Zeolite, resin composition, liquid sealant, underfill material, method for producing sealant, and electronic device

Abstract

To provide a zeolite for obtaining a resin composition having low hygroscopicity and low thermal expansion coefficient after curing, and low viscosity with high gap penetration properties.SOLUTION: There is provided a zeolite which, by thermogravimetric analysis (TGA), 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, has a weight loss rate at 800°C of 1% or more based on the weight at 400°C, has a circularity of primary particles of 0.800 or more, and has 40% or less of particles having a particle diameter of 3 μm or more as measured by volume-based particle size distribution.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a zeolite, a resin composition, a liquid sealant, an underfill material, a method for producing a sealant, and an electronic device. [Background technology]

[0002] Liquid sealants used as underfill materials are required to have excellent injectability, adhesion, curing properties, storage stability, etc., and to be free of voids. Furthermore, the areas sealed with the liquid sealant are required to have excellent moisture resistance, thermal cycle resistance, reflow resistance, crack resistance, warpage resistance, etc. To satisfy the above requirements, liquid sealants based on epoxy resins are widely used as underfill materials.

[0003] Furthermore, in order to improve the moisture resistance and thermal cycle resistance, particularly the thermal cycle resistance, of the portion sealed with the liquid sealant, it is known that by using a filler made of an inorganic substance such as silica filler (hereinafter, sometimes referred to as "inorganic filler") in the liquid sealant, the difference in thermal expansion coefficient between the substrate made of an organic material such as epoxy resin and the semiconductor element can be controlled and the bump electrodes can be reinforced (see Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-56070 Summary of the Invention [Problem to be solved by the invention]

[0005] Liquid sealants (resin compositions) that use inorganic fillers such as silica fillers do not have a sufficiently low coefficient of thermal expansion, and there is a demand for a further reduction in the coefficient of thermal expansion from the viewpoint of thermal cycle resistance, etc. Zeolite is known as an inorganic filler with a low coefficient of thermal expansion, but liquid sealants containing zeolite tend to have high viscosity, which reduces injectability (gap penetration ability) when used as an underfill material, making it difficult to obtain a liquid sealant that has good injectability while also having a low coefficient of thermal expansion of the cured product.

[0006] Zeolites are also known to be highly hygroscopic, and the presence of water can reduce the dielectric constant and reliability of electronic materials, so zeolites used in this application are required to have low hygroscopicity.

[0007] Therefore, an object of the present invention is to provide a zeolite for obtaining a resin composition that has low moisture absorption, a low coefficient of thermal expansion after curing, a low viscosity, and good gap penetration properties. [Means for solving the problem]

[0008] As a result of extensive research into the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a zeolite having a specific structure, and have thus completed the present invention. The gist of the present invention is as follows. [1] A zeolite that, when heated to 800°C at a rate of 10°C / min in an air atmosphere and held at 800°C for 10 minutes by thermogravimetric analysis (TGA), has a weight loss of 1% or more at 800°C based on the weight at 400°C, a circularity of primary particles of 0.800 or more, and particles with a particle size of 3 μm or more as determined by volumetric particle size distribution measurement, of which the percentage is 40% or less. [2] The zeolite according to [1] above, having d6r as CBU. [3] The zeolite according to [1] or [2] above, which has an oxygen ring structure of 8 or less members. [4] The zeolite according to any one of the above [1] to [3], which has a CHA structure. [5] A resin composition containing the zeolite according to any one of the above [1] to [4] and a resin. [6] The resin composition according to [5] above, wherein the resin comprises at least one resin selected from the group consisting of epoxy resins and polyimide resins. [7] The resin composition according to [5] or [6] above, wherein the resin comprises an epoxy resin. [8] A liquid sealant comprising the resin composition according to any one of the above [5] to [7]. [9] An underfill material comprising the resin composition according to any one of [5] to [7] above.

[10] A method for producing an encapsulant, comprising the steps of filling a gap with the resin composition according to any one of the above [5] to [7], and then curing the composition.

[11] An electronic device comprising an encapsulant obtained by the manufacturing method described in

[10] above. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a zeolite for obtaining a resin composition that has low moisture absorption and a low coefficient of thermal expansion after curing, and that has low viscosity and high gap penetration. DETAILED DESCRIPTION OF THE INVENTION

[0010] [Zeolite] Zeolites generally refer to a group of crystalline substances that have a three-dimensional network framework composed of silicon or aluminum and oxygen, and pores derived from this framework structure. This characteristic structure is used in adsorbents and catalysts. Therefore, organic substances, such as organic structure-directing agents, that are incorporated into the pores during zeolite synthesis generally clog the pores and reduce the adsorption and catalytic capabilities of the zeolite, and are therefore generally removed by calcination or other methods. However, the zeolite of the present invention (hereinafter sometimes referred to as "the present zeolite") is characterized by containing organic substances, preferably components derived from the organic structure-directing agent that is the raw material for zeolite, within the pores. Methods for producing zeolites that contain organic substances, preferably components derived from the organic structure-directing agent, within the pores include, but are not limited to, a method in which the calcination process typically performed during the zeolite production process is not performed or is only partially performed. A specific characteristic of zeolite containing an organic substance, preferably a component derived from an organic structure-directing agent, inside its pores is that, when heated to 800°C at a heating rate of 10°C / min in an air atmosphere and held at 800°C for 10 minutes, thermogravimetric analysis (TGA) shows a weight loss rate of 1% or more at 800°C, based on the weight at 400°C. When zeolite containing an organic substance, preferably a component derived from an organic structure-directing agent, inside its pores is heat-treated in a high temperature range of 400°C to 800°C, the absorbed water and organic substance, preferably the organic structure-directing agent, present in the zeolite pores are desorbed, and this is thought to result in a larger weight loss rate than that of ordinary calcined zeolite (hereinafter sometimes referred to as "calcined zeolite"). The resin composition of the present invention (hereinafter sometimes referred to as "the resin composition") described below uses a zeolite containing an organic substance, preferably a component derived from an organic structure-directing agent, inside the pores, and thereby 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. Zeolite exhibits adsorption properties for water and other substances because it has a porous structure and contains acid sites that serve as adsorption sites. It is presumed that the presence of an organic substance, preferably a component derived from an organic structure-directing agent, within the pores prevents the zeolite from becoming completely porous, which reduces its adsorption properties for water and other substances and reduces its moisture absorption properties. From the above viewpoints, when the present zeolite is heated to 800°C at a heating rate of 10°C / min in an air atmosphere and held at 800°C for 10 minutes by thermogravimetric analysis (TGA), the weight loss rate at 800°C based on the weight at 400°C (hereinafter sometimes simply referred to as "weight loss rate") is 1% or more, preferably 2% or more, and more preferably 3% or more. The weight loss rate may be 5% or more, 10% or more, or 20% or more. There is no particular upper limit as long as the effects of the present invention are achieved, but it may be, for example, 50% or less.

[0011] (Zeolite particle size distribution) The present zeolite is characterized in that, in the volumetric particle size distribution, particles having a particle size of 3 μm or more account for 40% or less. By having particles having a particle size of 3 μm or more account for 40% or less in the volumetric particle size distribution, when a resin composition is formed, the resin composition can be sufficiently filled even in a narrow gap. From this perspective, in the volumetric particle size distribution, particles having a particle size of 3 μm or more account for preferably 40% or less, more preferably 30% or less, even more preferably 20% or less, particularly preferably 10% or less, and most preferably 5% or less. Furthermore, in the volumetric particle size distribution, the lower limit of particles having a particle size of 3 μm or more is not particularly limited, and it is sufficient if it is 0% or more. The volumetric particle size distribution of the present zeolite is obtained by measurement using a laser diffraction / scattering particle size distribution measurement method. Specifically, it can be measured using the method described in the Examples. Methods for satisfying the above particle size distribution include performing a classification treatment after hydrothermal synthesis and adding seed crystals or alkali metals in any ratio during hydrothermal synthesis. These steps may be used alone or in combination.

[0012] (Zeolite particle size) When the zeolite is added to a resin, a large particle size is preferable so that the viscosity of the resin is not easily increased. Specifically, the particle size is preferably 0.1 μm or more, more preferably 0.2 μm or more, even more preferably 0.3 μm or more, and particularly preferably 0.4 μm or more, particularly preferably 0.5 μm or more, particularly preferably 0.6 μm or more, particularly preferably 0.7 μm or more, particularly preferably 0.8 μm or more, particularly preferably 0.9 μm or more, and most preferably 1.0 μm or more. On the other hand, a small particle size is preferable so that the zeolite can be easily mixed uniformly with other components such as resins and the surface smoothness is easily increased. Specifically, 3.0 μm or less is preferable, 2.95 μm or less is more preferable, 2.9 μm or less is even more preferable, 2.8 μm or less, 2.7 μm or less, 2.5 μm or less, 2.4 μm or less, 2.3 μm or less, 2.2 μm or less is particularly preferable, 2.1 μm or less is particularly preferable, and 2.0 μm or less is most preferable. The particle size of the present zeolite means the median diameter obtained from the volume-based particle size distribution, and the volume-based particle size distribution is obtained by measurement using a laser diffraction / scattering particle size distribution measuring method. Furthermore, the present zeolite may be in the form of secondary particles formed by aggregation of a plurality of zeolite particles, but in this case the particle size of the zeolite is the particle size of the primary particles.

[0013] (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).

[0014] (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 particularly preferred because the structure is stable even when the shape is controlled, and zeolites with CHA structure are most preferred. In this specification, a structure having an 8-membered oxygen ring means a structure in which the number of oxygen elements is 8 when the number of oxygen elements is the largest among the pores 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.

[0015] (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 the zeolite is also preferred because the various physical properties of the resin are less likely to change due to the addition of the 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 particularly preferably -5 ppm / K or less.

[0016] On the other hand, considering that the zeolite will be used as a liquid composition containing the zeolite and a resin (described later), a high average thermal expansion coefficient is preferable so that the difference with the average thermal expansion coefficient of the resin is small and the zeolite and the resin are less likely to separate. Therefore, the average thermal expansion coefficient of the zeolite is usually −1000 ppm / K or higher, preferably −900 ppm / K or higher, more preferably −800 ppm / K or higher, even more preferably −700 ppm / K or higher, particularly preferably −500 ppm / K or higher, and most preferably −300 ppm / K or higher. Especially when used as a sealing material, a high average thermal expansion coefficient is preferable. Specifically, the average thermal expansion coefficient is usually −100 ppm / K or higher, preferably −50 ppm / K or higher, more preferably −40 ppm / K or higher, even more preferably −30 ppm / K or higher, particularly preferably −25 ppm / K or higher, and most preferably −20 ppm / K or higher. The average thermal expansion coefficient of zeolite can be measured by calculating the lattice constant using a BRUKER X-ray diffractometer "D8ADVANCE" and X-ray diffraction analysis software "JADE." 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.

[0017] 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.

[0018] (Zeolite shape) The present zeolite is preferably spherical. When the zeolite has a spherical shape, an increase in viscosity of a resin composition containing the zeolite can be suppressed. Specifically, 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 scanning electron microscope (SEM).

[0019] <<Roundness>> The circularity of the primary particles of the present zeolite is 0.800 or more, preferably 0.810 or more, more preferably 0.820 or more, even more preferably 0.830 or more, and particularly preferably 0.835 or more. There is no particular upper limit to the circularity of the primary particles, as long as it is 1 or less. The circularity of cubic zeolites, which are common in ordinary zeolites, is 0.785. In this specification, "roundness" is defined as "4 x π x area / (circumference) 2 The area and circumference can be determined by observation with a scanning electron microscope (SEM). In this specification, "roundness" is the average value of 100 particles obtained with a scanning electron microscope (SEM). 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.

[0020] (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 3 More preferably, 14.0T / 1000Å or more 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.

[0021] 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.

[0022] (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.

[0023] 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.

[0024] (Silica / Alumina Molar Ratio (SAR) of Zeolite) The silica / alumina molar ratio (hereinafter sometimes referred to as "SAR," "Si / Al2 molar ratio," 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 2000 or less, preferably 1000 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 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 Si / Al2 ratio of the zeolite can be adjusted by the type and ratio of the silicon-containing compound and aluminum-containing compound used as raw materials, the type and amount of the structure-directing agent, the use of seed crystals, and synthesis conditions such as temperature and time.

[0025] (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"), a proton type, or an alkali metal type, more preferably an as-made, proton type, Li type, Na type, or K type, and even more preferably an as-made type.

[0026] (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.

[0027] (Surface treatment for zeolite) The present zeolite may be subjected to a surface treatment such as silylation treatment or fluorination treatment, as long as the effects of the present invention are not impaired. The surface treatment may be a physical treatment or a chemical treatment.

[0028] (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.

[0029] <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.

[0030] 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 5 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, the ability to fill narrow gaps is improved. From the above perspectives, the average particle size of the other inorganic filler is more preferably in the range of 0.2 μm to 4 μm, and even more preferably in the range of 0.5 μm to 2 μm.

[0031] 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.

[0032] <Total amount of inorganic filler> The total content of all inorganic fillers (total inorganic fillers) contained in the present resin composition is preferably high in order to facilitate the 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 resin 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.

[0033] <Dispersant> The resin composition may contain a dispersant to enhance the dispersibility of inorganic fillers such as the zeolite. The dispersant contained in the liquid composition containing a resin and a filler is 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.

[0034] 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 volatilization of the dispersant when the resin 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.

[0035] 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.

[0036] 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 an 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 resin composition.

[0037] <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.

[0038] 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, it is preferable not to perform the calcination treatment that is usually performed, or to perform partial calcination 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 this 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 in turn, it is possible to easily produce a zeolite for obtaining a resin composition that has low moisture absorption, a low thermal expansion coefficient after curing, low viscosity, and good gap penetration properties. If necessary, a desired zeolite (hereinafter, sometimes referred to as "seed zeolite") may be used.

[0039] <<Silicon atom raw material>> The silicon atom source used in the present invention is not particularly limited, and various known substances can be used. For example, colloidal silica, amorphous silica, sodium silicate, trimethylethoxysilane, tetraethyl orthosilicate, aluminosilicate gel, and zeolite can be used. These may be used alone or in any combination and ratio of two or more.

[0040] <<Aluminum atomic raw material>> The aluminum atom source is preferably a water-soluble source, and aluminum hydroxide is preferred because it contains a small amount of alkali metal.

[0041] <<Organic matter>> As described above, the present zeolite contains organic matter 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, organic structure-directing agents, etc. Examples of amines include trimethylamine, adamantylamine, morpholine, etc. Examples of amino acids include lysine, arginine, and ornithine. Examples of fatty acids include oleic acid and stearic acid. Examples of surfactants include sodium oleate and sodium stearate. Examples of polymers include 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 within the pores and reducing hygroscopicity. In other words, it is preferable that the present zeolite contains a component derived from an organic structure-directing agent as an organic substance. When an organic substance is used, one type may be used alone, or two or more types may be used in any combination and ratio.

[0042] <<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, even more preferably 0.04 or more, and particularly 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.

[0043] <<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 facilitates crystal formation, which is preferable. 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, from the viewpoint of easily achieving a cost reduction effect for waste liquid treatment, the molar ratio to silicon (Si) is preferably typically 50 or less, preferably 40 or less, more preferably 30 or less, and even more preferably 25 or less.

[0044] <<Alkali metal atom source>> An alkali metal atom raw material may be used to produce a zeolite. When using an alkali metal atom raw material, the alkali metal atom is not particularly limited, and any known alkali metal atom used in the synthesis of zeolites may be used, but at least one alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium is preferred. Note that multiple types of alkali metal atoms may also be used.

[0045] <<Seed Zeolite>> In the present 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.

[0046] <<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.

[0047] <<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.

[0048] <<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 the mixture at 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.

[0049] <<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 from 50° C. to 200° C., and more preferably from 70° C. to 150° C. 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.

[0050] <<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 preferably 200 to 1000°C. By calcining at 300°C or higher, the organic structure-directing agent and the like can be removed, while at 1000°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.

[0051] [Resin composition] The resin composition contains zeolite and a resin. The resin composition is preferably liquid at room temperature. When the resin composition is liquid at room temperature (hereinafter, sometimes referred to as a "liquid composition"), it is preferably used as a liquid sealant and is particularly suitable as an underfill material. 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.

[0052] <Resin> The resin in the present resin composition is not particularly limited as long as the effects of the present invention are achieved, and examples thereof include thermosetting resins, thermoplastic resins, etc. Among these, when considering a liquid sealant such as an underfill material, it is preferable to include a thermosetting resin.

[0053] <<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.

[0054] (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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] (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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] <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.

[0068] <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.

[0069] 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.

[0070] <Method of manufacturing the present resin composition> The resin composition can be obtained by mixing and kneading the zeolite, resin, and optionally inorganic fillers other than zeolite, curing agents, dispersants, reactive diluents, and other additives using a vacuum mixer, mixing rolls, planetary mixer, etc., and degassing as needed. 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.

[0071] <Physical properties of the resin composition> (Average Coefficient of Thermal Expansion (CTE)) When the resin composition is cured to a gel fraction of 80% or more, the average coefficient of thermal expansion (CTE) of the cured product at 25 to 100°C is preferably 0 ppm / K or more, more preferably 2 ppm / K or more, even more preferably 4 ppm / K or more, and particularly preferably 10 ppm / K or more, 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.

[0072] 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.

[0073] (viscosity) 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 resin 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 resin 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.

[0074] 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.

[0075] (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.

[0076] (gap filling distance) The resin composition has a gap-filling distance of preferably 10.0 cm or more, more preferably 10.5 cm or more, and even more preferably 11.0 cm or more, which is required to penetrate into a 7 μm gap when held at 80° C. for 10 minutes. If the gap-filling distance is greater than this length, the resin composition can penetrate into a narrow gap well when used as a part of an electronic component, such as an underfill material. The gap filling distance can be measured by the method described in the Examples.

[0077] [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 between the electrodes 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.

[0078] <Liquid sealant> When the present resin composition is in a liquid state, it is preferably used as a liquid sealant, and in this case, the liquid composition is cured to become a sealant. The liquid sealant may be used as a sealant that fills gaps formed in components by filling the gaps and then curing the gaps. Note that a method for producing a sealant that includes a step of filling the gaps with a resin composition and then curing the resin composition is also within the scope of the present invention. Furthermore, the liquid sealant may be used as a sealant to fill gaps between various components, for example, by applying the liquid sealant to various components, overlaying another component on the liquid sealant, and then appropriately curing the liquid sealant. In this case, the liquid sealant may be appropriately cured to a B-stage before the other component is overlaid. 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 a gap and curing it, i.e., it is preferable to produce a sealant by filling the present resin composition into a gap and then curing it.

[0079] The resin composition is preferably used as a liquid sealant, 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.

[0080] The underfill material is preferably used as a sealant that fills the gap between the substrate and the semiconductor chip in a laminate in which a semiconductor chip is 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.

[0081] The underfill material may be used in the manufacture of semiconductor devices using a pre-apply method. Specifically, the underfill material is filled between the bumps on the surface of a semiconductor chip on which 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 an encapsulant, and the semiconductor chip may be bonded via the bumps to the surface of the substrate on which a wiring pattern is formed.

[0082] 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 an 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.

[0083] In the above description, the underfill material is used as a sealing material to fill 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 sealing material to fill 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. [Example]

[0084] 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.

[0085] (Physical property evaluation) The physical properties were evaluated as follows.

[0086] (gel fraction) The gel fraction of the cured product was measured using the following procedure. After heat treatment at 80°C for 2 hours, the cured product was cured at 120°C for 2 hours. The product was cut into pieces of 0.5 to 0.6 g and placed on a wire mesh. The wire mesh was immersed in acetone and allowed to stand for 24 hours. The wire mesh was then removed from the acetone and vacuum dried. The ratio of the weight of the cured product after immersion to the weight before immersion was taken as the gel fraction.

[0087] (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)".

[0088] (Primary particle roundness) The circularity of primary zeolite particles was measured using the following procedure. The particles were observed using a scanning electron microscope (SEM) (device name: JSM-6701F, manufactured by JEOL). The area and circumference of 100 particles that could be considered primary particles were then determined, and the formula "Circularity = 4 x π x Area / (Circumference)" was used. 2 The average value of the circularity values of 100 particles obtained was calculated, and this was taken as the circularity of the primary particles of the zeolite.

[0089] (particle size distribution) The particle size distribution of the zeolite was measured using the following procedure. Zeolite powder was added to pure water to form a slurry of approximately 0.2% by mass. This was then placed in a laser diffraction / scattering particle size analyzer (instrument name: Laser diffraction / scattering particle size analyzer Partica mini LA-350, manufactured by HORIBA) through which pure water was flowing and subjected to ultrasonic treatment for 1 minute, after which a volumetric particle size distribution was obtained. The refractive index of water was 1.33, and the refractive index of the zeolite powder was 1.50. In the volumetric particle size distribution measurement, the proportion of particles with a particle size of 3 μm or more relative to the total particles detected by the instrument was calculated, and this was taken as the percentage of particles with a particle size of 3 μm or more obtained in the volumetric particle size distribution measurement.

[0090] (particle size) The particle size of the zeolite was measured by the following procedure. Zeolite powder was added to pure water to make a slurry of approximately 0.2 mass%, which was then placed in a laser diffraction / scattering particle size distribution analyzer (device name: laser diffraction / scattering particle size distribution analyzer Partica mini LA-350, manufactured by HORIBA) through which pure water was flowing and subjected to ultrasonic treatment for 1 minute, after which a volumetric particle size distribution was obtained. The refractive index of water was 1.33, and the refractive index of the zeolite powder was 1.50. From the obtained volumetric particle size distribution measurement, the median diameter was calculated and used as the particle size of the zeolite.

[0091] (Average coefficient of thermal expansion (CTE) of zeolite) The average thermal expansion coefficient of zeolite was measured using the following procedure. Pre-dried zeolite was placed in an X-ray diffractometer (D8ADVANCE, manufactured by BRUKER) and X-ray diffraction measurements were performed over a temperature range of 50 to 100°C. The obtained results were used to calculate the a-axis, b-axis, and c-axis lattice constants at each temperature using X-ray diffraction analysis software (JADE, manufactured by Materials Data). The average thermal expansion coefficient of zeolite was calculated using the formula: "Average thermal expansion coefficient of zeolite = {(average lattice constant at 100°C) - (average lattice constant at 50°C)} / {(average lattice constant at 50°C) × (100°C - 50°C)}." Here, the average lattice constant at each temperature is the average value of the a-axis, b-axis, and c-axis lattice constants.

[0092] (Average coefficient of thermal expansion (CTE) of cured product) 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 decreasing the temperature from 200°C to 20°C at a rate of 5°C / min using a compression method.The temperature change in the change in sample length from 25 to 100°C was measured, and the slope of the tangent was taken as the average coefficient of thermal expansion (CTE).

[0093] (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.

[0094] (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.

[0095] (gap filling distance) A 7 μm gap was created on a 10 mm wide glass plate, and a test piece was prepared by sandwiching the gap between two glass plates. This test piece was placed on a horizontal hot plate heated to 80°C so that one glass plate surface was in contact with the other, and a resin composition was applied to one end of the glass plate and allowed to stand for 10 minutes. After 10 minutes, the distance the resin composition had advanced within the gap was measured to evaluate the gap filling distance.

[0096] First, examples of the zeolite of the present invention will be shown.

[0097] Manufacturing Example 1 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 aluminum hydroxide, and Snowtex N-40 manufactured by Nissan Chemical Industries, Ltd. as silica. 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 obtained zeolite had 1% particles of 3 μm or larger on a volume basis. The particle size of the obtained zeolite was 1.21 μm. The circularity of the primary particles was 0.839. XRD analysis of the obtained powder confirmed that it was a CHA-type zeolite. The weight loss rate of the obtained zeolite was determined using the above method and was 22.6%. The average thermal expansion coefficient of the zeolite at 50 to 100°C was -6.8 ppm / K.

[0098] Manufacturing Example 2 Zeolite was produced in the same manner as in Production Example 1. The produced zeolite was calcined at 600°C for 6 hours in an air stream to obtain a calcined zeolite. The obtained zeolite had 15% particles of 3 μm or larger on a volume basis. The particle size of the obtained zeolite was 2.07 μm. The circularity of the primary particles was 0.845. XRD analysis of the obtained powder confirmed that it was a CHA-type zeolite. The weight loss rate of the obtained zeolite was determined by the above method and was 0.40%. The average thermal expansion coefficient of the zeolite at 50 to 100°C was -9.4 ppm / K.

[0099] Manufacturing Example 3 N,N,N-trimethyl-1-adamantylammonium hydroxide (TMAdaOH) manufactured by Seichem Corporation as an organic structure directing agent (SDA), "aluminum hydroxide" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. as aluminum hydroxide, and "CAB-O-SIL M-5" manufactured by Cabot Corporation as silica were sequentially added to the vessel. The composition and molar ratio of the resulting mixture was SiO2:Al2O3:TMAdaOH:H2O = 1.0:0.025:0.4:20. After thorough mixing, 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 obtained zeolite had a particle size of 3 μm or more on a volume basis of 50%. The particle size of the obtained zeolite was 2.98 μm. The circularity of the primary particles was 0.840. XRD analysis of the obtained powder confirmed that it was a CHA-type zeolite. The weight loss rate of the obtained zeolite was determined by the above method and was 24.2%. The average thermal expansion coefficient of the zeolite at 50 to 100°C was -5.0 ppm / K.

[0100] 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:

[0101] <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. <Additives> (G) Additive: BYK Japan, wetting and dispersing agent, product name "DISPERBYK-2152" (amino group-containing ultra-molecular weight polyester, comb type, solvent-free)

[0102] 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. Next, the gap-filling distance of 5 g of this liquid composition was evaluated by the above-mentioned method. 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.

[0103] Comparative Examples 1-2 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.

[0104] [Table 1]

[0105] The results of Example 1 and Comparative Example 1 revealed that using zeolite containing a component derived from an organic structure-directing agent (Example 1) as a filler reduced viscosity and water absorption, and increased gap-filling distance compared to using calcined zeolite (Comparative Example 1). The calcined zeolite obtained in Comparative Example 1 had a higher proportion of primary particles with a volumetric particle size of 3 μm or more than that of the zeolite containing a component derived from an organic structure-directing agent obtained in Example 1. This is presumably due to the particles adhering to each other after the calcination treatment. Furthermore, the resin composition obtained in Comparative Example 1 had a higher viscosity than the resin composition obtained in Example 1. This is presumably due to the increase in isolated silanol groups on the particle surface caused by the calcination treatment of the zeolite, resulting in an interaction between the isolated silanol groups and the resin. Furthermore, the results of Example 1 and Comparative Example 2 show that the gap filling distance increases when zeolite having 40% or less of primary particles with a particle size of 3 μm or more on a volume basis is used as a filler. That is, the zeolite of the present invention can provide a resin composition that has low moisture absorption and a low thermal expansion coefficient after curing, and also has low viscosity and high gap penetration. [Industrial Applicability]

[0106] According to the present invention, a zeolite can be provided for obtaining a resin composition that has low moisture absorption, low thermal expansion coefficient after curing, low viscosity, and high gap penetration. Such a resin composition is suitable for use as a liquid sealant, and is particularly useful as an underfill material.

Claims

1. A resin composition containing zeolite and a resin, wherein the zeolite has a weight loss rate of 1% or more at 800°C based on the weight at 400°C when heated to 800°C at a rate of 10°C / min in an air atmosphere and held at 800°C for 10 minutes as determined by thermogravimetric analysis (TGA), the circularity of the primary particles is 0.800 or more, and the percentage of particles with a particle size of 3 μm or more obtained by volume-based particle size distribution measurement is 40% or less.

2. A resin composition as described in claim 1, wherein the zeolite has d6r as CBU.

3. A resin composition described in claim 1, wherein the zeolite has a structure of an oxygen ring with 8 or fewer members.

4. A resin composition as described in claim 1, wherein the zeolite has a CHA type structure.

5. The resin composition according to any one of claims 1 to 4, wherein the resin comprises at least one resin selected from the group consisting of epoxy resins and polyimide resins.

6. The resin composition of claim 5 , wherein the resin comprises an epoxy resin.

7. A liquid sealant comprising the resin composition according to any one of claims 1 to 4.

8. An underfill material comprising the resin composition according to any one of claims 1 to 4.

9. A method for producing a sealing material, comprising a step of filling a gap with the resin composition according to any one of claims 1 to 4 and then curing the composition.

10. An electronic device comprising an encapsulant obtained by the manufacturing method according to claim 9.