazole-based curing agent: Shikoku Chemicals Corporation, product name "2E4MZ-CN" <Filler> (D) Zeolite filler 1: The zeolite produced in the above Production Example 1 was used. (E) Zeolite filler 2: The zeolite produced in Production Example 2 above was used. (F) Zeolite filler 3: The zeolite produced in the above Production Example 3 was used. (G) Zeolite filler 4: The zeolite produced in the above Production Example 4 was used. (H) Zeolite filler 5: The zeolite produced in the above Production Example 5 was used. (I) Zeolite filler 6: The zeolite produced in the above Production Example 6 was used. <Additives> (J) Additive: BYK Japan, wetting and dispersing agent, product name "DISPERBYK-2152" (amino group-containing ultra-molecular weight polyester, comb type, solvent-free)

[0111] Example 1 The fillers, resins, curing agents, and additives shown in Table 1 were blended in the amounts shown in Table 1. The mixture was then mixed at 1500 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. The liquid composition was then poured into a mold and heated at 80°C for 2 hours, then at 120°C for 2 hours to cure to a gel fraction of 80% or more, after which the composition was demolded to obtain a cured product. The CTE and water absorption of this cured product were evaluated using the methods described above. The results are shown in Table 1.

[0112] Example 2, Comparative Examples 1 to 3, and Reference Example 1 In Example 1, the zeolite filler was replaced with one shown in Table 1, and a resin composition (liquid composition) and a cured product 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.

[0113] [Table 1]

[0114] The zeolites used in Examples 1 and 2 have an extremely low sodium content compared to Comparative Examples 1 to 3, and electronic devices using the cured products prepared in Examples 1 and 2 as semiconductor encapsulants are expected to be less susceptible to corrosion of device wiring and performance degradation of semiconductor elements. Furthermore, the zeolites used in Examples 1 and 2 also have a low potassium content, so even greater effects can be expected. Furthermore, the zeolite fillers used in Examples 1 and 2 contained small amounts of uranium and thorium, and it is expected that electronic devices using the cured products prepared in Examples 1 and 2 as semiconductor encapsulants will have an extremely low possibility of experiencing operational errors (soft errors). Furthermore, the water absorption of the cured products prepared in Examples 1 and 2 was lower than that of the cured product prepared in Reference Example 1. This is presumably because the zeolite filler used in Examples 1 and 2 contains components derived from the organic structure-directing agent and has low water adsorption properties. That is, the zeolite of the present invention has an extremely low sodium content, and when used as a semiconductor encapsulant, it is unlikely to cause a decrease in the performance of semiconductor elements. Furthermore, a resin composition can be obtained that has low moisture absorption, a low coefficient of thermal expansion after curing, and a low viscosity. [Industrial Applicability]

[0115] According to the present invention, it is possible to provide a zeolite with a reduced sodium content, and by sealing an electronic device such as an electronic device with a semiconductor encapsulant using the zeolite, it is possible to make it less likely that corrosion of the device wiring or deterioration of the performance of the semiconductor element will occur. Furthermore, the zeolite of the present invention can be used to obtain a resin composition that has a low thermal expansion coefficient and low viscosity after curing. The resin composition is suitable for use as a liquid semiconductor encapsulant for underfill applications and is also suitable as an encapsulant that covers the entire semiconductor element, making it an extremely useful industrial material.

Claims

1. A zeolite having a sodium content of less than 100 ppm by mass.

2. 2. The zeolite according to claim 1, having a potassium content of 180 ppm by mass or less.

3. 3. The zeolite according to claim 2, wherein the total content of sodium and potassium is 280 mass ppm or less.

4. 3. The zeolite according to claim 2, wherein the ratio of sodium to potassium contained in the zeolite (sodium content / potassium content) is 0.5 or more and 10,000 or less.

5. 2. The zeolite according to claim 1, wherein, 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, based on the weight at 400°C, is 1% or more, as determined by thermogravimetric analysis (TGA).

6. The zeolite according to claim 1, which is an as-made type.

7. SAR (Si / Al ２ 2. The zeolite according to claim 1, wherein the zeolite has a β-molecular weight ratio of 14 or more and 50 or less.

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

9. 2. The zeolite of claim 1 having d6r as CBU.

10. 2. The zeolite according to claim 1, wherein the zeolite has an oxygen ring structure of 8 or less members.

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

12. 2. The zeolite according to claim 1, wherein the total content of uranium and thorium is 200 ppb by mass or less.

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

14. The resin composition according to claim 13, wherein the resin comprises at least one resin selected from the group consisting of epoxy resins and polyimide resins.

15. The resin composition of claim 13 , wherein the resin comprises an epoxy resin.

16. A semiconductor encapsulant comprising the resin composition according to claim 13.

17. A method for producing a semiconductor encapsulant, comprising a step of curing the resin composition according to claim 13.

18. An electronic device comprising the semiconductor encapsulant of claim 16.

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