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

Abstract

Disclosed is a zeolite wherein: the weight loss rate thereof is 1% or more at 800°C based on the weight at 400°C, as determined by thermogravimetric analysis (TGA), when the temperature thereof is raised to 800°C at the temperature increase rate of 10°C / min in the air atmosphere and held at 800°C for 10 minutes; the circularity of primary particles is 0.800 or more; and particles having a particle diameter of 3 μm or more as determined by a volume-based particle size distribution measurement are 40% or less.　The present invention makes it possible to provide a zeolite for obtaining a resin composition that has low hygroscopicity and low coefficient of thermal expansion after curing, and that has low viscosity and high gap penetration properties.

Description

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

[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.

[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).

[0004] Japanese Patent Application Laid-Open No. 2007-56070

[0005] Liquid sealants (resin compositions) using 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 with good injectability while reducing the 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.

[0008] The present inventors conducted extensive research into the above-mentioned problems and discovered that the above-mentioned problems can be solved by using a zeolite having a specific structure, leading to the completion of the present invention. The gist of the present invention is as follows: [1] A zeolite that, when heated to 800°C in an air atmosphere at a heating rate of 10°C / min and held at 800°C for 10 minutes, exhibits a weight loss at 800°C of 1% or more based on the weight at 400°C, a primary particle circularity of 0.800 or more, and 40% or less of particles having a particle size of 3 μm or more as measured by volumetric particle size distribution. [2] The zeolite according to [1] above, which has d6r as the CBU. [3] The zeolite according to [1] or [2] above, which has a structure with an oxygen ring of 8 or less members. [4] The zeolite according to any one of [1] to [3] above, which has a CHA-type structure. [5] A resin composition containing the zeolite according to any one of [1] to [4] above and a resin. [6] The resin composition according to [5] above, wherein the resin comprises at least one 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 [5] to [7] above. [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 [5] to [7] above, and then curing the composition.

[11] An electronic device comprising an encapsulant obtained by the method according to

[10] above.

[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.

[0010] First Aspect [Zeolite] Zeolites generally refer to a group of crystalline substances having 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, incorporated into the pores during the synthesis of zeolites generally clog the pores and reduce the adsorption and catalytic capabilities of the zeolite, and are therefore removed by calcination or other methods. However, the zeolite according to the first aspect of the present invention (hereinafter sometimes referred to as "the present zeolite I") is characterized in that it contains an organic substance, preferably a component derived from the organic structure-directing agent, which is a raw material for the zeolite, within its pores. Methods for producing zeolites containing an organic substance, preferably a component derived from the organic structure-directing agent, within their pores include, but are not limited to, a method in which the calcination treatment typically performed during the zeolite production process is not performed or is only partially performed. A specific characteristic of a 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 by thermogravimetric analysis (TGA), the weight loss rate at 800°C is 1% or more, based on the weight at 400°C. When a 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 a normal calcined zeolite (hereinafter sometimes referred to as "calcined zeolite"). The resin composition according to the first aspect of the present invention (hereinafter sometimes referred to as "the present resin composition I") 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 organic substances, preferably components derived from organic structure-directing agents, in the pores prevents the zeolite from becoming completely porous, resulting in reduced adsorption to water and other substances and reduced hygroscopicity. From the above perspective, when the present zeolite I 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, its weight loss at 800°C (hereinafter sometimes simply referred to as "weight loss rate") based on the weight at 400°C 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 limitation on the 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 I is characterized in that, in the volumetric particle size distribution, particles with a particle size of 3 μm or more account for 40% or less. By having particles with a particle size of 3 μm or more account for 40% or less in the volumetric particle size distribution, the resin composition can be sufficiently filled, even in narrow gaps, when formed into a resin composition. From this perspective, in the volumetric particle size distribution, particles with a particle size of 3 μm or more account for 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 with a particle size of 3 μm or more is not particularly limited, as long as it is 0% or more. The volumetric particle size distribution of the present zeolite I is measured using a laser diffraction / scattering particle size distribution measurement method. Specifically, it can be measured using the method described in the Examples. Methods for achieving the above particle size distribution include performing a classification treatment after hydrothermal synthesis and adding seed crystals or alkali metals in any proportion during hydrothermal synthesis. These steps may be used alone or in combination.

[0012] (Zeolite particle size) When adding zeolite to a resin, the particle size of the present zeolite I is preferably large in order to prevent the viscosity from increasing. Specifically, it is preferably 0.1 μm or more, more preferably 0.2 μm or more, even more preferably 0.3 μm or more, among which 0.4 μm or more, among which 0.5 μm or more, among which 0.6 μm or more, among which 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, it is preferably small in order to be easily mixed uniformly with other components such as resin and to easily increase the surface smoothness. Specifically, the particle size is preferably 3.0 μm or less, more preferably 2.95 μm or less, even more preferably 2.9 μm or less, and even more preferably 2.8 μm or less, especially 2.7 μm or less, especially 2.5 μm or less, especially 2.4 μm or less, especially 2.3 μm or less, especially 2.2 μm or less, especially 2.1 μm or less, and most preferably 2.0 μm or less. 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 measurement method. In addition, the present zeolite I may be formed by agglomeration of multiple zeolite particles to form secondary particles, and in this case, the particle size of the zeolite is the particle size of the primary particles.

[0013] (Zeolite Structure) Zeolite is a type of zeolite containing silicon or aluminum and oxygen. ４ It is a compound having a unit (T element is an element other than oxygen that constitutes the framework) as a basic unit. Specific examples of zeolites include crystalline porous aluminosilicates, crystalline porous aluminophosphates (ALPOs), and crystalline porous silicoaluminophosphates (SAPOs). The present zeolite I may have any of the above structures, but aluminosilicates are preferred. Zeolites are generally TO ４Zeolite is composed of structural units called Composite Building Units (hereinafter sometimes referred to as "CBUs"), which are composed of several (several to several tens) connected units. As a result, it has regular channels (tubular pores) and cavities. The CBUs and the crystalline structure of zeolites described below can be represented by codes defining the structure of zeolites established by the International Zeolite Association (IZA). The structure of zeolites can be identified using the Zeolite Structure Database 2018 Edition (http: / / www.iza-structure.org / databases / ) based on X-ray diffraction patterns obtained using an X-ray structure analyzer (e.g., a BRUKER D2PHASER tabletop X-ray diffractometer).

[0014] (Zeolite Skeleton) The skeleton of the present zeolite I preferably has d6r as the CBU. By having d6r, a resin composition with a low thermal expansion coefficient after curing is easily obtained. Zeolites having d6r as the CBU include AEI, AFT, AFV, AFX, AVL, CHA, EAB, EMT, ERI, FAU, GME, JSR, KFI, LEV, LTL, LTN, MOZ, MSO, MWW, OFF, SAS, SAT, SAV, SBS, SBT, SFW, SSF, SZR, TSC, and zeolites with a -WEN structure. Of these, zeolites with a structure of 8 or less oxygen-membered rings are particularly preferred from the viewpoint that water molecules are less likely to penetrate into the pores. Zeolites having an 8-membered oxygen ring or less structure include zeolites having an AEI, AFT, AFX, CHA, ERI, KFI, SAT, SAV, SFW, and TSC structure. Among these, zeolites having an AEI, AFX, CHA, and ERI structure are particularly preferred because the structure is stable even when the shape is controlled, and zeolites having a 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 formed by oxygen and T elements (elements other than oxygen that constitute the framework) that form the zeolite framework. Furthermore, the above-mentioned zeolites may be used alone or in combination of two or more types.

[0015] (Average Thermal Expansion Coefficient of Zeolite) The average thermal expansion coefficient of the present zeolite I is preferably low because a small amount of zeolite can easily reduce the average thermal expansion coefficient of liquid composition I, which will be described later. A small amount of zeolite is also preferred because the various physical properties of the resin are less likely to change due to the addition of zeolite. A low average thermal expansion coefficient is particularly preferred because it can suppress an increase in the viscosity of liquid composition I, which will be described later. Specifically, the average thermal expansion coefficient of zeolite is usually less than 0 ppm / K, preferably −2 ppm / K or less, more preferably −3 ppm / K or less, even more preferably −4 ppm / K or less, and particularly preferably −5 ppm / K or less.

[0016] On the other hand, considering that the zeolite will be used as a liquid composition I containing zeolite and a resin, which will be 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 separation of the zeolite and the resin is difficult. Therefore, the average thermal expansion coefficient of the zeolite is usually −1000 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. 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 more, preferably −50 ppm / K or more, more preferably −40 ppm / K or more, even more preferably −30 ppm / K or more, particularly 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." Here, to eliminate the influence of moisture desorption, the zeolite is usually measured in a dried state. The average thermal expansion coefficient of zeolite is usually measured in the range of 50 to 100°C. That is, it is a numerical value representing the change in lattice constant per degree Celsius from the average lattice constant at 50°C and the average lattice constant at 100°C when the zeolite is heated. Here, the average lattice constant at each temperature is the average value of the lattice constants of the a-axis, b-axis, and c-axis. The average thermal expansion coefficient is measured by gradually increasing the temperature after waiting until the lattice constant stabilizes.

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

[0018] (Zeolite Shape) The present zeolite I is preferably spherical. The spherical shape of the zeolite can suppress an increase in viscosity of a resin composition containing the zeolite. Specifically, the primary particles have the following circularity. Note that "primary particles" refer to unit particles that do not contain crystal grain boundaries inside. Furthermore, "primary particles" can be determined by observation using a scanning electron microscope (SEM).

[0019] <<Circularity>> The circularity of the primary particles of the present zeolite I 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, and it may be 1 or less. In the case of a cube, which is common in ordinary zeolites, the circularity is 0.785. In this specification, "circularity" is defined as "4 x π x area / (circumference)" ２ ". The area and circumference can be determined by observation with a scanning electron microscope (SEM). In this specification, "circularity" is the average value of 100 particles obtained with a scanning electron microscope (SEM). Methods for making the circularity of the primary particles of this zeolite I within the above range include performing a classification treatment after hydrothermal synthesis and adding seed crystals, amino acids, surfactants, or organic structure-directing agents in any proportion during hydrothermal synthesis.

[0020] (Zeolite Framework Density) The framework density of the present zeolite I 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 I is preferably 17.0 T / 1000 Å. ３ or less, more preferably 16.0T / 1000Å ３ On the other hand, the framework density of zeolite I is preferably high in order to increase the structural stability of the zeolite. The framework density of the zeolite is preferably 12.0 T / 1000 Å or less. ３ More preferably, 13.0T / 1000Å or more ３ More preferably, 14.0T / 1000Å ３ That's all. When the framework density is within the above range, the zeolite can be used as a stable filler. The framework density indicates the number of T atoms present per unit volume of the zeolite, and is a value determined by the structure of the zeolite. In this specification, the numerical values ​​listed in the IZA Zeolite Structure Database 2017 Edition (http: / / www.iza-structure.org / databases / ) may be used.

[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, and framework densities of 15.0T / 1000Å and above. ３ Larger, 16.0T / 1000Å ３ Examples of the following zeolites include zeolites of the AEI, AFT, AFV, AFX, AVL, EAB, GME, LEV, MWW, and SFW structure types, with a framework density of 14.0 T / 1000 Å. ３ Larger, 15.0T / 1000Å ３Examples of the following zeolites include CHA, KFI, SAS, and SAV structure zeolites with a framework density of 14.0 T / 1000 Å. ３ Examples of zeolites in the following ranges include zeolites of the EMT, FAU, JSR, SBS, SBT, and TSC type structures.

[0022] (Zeolite Composition) The composition of the present zeolite I 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 referred to as "SAR" or "Si / Al") of the present zeolite I is ２ "Si / Al molar ratio" or "Si / Al ２ The SAR (Si / Al ratio) of the zeolite is not particularly limited as long as the effect of the present invention is not impaired. ２ A high SAR (Si / Al ratio) of zeolite is preferable in that the moisture resistance of the cured product is increased and the amount of counter cations is easily controlled. ２ The SAR (Si / Al ratio) of the zeolite is usually 2 or more, preferably 5 or more, more preferably 10 or more, even more preferably 14 or more, among which 18 or more, among which 20 or more, among which 22 or more, among which 23 or more, among which 23.5 or more, particularly preferably 24 or more, especially more preferably 24.5 or more, and most preferably 25 or more. ２The SAR (Si / Al ratio) of zeolite is preferably low in terms of easy and inexpensive production. ２ The Si / Al ratio is usually 2000 or less, preferably 1000 or less, more preferably 500 or less, even more preferably 100 or less, of which 50 or less, of which 47.5 or less, of which 45 or less, of which 42.5 or less, of which 40 or less, of which 39 or less, of which 38 or less, particularly preferably 37 or less, even more preferably 36 or less, and most preferably 35 or less. ２ When the ratio is within the above range, the amount of counter cations can be easily controlled, and the production cost of the zeolite can be reduced. ２ The ratio can be adjusted by the types and ratio of the silicon-containing compound and aluminum-containing compound 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] (Counter cation of zeolite) The counter cation of the present zeolite I is not particularly limited as long as the effects of the present invention are not impaired. The counter cation of the zeolite is usually a component derived from the organic structure-directing agent, a proton, an alkali metal ion, or an alkaline earth metal ion. Preferably, it is a component derived from the organic structure-directing agent, a proton, or an alkali metal ion, more preferably a component derived from the organic structure-directing agent, a proton, a Li ion, a Na ion, or a K ion, and even more preferably a component derived from the organic structure-directing agent. In the case of alkali metal ions or alkaline earth metal ions, the smaller their size, the more likely the zeolite will exhibit an average thermal expansion coefficient of less than 0 ppm / K, which is preferable. In the case of components derived from the organic structure-directing agent, they are more flexible than alkali metal ions or alkaline earth metal ions, and therefore the zeolite will more likely exhibit an average thermal expansion coefficient of less than 0 ppm / K, which is preferable. That is, the zeolite is preferably a component type derived from an organic structure-directing agent (hereinafter, sometimes referred to as "as-made"), 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 I is not particularly limited as long as the effects of the present invention are not impaired. This is because it is presumed that the Composite Building Unit (CBU) is a factor that has a greater influence on the average thermal expansion coefficient of the cured product than the structure specified by the IZA code. The crystallinity of 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 of Zeolite) The present zeolite I 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) From the viewpoint of reducing the thermal expansion coefficient of the resin composition, the content of the zeolite I in the resin composition I is preferably 40% by mass or more, more preferably 45% by mass or more, and even more preferably 50% by mass or more, relative to the total amount of the resin composition. On the other hand, from the viewpoint of suppressing an increase in the viscosity of the resin composition, the content of the zeolite I in the resin composition I is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, relative to the total amount of the resin composition.

[0029] <Inorganic Filler Other Than Zeolite> The resin composition I may contain an inorganic filler other than the zeolite I (hereinafter, sometimes referred to as "other inorganic filler I"). The other inorganic filler I is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include at least one selected from the group consisting of metals, carbon, metal carbides, metal oxides, and metal nitrides. Examples of metals include silver, copper, aluminum, gold, nickel, iron, and titanium. Examples of carbon include carbon black, carbon fiber, graphite, fullerenes, and diamond. Examples of metal carbides include silicon carbide, titanium carbide, and tungsten carbide. Examples of metal oxides include magnesium oxide, aluminum oxide (alumina), silicon oxides such as silica, calcium oxide, zinc oxide, yttrium oxide, zirconium oxide, cerium oxide, ytterbium oxide, and sialon (ceramics composed of silicon, aluminum, oxygen, and nitrogen). Examples of metal nitrides include boron nitride, aluminum nitride, silicon nitride, etc. Among these inorganic fillers, silica is preferred from the viewpoint of being able to lower the viscosity of the resin composition.

[0030] The average particle size of the other inorganic filler I 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 I 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 I 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, i.e., the low CTE.

[0032] <Total Amount of Inorganic Filler> The total content of all inorganic fillers (total inorganic fillers) contained in the present resin composition I is preferably high in order to easily exhibit the effect as a filler. On the other hand, when the present resin composition I is liquid at room temperature, it is preferably low in order to have high fluidity and to easily fill narrow spaces. Specifically, the total content of all inorganic fillers is preferably 40% by mass or more, more preferably 45% by mass or more, and even more preferably 50% by mass or more, relative to the total amount of the 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 present resin composition I may contain a dispersant to improve the dispersibility of an inorganic filler such as the present zeolite I. The dispersant contained in the liquid composition I containing a resin and a filler is added mainly to the liquid composition I containing a resin and a filler having a large polarity difference, thereby improving the interfacial state between the two and improving compatibility. This can produce effects such as reducing viscosity, improving the dispersibility of the filler, 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. Polymeric dispersants are preferred. The main chain structure of the polymeric dispersant is not particularly limited, but examples include polyurethane, polyacrylic, polyester, polyamide, polyimide, and polyurea skeletons. From the perspective of storage stability, polyurethane, polyacrylic, and polyester skeletons are preferred. The structure of the polymeric dispersant is also not particularly limited, but examples include random structures, block structures, comb structures, and star structures. Similarly, from the perspective of storage stability, block structures and comb structures are preferred. Furthermore, solvent-free dispersants, particularly solvent-free polymeric dispersants, are preferred. The absence of a solvent in the dispersant can prevent volatilization of the dispersant and the generation of voids when the resin composition is heated and cured. Commercially available dispersants can be used. The following dispersants are commercially available, and among these, a dispersant having at least one functional group selected from the group consisting of an amino group and an amine salt may be used.

[0035] Commercially available polymeric dispersants include the DISPERBYK series of wetting dispersants 101, 102, 103, 106, 108, 109, 110, 111, 112, 116, 130, 140, 142, 145, 161, 162, 163, 164, 166, 167, 168, 170, 171, 174, 108, 182, 183, 184, 185, 2000, 2001, 2008, 2020, 2050, 2070, 2096, 2150, 2152, and 2155 available from BYK-Chemie, and the EFKA series 4008 available from BASF Japan. 4009, 4010, 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4340, 4400, 4401, 4402, 4403, 4406, 4800, 5010, 5044, 5054, 5055, 5063, 5064, 5065, 5066, 5070, 5244, and 3000, 5000, 11200, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000SC, and 24 000GR, 26000, 28000, 31845, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 36000, 36600, 37500, 38500, 39000, 53095, 54000, 55000, 56000, 71000, DISPARLON series 1210, 1220, 1831, 1850, 1860, 2100, 2150, 2200, 7004, KS-260, KS-273N, KS-860, KS-873N, PW-36, DN-900 commercially available from Kusumoto Chemical Co., Ltd. DA-234, DA-325, DA-375, DA-550, DA-1200, DA-1401, DA-7301, PB-711, PB-821, PB-822, PN-411, PA-111 of the Ajisper series commercially available from Ajinomoto Co., Inc., 104A, 104C, 104E, 104H, 104S, 104BC, 104DPM, 104PA, 104PG-50, 420, 440, DF110D, DF110L, DF37, DF58, DF75, DF210, CT111, CT121 of the Surfynol series commercially available from Air Products Co., Ltd.Examples of such compounds include CT131, CT136, GA, TG, TGE, STG and E1004 of the Olfin series commercially available from Nissin Chemical Industry Co., Ltd., 70, 2120, and 2190 of the SN Sparse series manufactured by San Nopco Ltd., the Adekacol and Adekatol series commercially available from ADEKA Corporation, and the Sannonik series, Naroacty CL series, Emulmin series, Newpol PE series, Ionet M series, Ionet D series, Ionet S series, Ionet T series, and Sunseparator 100 commercially available from Sanyo Chemical Industries, Ltd.

[0036] The content of the dispersant is preferably high, for example, in terms of facilitating uniform dispersion of the inorganic filler in the liquid composition I. On the other hand, the content of the dispersant is preferably low in terms of preventing 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 facilitate filling of the liquid composition I into a narrow space and to facilitate achieving 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] <Method for Producing Zeolite> Known methods can be applied to the method for producing zeolite. For example, when producing CHA-type zeolite, production can be performed with reference to the method described in JP 2009-097856 A. More specifically, an aluminum atom raw material, a silica atom raw material, an organic structure-directing agent, and the like are mixed to prepare an aqueous gel. The mixing order is usually such that the aluminum atom raw material is mixed with water, and then the silica atom raw material and the organic structure-directing agent are mixed therewith. Next, the prepared aqueous gel is subjected to hydrothermal synthesis, and the product is separated. Adhering components derived from the raw materials are removed by methods such as washing with water and drying, thereby obtaining 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 I"). The present production method I includes a step of hydrothermally synthesizing a raw material composition containing a silicon atom raw material, an aluminum atom raw material, an organic structure-directing agent, and water. Furthermore, as described above, the present production method I preferably does not perform the commonly performed calcination treatment, or performs 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 the present production method I, partial calcination can also be performed as described above, but it is preferable not to perform the calcination treatment. In other words, the present zeolite I is preferably not calcined (uncalcined). By not performing the calcination treatment, it is easy to achieve a weight loss rate of 1% or more, and ultimately, 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, a low viscosity, and good gap penetration. If necessary, a desired zeolite (hereinafter sometimes referred to as "seed zeolite") may be used.

[0039] <<Silicon Atom Source>> 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 Atom Source>> It is preferable to use a water-soluble aluminum atom source, and aluminum hydroxide is preferred because it contains a small amount of alkali metal.

[0041] <<Organic Substance>> As described above, the present zeolite I 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. 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 into the pores and reducing hygroscopicity. That is, the present zeolite I preferably contains a component derived from an organic structure-directing agent as the 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. Of these, N,N,N-trimethyl-1-adamantylammonium hydroxide (TMadaOH) is preferred from the viewpoints of its ability to easily retain organic substances within the pores of the zeolite at temperatures ranging from room temperature to 200°C and its ability to reduce the hygroscopicity of the zeolite. These agents may be used alone, or two or more may be used in any combination and ratio. The amount of the organic structure directing agent used is typically 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, in terms of the molar ratio relative to the silicon (Si) contained in the raw material composition. On the other hand, it is usually not more than 1, preferably not more than 0.6, more preferably not more than 0.55, even more preferably not more than 0.5, particularly preferably not more than 0.45, and most preferably not more than 0.4. By using it within this range, it is thought that high-purity spherical zeolite with few by-products can be easily grown.

[0043] <<Water>> When a seed zeolite described below is used, the amount of water used is, from the viewpoint of facilitating crystal formation, typically 5 or more, preferably 7 or more, more preferably 9 or more, and even more preferably 10 or more in terms of the molar ratio to silicon (Si) contained in the raw material composition other than the seed zeolite. Setting the amount of water within this range is preferred because crystal formation is facilitated. Furthermore, when zeolite is hydrothermally synthesized under conditions in which the amount of water is increased and the raw material concentration is diluted, zeolite with large particle sizes tends to be obtained. Furthermore, from the viewpoint of facilitating the cost reduction effect of waste liquid treatment, the molar ratio to silicon (Si) is 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 source may be used to produce a zeolite. When using an alkali metal atom source, the alkali metal atom is not particularly limited, and any known alkali metal atom used in the synthesis of zeolites can 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 be used.

[0045] <<Seed Zeolite>> Zeolite as seed crystals may be used in Production Method I. 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 a silicon atom raw material, an aluminum atom raw material, an organic structure-directing agent, and water, and then adding a seed zeolite, if used. In addition to the above-mentioned components, in the production of zeolite, components such as an acid component that promotes the reaction and a metal stabilizer such as a polyamine may be added in any step as needed.

[0047] <<Aging>> The raw material composition prepared as described above may be hydrothermally synthesized immediately after preparation. However, to obtain a zeolite with higher crystallinity, it is preferable to age the raw material for a certain period of time under predetermined temperature conditions. Particularly when scaling up the reaction, it is preferable to age the raw material while stirring it for a certain period of time, as this improves agitation and makes it easier to make the raw material more uniform. The temperature during aging is usually 100°C or lower, preferably 95°C or lower, and more preferably 90°C or lower. While the lower limit is not particularly limited, the temperature during aging is usually 0°C or higher, preferably 10°C or higher. The aging temperature may be constant during aging, or may be changed stepwise or continuously. The aging time is not particularly limited, but is usually 2 hours or longer, preferably 3 hours or longer, and more preferably 5 hours or longer. On the other hand, it is usually 30 days or shorter, preferably 10 days or shorter, and more preferably 4 days or shorter.

[0048] <<Hydrothermal Synthesis>> Next, the obtained raw material composition is subjected to hydrothermal synthesis. Hydrothermal synthesis is typically carried out by placing the raw material composition prepared as described above or an aqueous gel obtained by aging the raw material composition in a pressure-resistant container and maintaining the mixture at a predetermined temperature under self-generated pressure or under a gas pressure sufficient to prevent crystallization, while stirring, rotating or rocking the container, or while standing still. The reaction temperature during hydrothermal synthesis is typically 120°C or higher, preferably 130°C or higher, more preferably 140°C or higher, and even more preferably 150°C or higher, in order to increase the reaction rate. On the other hand, the reaction temperature is typically 230°C or lower, preferably 220°C or lower, more preferably 200°C or lower, and even more preferably 190°C or lower. The reaction time is not particularly limited, but is typically 2 hours or longer, preferably 3 hours or longer, and more preferably 5 hours or longer. On the other hand, the reaction time is typically 30 days or shorter, preferably 10 days or shorter, more preferably 7 days or shorter, and even more preferably 5 days or shorter. The reaction temperature may be constant during the reaction, or may be varied stepwise or continuously.

[0049] <<Drying Step>> After hydrothermal synthesis, the zeolite is separated from the composition after hydrothermal synthesis (hydrothermal synthesis reaction liquid). The separation method is not particularly limited, but is usually separated by filtration, decantation, direct drying, or the like after washing with water. Even when separated by filtration or decantation, it is usually dried thereafter. The drying conditions are not particularly limited, and for example, the drying temperature is preferably 50°C or higher and 200°C or lower, and more preferably 70°C or higher and 150°C or lower. The drying atmosphere is not particularly limited, but may be performed in air or in an inert gas atmosphere such as nitrogen or argon.

[0050] <<Caking>> The dried zeolite may be subjected to calcination or the like to remove the organic structure-directing agent and other components used during production in any proportion, as long as the pores contain organic matter, preferably components derived from the organic structure-directing agent. By using a zeolite containing an organic matter, preferably components derived from the organic structure-directing agent, in the present resin composition I, a resin composition that gives a cured product with a low CTE and low moisture absorption can be provided. When calcining is performed, the calcination temperature is usually preferably 200 to 1000°C. Calcining at 300°C or higher can remove the organic structure-directing agent and other components, while calcining at 1000°C or lower does not impair the physical properties of the zeolite. From the above perspectives, the calcination temperature is preferably 300°C or higher, more preferably 350°C or higher, even more preferably 400°C or higher, and preferably 900°C or lower, more preferably 800°C or lower, and even more preferably 700°C or lower. The calcination atmosphere is not particularly limited, and may be performed in air or an inert gas atmosphere such as nitrogen or argon. The calcination method is not particularly limited, and a muffle furnace, kiln, fluidized bed calcination furnace, etc. can be used, but a method of calcining by passing the above-mentioned gas is preferred. The gas flow rate is not particularly limited, but the amount of gas flow per 1 g of powder is preferably in the range of 0.1 ml / min to 100 ml / min, and more preferably 5 ml / min to 20 ml / min.

[0051] [Resin Composition] The resin composition I contains zeolite and a resin. The resin composition I is preferably liquid at room temperature. When the resin composition I is liquid at room temperature (hereinafter, sometimes referred to as "liquid composition I"), 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 term "resin composition" will be read as a liquid composition. In this specification, "liquid at room temperature" means that the resin composition has fluidity between 10°C and 35°C.

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

[0053] <<Thermosetting Resin>> The resin composition I preferably contains a thermosetting resin. The thermosetting resin is not particularly limited, and examples thereof include epoxy resins, polyimide resins, maleimide resins, polyamide resins, phenolic resins, vinyl ester resins, unsaturated polyester resins, and melamine resins. Among these thermosetting resins, in the present invention, it is preferable to contain at least one selected from the group consisting of epoxy resins and polyimide resins, and it is more preferable to contain an epoxy resin.

[0054] (Epoxy Resin) As the epoxy resin that can be used in the present invention, it is preferable to use an epoxy compound having an aromatic ring such as a bisphenol A skeleton, a bisphenol F skeleton, or a biphenyl skeleton, since these 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, it is preferable to use a polyfunctional epoxy resin in the resin composition I, since the glass transition temperature after heat curing is likely to be high. As the polyfunctional epoxy resin, various phenols such as phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, dicyclopentadiene phenol resin, phenol aralkyl resin, naphthol novolac resin, biphenyl novolac resin, terpene phenol resin, heavy oil modified phenol resin, and glycidyl ether type polyfunctional epoxy resins such as epoxy resins produced from various phenolic compounds, such as polyhydric phenol resins obtained by the condensation reaction of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, and epihalohydrin are preferred.

[0056] From the viewpoint of fluidity, the viscosity of the epoxy resin at 23°C is preferably 5 Pa·s or less, and more preferably 0.1 to 3 Pa·s. The method for measuring the viscosity of epoxy resins is specified in JIS K7233 (1986), and the single cylinder rotational viscometer method is suitable. The viscosity of the epoxy resin used in the present invention at 23°C may be measured using a B-type rotational viscometer ("LVDV-1 Pri", manufactured by Brookfield, spindle: S62), which is one of the single cylinder rotational viscometer methods.

[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 a lower melting point and lower viscosity of the epoxy resin improve the filling properties of the resin composition I and tend to improve bonding properties due to filling. One type of epoxy resin may be used alone, or two or more types may be mixed in any combination and ratio, and when mixed, the epoxy equivalent is the equivalent of the mixture.

[0058] The content of the epoxy resin in the present resin composition I is preferably low, since this relatively increases the content of inorganic fillers such as zeolite and makes it easier to reduce the thermal expansion coefficient. On the other hand, a high content is preferable, since it makes it easier to maintain the excellent physical properties of the epoxy resin. As described above, from the viewpoint of achieving both the maintenance of the excellent physical properties of the resin and the heat resistance (resistance to thermal expansion) of the cured resin composition, specifically, the content is preferably 5% by mass or more, and more preferably 10% by mass or more, relative to the total amount of the resin composition. On the other hand, the content is preferably 50% by mass or less, more preferably 35% by mass or less, and even more preferably 20% by mass or less.

[0059] (Curing Agent) The resin composition I preferably further contains a curing agent. The curing agent refers to a substance that contributes to the crosslinking reaction between crosslinking groups of a resin, particularly preferably an epoxy resin. The curing agent is not particularly limited, and those generally known as resin curing agents, particularly preferably epoxy resin curing agents, can be used. Examples include phenol-based curing agents, amine-based curing agents such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, acid anhydride-based curing agents, amide-based curing agents, tertiary amines, imidazole and its derivatives, organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan-based curing agents, isocyanate-based curing agents, blocked isocyanate-based curing agents, and dicyandiamine compounds. From the viewpoints of imparting fluidity and fast curing, acid anhydride-based curing agents are preferred as the curing agent.

[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, tetra(hydroxyethyl)ethylenediamine, etc. Specific examples of polyether amines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propylamine), polyoxypropylene diamine, polyoxypropylene triamines, etc. Examples of alicyclic amines include isophoronediamine, methacenediamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, and norbornenediamine. Examples of aromatic amines include tetrachloro-p-xylylenediamine, m-xylylenediamine, p-xylylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethylphenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl)ethylamine, diaminodiethyldimethyldiphenylmethane, and α,α'-bis(4-aminophenyl)-p-diisopropylbenzene.

[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 ethylene glycol bistrimellitate dianhydride, HET acid anhydride, Nadic acid anhydride, methyl Nadic acid anhydride, hydrogenated Nadic acid, hydrogenated methyl Nadic acid, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid anhydride, 3,4-dimethyl-6-(2-methyl-1-propenyl)-4-cyclohexene-1,2-dicarboxylic acid anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride, and 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride.

[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, and 2,4-diamino-6-[2'-methylimidazole]. Examples include 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of the above imidazoles with epoxy resins or polymer-encapsulated imidazole.

[0064] Examples of organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, etc., examples of phosphonium salts include tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, tetrabutylphosphonium tetrabutylborate, etc., and examples of tetraphenylboron salts include 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate, etc. One of these curing agents may be used alone, or two or more may be mixed in any combination and ratio.

[0065] When the present resin composition I contains a curing agent, the content of the curing agent is preferably such that the equivalent ratio of the epoxy groups in the epoxy resin to the functional groups in the curing agent (functional groups in the curing agent / epoxy groups in the epoxy resin) is in the range of 0.8 to 2.0, and more preferably in the range of 0.8 to 1.5, when the curing agent is a phenolic curing agent, an amine curing agent, or an acid anhydride curing agent, because this makes it less likely to be affected by residual unreacted epoxy groups or functional groups of the curing agent.

[0066] When the curing agent is an amide-based curing agent, a tertiary amine, imidazole and its derivatives, organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan-based curing agents, isocyanate-based curing agents, blocked isocyanate-based curing agents, etc., it is preferably used in an amount of 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, per 100 parts by mass of the epoxy resin. On the other hand, it is preferably used in an amount of 20 parts by mass or less, more preferably 15 parts by mass or less. In the case of a dicyandiamine compound, it is preferably used in an amount of 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, per 100 parts by mass of the epoxy resin. On the other hand, it is preferably used in an amount of 10 parts by mass or less, more preferably 6 parts by mass or less.

[0067] <Reactive Diluent> When the present resin composition I is in a liquid state, the present resin composition I 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. A monofunctional epoxy compound is an epoxy compound having one epoxy group, and has conventionally been used as a reactive diluent to adjust the viscosity of an epoxy resin composition. 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 I 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 I is liquid, the present resin composition I 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 I is heat-cured. The term "solvent" refers to a volatile component, and in this specification, this term encompasses water and organic solvents. The solvent-free liquid composition I 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 I.

[0070] <Method for producing the present resin composition I> The present resin composition I can be obtained by mixing and kneading the zeolite, resin, and optionally an inorganic filler other than the zeolite, a curing agent, a dispersant, a reactive diluent, and other additive components using a vacuum mixer, mixing roll, planetary mixer, etc., and degassing as necessary. The order in which these components are mixed is arbitrary, as long as there are no particular problems, such as the generation of reactions or precipitates. Two or more of the constituent components may be mixed in advance, and then the remaining components may be mixed, or all of the components may be mixed at once.

[0071] <Physical Properties of Resin Composition I> (Average Coefficient of Thermal Expansion (CTE)) When Resin Composition I is cured to a gel fraction of 80% or more, the average coefficient of thermal expansion (CTE) of the cured product at 25 to 100°C is preferably 0 ppm / K or more, more preferably 2 ppm / K or more, even more preferably 4 ppm / K or more, and particularly preferably 10 ppm / K or more. On the other hand, it is preferably 100 ppm / K or less, more preferably 50 ppm / K or less, and even more preferably 30 ppm / K or less. Such a resin composition has a low average coefficient of thermal expansion at temperatures below the glass transition temperature, and is therefore useful as a material for which various heat resistance properties are required, 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 present resin composition I is preferably a composition that has fluidity at room temperature (23°C). The viscosity of the present resin composition I is preferably low in order to facilitate filling of the resin composition into a narrow space. On the other hand, a high viscosity is preferable in order to prevent dripping and the like when filling the resin composition. The viscosity of the present resin composition I 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) When the present resin composition I is cured to a gel fraction of 80% or more, the cured product preferably has a water absorption rate of 5% or less. If the water absorption rate is 5% or less, problems caused by moisture absorption are unlikely to occur, even when the resin composition I is used as part of an electronic component such as an underfill material. From the above viewpoint, the lower the water absorption rate, the more preferable, 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) When the resin composition I is held at 80°C for 10 minutes, the gap filling distance for penetrating a 7 μm gap is preferably 10.0 cm or more, more preferably 10.5 cm or more, and even more preferably 11.0 cm or more. If the gap filling distance is this length or more, for example, when used as a part of an electronic component such as an underfill material, it can penetrate into a narrow gap well. The gap filling distance can be measured by the method described in the examples.

[0077] [Applications] The present resin composition I can be used, for example, in catalyst modules, molecular sieve membrane modules, optical components, moisture-absorbing materials, food products, building materials, and components and packaging materials for electronic devices, among which electronic devices are preferred. Electronic devices include devices that have two or more electrodes and control the current flowing between the electrodes or the voltage generated therefrom using electricity, light, magnetism, or chemicals, or devices that generate light, an electric field, or a magnetic field using an applied voltage or current. Specific examples include resistors, rectifiers (diodes), switching elements (transistors, thyristors), amplifier elements (transistors), memory elements, chemical sensors, and devices that combine or integrate these elements. Other examples include photodiodes or phototransistors that generate photocurrent, electroluminescent elements that emit light when an electric field is applied, and optical elements such as photoelectric conversion elements or solar cells that generate electromotive force when exposed to light. The electronic device is preferably a semiconductor device. The semiconductor device preferably has at least a semiconductor substrate, and examples include devices in which a semiconductor chip is mounted on a substrate, and devices in which semiconductor chips and semiconductor substrates are stacked in multiple layers.

[0078] <Liquid Sealant> When the present resin composition I is in a liquid state, it is preferably used as a liquid sealant, and in this case, the liquid composition I is cured to form a sealant. The liquid sealant may be used as a sealant that fills gaps formed in components by filling the gaps and then curing. A method for producing a sealant that includes a step of filling the gaps with the resin composition and then curing is also within the scope of the present invention. The liquid sealant may also be used as a sealant that fills gaps between components, for example, by applying it to various components, then overlaying another component on the liquid sealant, and then appropriately curing it. In this case, the liquid sealant may be appropriately cured to a B-stage before overlaying the other component. Among these, the present resin composition I, particularly a liquid composition I in which the present resin composition I is in a liquid state, is preferably used for applications in which the resin composition I is filled into gaps and cured. That is, it is preferable to produce a sealant by filling the gaps with the present resin composition I and then curing it.

[0079] The present resin composition I 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 between a substrate and a semiconductor chip, between substrates, or between semiconductor chips. Known substrates can be used as the substrate, and substrates made of organic materials such as epoxy resin substrates and phenolic resin substrates are preferably used. The semiconductor chip is preferably formed from a semiconductor substrate such as a silicon substrate. The present resin composition I has a low thermal expansion coefficient when cured, and its use as an underfill material reduces the difference with the thermal expansion coefficient of the semiconductor substrate, thereby improving thermal cycle resistance, etc.

[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 a plurality of bumps are formed, forming an underfill layer. The filled underfill material may be B-staged as necessary. The semiconductor chip on which the underfill layer is formed may then be placed on the surface of the substrate with the underfill layer facing the substrate. The underfill layer is then cured by heating and pressurizing, etc., to form 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.

[0084] Second Aspect [Resin Composition] The resin composition according to the second aspect of the present invention (hereinafter sometimes referred to as "the present resin composition II") contains zeolite, an inorganic filler other than zeolite, and a resin. The present resin composition II is preferably liquid at room temperature. When the present resin composition II is liquid at room temperature (hereinafter sometimes referred to as "liquid composition II"), 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 term "resin composition" will be read as a liquid composition. In this specification, "liquid at room temperature" means that the resin composition has fluidity between 10°C and 35°C.

[0085] In a second aspect, the present resin composition II has an object to provide a resin composition that has a low coefficient of thermal expansion after curing, low moisture absorption, and low viscosity.

[0086] According to the present resin composition II, it is possible to provide a resin composition that has a low coefficient of thermal expansion after curing, low moisture absorption, and low viscosity.

[0087] More specifically, the gist of this resin composition II is as follows. [1'] A resin composition comprising a zeolite, an inorganic filler other than zeolite, and a resin, wherein the zeolite exhibits a weight loss of 1% or more at 800°C based on the weight at 400°C 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, as determined by thermogravimetric analysis (TGA). [2'] The resin composition according to the above [1'], wherein the zeolite has a d6r CBU. [3'] The resin composition according to the above [1'] or [2'], wherein the zeolite comprises a zeolite having an 8- or less oxygen-membered ring structure. [4'] The resin composition according to any one of the above [1'] to [3'], wherein the zeolite comprises a zeolite with a CHA-type structure. [5'] The resin composition according to any one of the above [1'] to [4'], wherein the zeolite has a sphericity of 0.7 or more. [6'] The resin composition according to any one of the above [1'] to [5'], wherein the zeolite has a circularity of 0.800 or more. [7'] The resin composition according to any one of the above [1'] to [6'], wherein the zeolite is an aluminosilicate. [8'] The resin composition according to any one of the above [1'] to [7'], wherein the inorganic filler other than zeolite is silica. [9'] The resin composition according to any one of the above [1'] to [8'], wherein the inorganic filler other than zeolite has an average particle size of 0.1 to 5 μm. [10'] The resin composition according to any one of the above [1'] to [9'], wherein the mass ratio of the zeolite to the inorganic filler other than zeolite is 5 / 65 to 40 / 30. [11'] The resin composition according to any one of the above [1'] to [10'], wherein the content of the inorganic filler other than zeolite is 1 to 50 mass%. [12'] The resin composition according to any one of [1'] to [11'] above, wherein the resin comprises a thermosetting resin. [13'] The resin composition according to [12'] above, wherein the thermosetting resin comprises an epoxy resin. [14'] A liquid sealant comprising the resin composition according to any one of [1'] to [13'] above. [15'] An underfill material comprising the resin composition according to any one of [1'] to [13'] above.[16'] A method for producing an encapsulant, comprising a step of filling a gap with the resin composition according to any one of [1'] to [13'] above, and then curing the composition. [17'] An electronic device comprising the encapsulant obtained by the production method according to [16'] above.

[0088] <Zeolite> The zeolite used in the present resin composition II (hereinafter sometimes referred to as "the present zeolite II") is similar to the above-mentioned the present zeolite I, and is characterized in that it contains an organic substance, preferably a component derived from an organic structure-directing agent, which is a raw material for zeolite, inside its pores. Specifically, the present zeolite II exhibits a weight loss of 1% or more at 800°C, based on the weight at 400°C, 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, as measured by thermogravimetric analysis (TGA).

[0089] The zeolite structure, zeolite framework, zeolite average thermal expansion coefficient, zeolite framework density, zeolite composition, zeolite silica / alumina molar ratio (SAR), zeolite countercation, zeolite crystallinity, and specific and preferred aspects of the surface treatment of the zeolite of the present zeolite II are the same as those of the present zeolite I described above, and all of these can be used by reference.

[0090] (Zeolite Particle Size) The particle size of the present zeolite II is preferably 5.0 μm or less. When the zeolite particle size is 5.0 μm or less, the resin composition can be sufficiently filled even in a narrow gap. From the above viewpoints, the smaller the particle size of the present zeolite II, the more preferable, and there is no particular lower limit. In addition, a small particle size of the zeolite has the advantage that it can be easily mixed uniformly with other components such as resins. Specifically, the particle size of the present zeolite II is more preferably less than 5.0 μm, even more preferably 4.5 μm or less, and particularly preferably 4.0 μm or less.

[0091] On the other hand, the lower limit is not particularly limited, but may be 0.05 μm or more, 0.1 μm or more, 0.3 μm or more, 0.5 μm or more, or 1.0 μm or more, from the viewpoints of ease of handling and the viscosity of the present resin composition II being unlikely to increase. The particle size of the present zeolite II 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 scanning electron microscope (SEM). In addition, the present zeolite II may be formed into secondary particles by aggregation of multiple zeolite particles, and in this case, the particle size of the zeolite is the particle size of the primary particle.

[0092] When using zeolite, the zeolite particle is usually not a single particle but a group of multiple zeolite particles. That is, in one embodiment of the present invention, it is preferable to use a group of zeolites containing at least the present zeolite II particles. In one embodiment of the present invention, the zeolite consisting of multiple zeolite particles preferably has an average primary particle size in the range of 0.05 μm to 5.0 μm, more preferably 0.1 μm to 4.0 μm, and even more preferably 0.5 μm to 3.5 μm. The average primary particle size of the zeolite is determined by randomly selecting 50 particles of zeolite (powder, particles in liquid composition II) and measuring their particle sizes, and then averaging the measured values.

[0093] (Zeolite Shape) The present zeolite II is preferably spherical. The spherical shape of the zeolite can suppress an increase in viscosity of a resin composition containing the zeolite. Specifically, it is preferable that the zeolite has the following sphericity and roundness.

[0094] <<Sphericity>> The sphericity of the present zeolite II is preferably 0.7 or more, more preferably 0.8 or more. The upper limit of the sphericity is not particularly limited, and may be 1 or less. The sphericity of a cubic zeolite, which is common in ordinary zeolites, is 0.58. In this specification, "sphericity" is the average value of 10 particles obtained using a scanning electron microscope (SEM). In this specification, "sphericity" is defined as "the ratio of the minimum diameter to the maximum diameter of a particle." The maximum diameter and the minimum diameter can be determined by observation using a scanning electron microscope (SEM).

[0095] <<Circularity>> The circularity of the present zeolite II is preferably 0.800 or more, more preferably 0.810 or more, even more preferably 0.820 or more, particularly preferably 0.830 or more, and most preferably 0.840 or more. There is no particular upper limit to the circularity, and it may be 1 or less. In the case of a cube, which is common in ordinary zeolites, the circularity is 0.785. In this specification, "circularity" is defined as "4 x π x area / (circumference)" ２ The area and circumference can be determined by observation with a scanning electron microscope (SEM). In this specification, the "roundness" is the average value of 10 particles obtained with a scanning electron microscope (SEM).

[0096] (Zeolite Content) From the viewpoint of suppressing an increase in viscosity of the resin composition while lowering the thermal expansion coefficient, the content of the zeolite II in the resin composition II is preferably 40% by mass or more and 70% by mass or less, more preferably 45% by mass or more and 65% by mass or less, and even more preferably 50% by mass or more and 60% by mass or less, relative to the total amount of the resin composition.

[0097] <Inorganic Filler Other Than Zeolite> The present resin composition II contains an inorganic filler other than the present zeolite II (hereinafter, sometimes referred to as "other inorganic filler II"). Specific and preferred aspects of the other inorganic filler II are the same as those of the above-mentioned other inorganic filler I, and all of these can be used interchangeably. Furthermore, the average particle size of the other inorganic filler II and the content of the present zeolite II in all inorganic fillers are the same as the average particle size of the other inorganic filler I and the content of the present zeolite I in all inorganic fillers, respectively.

[0098] One of the features of this resin composition II is the use of a zeolite in combination with an inorganic filler other than zeolite, which allows for both a low CTE and a low viscosity. The mass ratio of the inorganic filler other than zeolite to the zeolite 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 5 / 65 to 40 / 30. This range makes it easier to achieve the above effects. From the above perspectives, the mass ratio is more preferably in the range of 10 / 60 to 35 / 35.

[0099] Furthermore, when the present resin composition II contains an inorganic filler II other than the present zeolite II, the content of the other inorganic filler II in the present resin composition II is preferably in the range of 1 mass % to 50 mass %, more preferably in the range of 5 mass % to 40 mass %, and even more preferably in the range of 10 mass % to 35 mass %. When the content is equal to or greater than the lower limit, a low viscosity of the liquid composition II can be achieved, and when the content is equal to or less than the upper limit, the content of the present zeolite II is sufficiently high, allowing a reduction in the CTE.

[0100] <Total Amount of Inorganic Filler> The total content of all inorganic fillers (total inorganic fillers) contained in the present resin composition II is preferably high in order to easily exhibit the effect as a filler. On the other hand, when the present resin composition II is liquid, it is preferably low in order to have high fluidity and to easily fill narrow spaces. Specifically, the total content of all inorganic fillers is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more, relative to 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.

[0101] <Dispersant> The present resin composition II may contain a dispersant to enhance the dispersibility of the inorganic filler such as the present zeolite II. The dispersant is the same as the dispersant that may be contained in the present resin composition I.

[0102] <Method for Producing Zeolite> Specific and preferred aspects of the method for producing the present zeolite II are the same as those of the above-described production method I, and all of these can be used. That is, in the method for producing the present zeolite II, partial calcination can be performed as in the above-described production method I, but it is preferable not to perform the calcination treatment, and it is preferable that the present zeolite II 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 that has a low thermal expansion coefficient after curing, low moisture absorption, and low viscosity.

[0103] <Resin, curing agent, reactive diluent, and other additives> Specific and preferred embodiments of the resin, curing agent, reactive diluent, and other additives in the present resin composition II are the same as those in the present resin composition I described above, and all of these can be used by reference.

[0104] The content of the epoxy resin in this resin composition II is preferably low, since this relatively increases the content of inorganic fillers such as zeolite and makes it easier to reduce the thermal expansion coefficient. On the other hand, a high content is preferable, since it makes it easier to maintain the excellent physical properties of the epoxy resin. As described above, from the viewpoint of achieving both the maintenance of the excellent physical properties of the resin and the heat resistance (resistance to thermal expansion) of the cured resin composition, specifically, the content is preferably 5% by mass or more, and more preferably 10% by mass or more, relative to the total amount of the resin composition. On the other hand, the content is preferably 50% by mass or less, more preferably 25% by mass or less, and even more preferably 15% by mass or less.

[0105] When the curing agent is an amide-based curing agent, a tertiary amine, imidazole and its derivatives, organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan-based curing agents, isocyanate-based curing agents, blocked isocyanate-based curing agents, etc., it is preferably used in an amount of 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, per 100 parts by mass of the epoxy resin. On the other hand, it is preferably used in an amount of 20 parts by mass or less, more preferably 10 parts by mass or less. In the case of a dicyandiamine compound, it is preferably used in an amount of 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, per 100 parts by mass of the epoxy resin. On the other hand, it is preferably used in an amount of 10 parts by mass or less, more preferably 6 parts by mass or less.

[0106] Furthermore, when the present resin composition II is liquid, the present resin composition II 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 II is heat-cured. Note that the term "solvent" refers to a volatile component, and in this specification, this term encompasses water and organic solvents. The solvent-free liquid composition II is one that does not substantially contain a solvent. For example, the solvent content is preferably less than 3% by mass, more preferably less than 1% by mass, and even more preferably 0% by mass, relative to the total amount of the liquid composition II.

[0107] <Method for producing the present resin composition II> The method for producing the present resin composition II is the same as the method for producing the present resin composition I.

[0108] <Physical Properties of Resin Composition II> (Average Coefficient of Thermal Expansion (CTE)) When Resin Composition II is cured to a gel fraction of 80% or more, the average coefficient of thermal expansion (CTE) of the cured product at 25 to 100°C is preferably 0 ppm / K or more, more preferably 2 ppm / K or more, even more preferably 4 ppm / K or more, and particularly preferably 10 ppm / K or more. On the other hand, it is preferably 100 ppm / K or less, more preferably 50 ppm / K or less, and even more preferably 25 ppm / K or less. Such a resin composition has a low average coefficient of thermal expansion at temperatures below the glass transition temperature, and is therefore useful as a material for which various heat resistance properties are required, and is particularly effective for application to electronic devices.

[0109] 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.

[0110] (Viscosity) The resin composition II is preferably a composition that has fluidity at room temperature (23°C). The viscosity of the resin composition II is preferably low in order to facilitate filling of the resin composition into a narrow space. On the other hand, a high viscosity is preferable in order to prevent dripping during filling of the resin composition. The viscosity of the resin composition II at 23°C is preferably 0.1 Pa·s or more, more preferably 1 Pa·s or more, even more preferably 5 Pa·s or more, and particularly preferably 10 Pa·s or more. On the other hand, it is preferably 250 Pa·s or less, more preferably 150 Pa·s or less, and even more preferably 60 Pa·s or less.

[0111] 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.

[0112] (Water absorption rate) When the present resin composition II is cured to a gel fraction of 80% or more, the cured product preferably has a water absorption rate of 15% or less. If the water absorption rate is 15% or less, problems caused by moisture absorption are unlikely to occur, even when the resin composition II is used as part of an electronic component such as an underfill material. From the above viewpoint, the lower the water absorption rate, the more preferable it is, more preferably 10% or less, even more preferably 5% or less, and particularly preferably 3% or less. The water absorption rate can be measured by the method described in the examples.

[0113] [Uses] The uses of the present resin composition II are the same as those of the present resin composition I. When the present resin composition II is liquid, it is preferably used as a liquid sealant, as in the case of the present resin composition I, and in this case, the liquid composition is cured to form a sealant. That is, the present resin composition II can be read as the present resin composition I, and the liquid composition II can be read as the liquid composition I.

[0114] 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.

[0115] <First Aspect> Examples and comparative examples relating to the first aspect will be described below. (Evaluation of physical properties) Physical properties were evaluated as follows.

[0116] (Gel Fraction) The gel fraction of the cured product was measured by the following procedure. After heat treatment at 80°C for 2 hours, the cured product produced under the conditions of 120°C for 2 hours 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.

[0117] (Weight Loss Rate) The weight loss rate of zeolite was measured by the following procedure. Approximately 5 mg of zeolite was placed in a platinum cup and placed in a thermal analyzer (apparatus name: TGA Q5000IR, manufactured by TA Instruments). The temperature was increased from room temperature to 800°C at a rate of 10°C / min in an air atmosphere and held at 800°C for 10 minutes. The weight loss rate was determined as the weight loss rate at 800°C relative to the weight at 400°C. Specifically, it was calculated by the formula "weight loss rate of zeolite = 100 × {(weight at 400°C) - (weight held at 800°C for 10 minutes)} / (weight at 400°C)."

[0118] (Circularity of Primary Particles) The circularity of primary particles of zeolite was measured by the following procedure. 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 as 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.

[0119] (Particle Size Distribution) The particle size distribution of the zeolite was measured by the following procedure. Zeolite powder was added to pure water to prepare a slurry of approximately 0.2 mass %, which was then introduced into a laser diffraction / scattering particle size distribution analyzer (apparatus name: Laser Diffraction / Scattering Particle Size Distribution Analyzer Partica mini LA-350, manufactured by HORIBA) through which pure water was flowing, and ultrasonic treatment was performed for 1 minute, after which a volume-based 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 obtained volume-based particle size distribution measurement, the proportion of particles having a particle size of 3 μm or more relative to all particles detected by the apparatus was calculated, and this was taken as the particles (%) having a particle size of 3 μm or more obtained in the volume-based particle size distribution measurement.

[0120] (Particle size) The particle size of the zeolite was measured by the following procedure. Zeolite powder was added to pure water to prepare a slurry of about 0.2% by mass, which was then introduced into a laser diffraction / scattering particle size distribution analyzer (apparatus name: Laser diffraction / scattering particle size distribution analyzer Partica mini LA-350, manufactured by HORIBA) through which pure water was flowing, and ultrasonic treatment was performed for 1 minute, after which a volume-based 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 obtained volume-based particle size distribution measurement, the median diameter was calculated, and this was taken as the particle size of the zeolite.

[0121] (Mean Coefficient of Thermal Expansion (CTE) of Zeolite) The mean coefficient of thermal expansion of zeolite was measured by the following procedure. Pre-dried zeolite was placed in an X-ray diffractometer (D8ADVANCE, manufactured by BRUKER) and X-ray diffraction measurements were performed in the temperature range of 50 to 100°C. From the obtained results, the lattice constants of the a-axis, b-axis, and c-axis at each temperature were calculated using X-ray diffraction analysis software (JADE, manufactured by Materials Data). The mean coefficient of thermal expansion of zeolite was calculated by the formula: "Mean coefficient of thermal expansion of zeolite = {(mean lattice constant at 100°C) - (mean lattice constant at 50°C)} / {(mean lattice constant at 50°C) x (100°C - 50°C)}." Here, the mean lattice constant at each temperature is the average value of the lattice constants of the a-axis, b-axis, and c-axis.

[0122] (Average Coefficient of Thermal Expansion (CTE) of Cured Product) The average coefficient of thermal expansion of the cured product when the resin composition was cured to a gel fraction of 80% or more was measured by thermomechanical analysis using a method in accordance with JIS K7197 (2012). It was measured by a compression method using a thermomechanical analyzer (model: TMA SS7100, manufactured by SII NanoTechnology, Inc.). Specifically, when the resin composition was cured to a gel fraction of 80% or more, the cured product was cut into a size of φ6 mm x 10 mm, and the temperature was decreased from 200°C to 20°C at a rate of 5°C / min using a thermomechanical analyzer by a compression method. The temperature change in the change in the sample length from 25 to 100°C was measured, and the slope of the tangent was taken as the average coefficient of thermal expansion (CTE).

[0123] (Viscosity) The viscosity of the resin composition at 23°C was measured using a Brookfield type rotational viscometer. When the viscosity was 0.1 to 100 Pa s, an "LVDV-1 Pri" manufactured by Brookfield, with spindles S64 and S63, was used as the Brookfield type rotational viscometer, and when the viscosity exceeded 100 Pa s, an "HBDV-E" manufactured by Brookfield, with spindle S-07, was used. The value measured at 5 rpm was used as the representative viscosity value for each sample.

[0124] (Water absorption rate) When the resin composition was cured to a gel fraction of 80% or more, the cured product was kept in a drying oven at 125°C for 3 hours, and then kept in a constant temperature and humidity chamber adjusted to 85°C and 85% humidity for 3 hours, after which the weight change rate (%) was evaluated.

[0125] (Gap filling distance) A 7 μm gap was provided 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 surface, 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 traveled in the gap was measured to evaluate the gap filling distance.

[0126] First, examples of the zeolite according to the first aspect of the present invention will be shown.

[0127] Production Example 1-1 To a vessel were sequentially added water, N,N,N-trimethyl-1-adamantylammonium hydroxide (TMadaOH) manufactured by Seichem Corporation as an organic structure directing agent (SDA), 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 were as follows: SiO ２ :Al ２ O ３ :TMadaOH:H ２ The ratio of O to surfactant was 1.0:0.025:0.3:25:0.02. Then, CHA-type zeolite was added as a seed crystal to SiO ２After adding 5% by mass of the zeolite to the powder and mixing 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 resulting zeolite had 1% of particles of 3 μm or larger by volume. The particle size of the resulting zeolite was 1.21 μm. The circularity of the primary particles was 0.839. XRD analysis of the resulting powder confirmed that it was CHA-type zeolite. The weight loss rate of the resulting zeolite, determined using the above method, was 22.6%. The average thermal expansion coefficient of the zeolite at 50 to 100°C was -6.8 ppm / K.

[0128] Production Example 1-2 Zeolite was produced in the same manner as in Production Example 1-1. The produced zeolite was calcined at 600°C for 6 hours under air flow to obtain calcined zeolite. 15% of the particles of the obtained zeolite were 3 μm or larger by volume. 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.

[0129] Production Example 1-3 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 a vessel. The composition and molar ratio of the resulting mixture were as follows: SiO ２ :Al ２ O ３ :TMadaOH:H ２The ratio of the zeolite to the total weight of the powder was 1.0:0.025:0.4:20. After thorough mixing, the resulting mixture was placed in a pressure-resistant container 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 resulting zeolite had 50% particles of 3 μm or larger by volume. The particle size of the resulting zeolite was 2.98 μm. The circularity of the primary particles was 0.840. XRD analysis of the resulting powder confirmed that it was CHA-type zeolite. The weight loss rate of the resulting zeolite, determined using the above method, was 24.2%. The average thermal expansion coefficient of the zeolite at 50 to 100°C was -5.0 ppm / K.

[0130] Next, examples of the resin composition according to the first aspect of the present invention will be described. <Components> The components used in preparing the resin composition are as follows.

[0131] <Epoxy Resins> (A-1) p-Aminophenol-Type Epoxy Resin; Mitsubishi Chemical Corporation, Product Name "jER630", Epoxy Equivalent: 97 g / equivalent <Curing Agents> (B-1) Acid Anhydride Curing Agent; Acid Anhydride (Main Component: Hydrogenated Methyl Nadic Anhydride): New Japan Chemical Co., Ltd., Product Name "RIKACID HNA-100" (Acid Anhydride Equivalent: 174-184) (C-1) Imidazole-Based Curing Agent; Shikoku Chemicals Corporation, Product Name "2E4MZ-CN" <Fillers> (D-1) Zeolite Filler 1-1; The zeolite produced in Production Example 1-1 above was used. (E-1) Zeolite Filler 1-2; The zeolite produced in Production Example 1-2 above was used. (F-1) Zeolite Filler 1-3; The zeolite produced in Production Example 1-3 above was used. <Additives> (G-1) Additive: Wetting and dispersing agent manufactured by BYK Japan, product name "DISPERBYK-2152" (amino group-containing ultra-molecular weight polyester, comb type, solvent-free)

[0132] Example 1-1 The filler, resin, curing agent, and additives shown in Table 1 were blended in the amounts shown in Table 1. A resin composition (liquid composition) was then prepared by mixing for 5 minutes at 1500 rpm using a vacuum mixer (EME Corporation, "V-mini 300"). 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 using the method described above. The results are shown in Table 1. Next, this liquid composition was poured into a mold and heated at 80°C for 2 hours, then heated at 120°C for 2 hours to cure to a gel fraction of 80% or more, and then demolded to obtain a cured product. The CTE and water absorption of this cured product were evaluated using the evaluation methods described above. The results are shown in Table 1.

[0133] Comparative Examples 1-1 to 1-2 Resin compositions (liquid compositions) and cured products were obtained in the same manner as in Example 1-1, except that the zeolite filler in Example 1-1 was replaced with one shown in Table 1. The results of evaluation in the same manner as in Example 1-1 are shown in Table 1.

[0134]

[0135] The results of Example 1-1 and Comparative Example 1-1 showed that using a zeolite containing a component derived from an organic structure-directing agent (Example 1-1) as a filler reduced viscosity and water absorption, and increased gap-filling distance compared to using a calcined zeolite (Comparative Example 1-1). The calcined zeolite obtained in Comparative Example 1-1 had a higher proportion of particles with a volumetric primary particle diameter of 3 μm or more than that of the zeolite containing a component derived from an organic structure-directing agent obtained in Example 1-1. This is presumably due to the particles adhering to each other through the calcination treatment. The resin composition obtained in Comparative Example 1-1 also had a higher viscosity than the resin composition obtained in Example 1-1. This is presumably due to the increase in isolated silanol groups on the particle surface when the zeolite was calcined, resulting in an interaction between the isolated silanol groups and the resin. The results of Example 1-1 and Comparative Example 1-2 also showed that using a zeolite containing 40% or less of primary particles with a volumetric primary particle diameter of 3 μm or more increased gap-filling distance. That is, the zeolite related to the first aspect 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.

[0136] <Second Aspect> Examples and comparative examples relating to the second aspect will be described below. (Evaluation of physical properties) Physical properties were evaluated as follows.

[0137] (Gel Fraction) The gel fraction of the cured product was measured by the following procedure. After heat treatment at 80°C for 2 hours, the cured product produced under the conditions of 120°C for 2 hours 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.

[0138] (Weight Loss Rate) The weight loss rate of zeolite was measured by the following procedure. Approximately 5 mg of zeolite was placed in a platinum cup and placed in a thermal analyzer (apparatus name: TGA Q5000IR, manufactured by TA Instruments). The temperature was increased from room temperature to 800°C at a rate of 10°C / min in an air atmosphere and held at 800°C for 10 minutes. The weight loss rate was determined as the weight loss rate at 800°C relative to the weight at 400°C. Specifically, it was calculated by the formula "weight loss rate of zeolite = 100 × {(weight at 400°C) - (weight held at 800°C for 10 minutes)} / (weight at 400°C)."

[0139] (Average Primary Particle Size) The average primary particle size of zeolite was measured by the following procedure. Particles were observed using a scanning electron microscope (SEM) (instrument name: JSM-6701F, manufactured by JEOL). 50 particles that could be considered to be primary particles were randomly selected, and for each particle, the diameter of the largest circle having an area equal to the projected area of ​​the particle (equivalent circle diameter) was determined. The average value of the equivalent circle diameters of the obtained 50 particles was calculated, and this was defined as the average primary particle size of the zeolite.

[0140] (Circularity of Primary Particles) The circularity of primary particles of zeolite was measured by the following procedure. Particles were observed using a scanning electron microscope (SEM) (device name: JSM-6701F, manufactured by JEOL). The area and circumference of 10 particles that could be considered as 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 the 10 particles obtained was calculated, and this was taken as the circularity of the primary particles of the zeolite.

[0141] (Sphericity of Primary Particles) The sphericity of primary particles of zeolite was measured by the following procedure. Particles were observed using a scanning electron microscope (SEM) (device name: JSM-6701F, manufactured by JEOL). The maximum and minimum diameters of 10 particles that could be considered primary particles were then determined, and the ratio of the minimum diameter to the maximum diameter of the particle was calculated. The average value of the sphericity values ​​of the obtained 10 particles was calculated, and this was taken as the sphericity of the primary particles of the zeolite.

[0142] (Mean Coefficient of Thermal Expansion (CTE) of Zeolite) The mean coefficient of thermal expansion of zeolite was measured by the following procedure. Pre-dried zeolite was placed in an X-ray diffractometer (D8ADVANCE, manufactured by BRUKER) and X-ray diffraction measurements were performed in the temperature range of 50 to 100°C. From the obtained results, the lattice constants of the a-axis, b-axis, and c-axis at each temperature were calculated using X-ray diffraction analysis software (JADE, manufactured by Materials Data). The mean coefficient of thermal expansion of zeolite was calculated by the formula: "Mean coefficient of thermal expansion of zeolite = {(mean lattice constant at 100°C) - (mean lattice constant at 50°C)} / {(mean lattice constant at 50°C) x (100°C - 50°C)}." Here, the mean lattice constant at each temperature is the average value of the lattice constants of the a-axis, b-axis, and c-axis.

[0143] (Average Coefficient of Thermal Expansion (CTE) of Cured Product) The average coefficient of thermal expansion of the cured product when the resin composition was cured to a gel fraction of 80% or more was measured by thermomechanical analysis using a method in accordance with JIS K7197 (2012). It was measured by a compression method using a thermomechanical analyzer (model: TMA SS7100, manufactured by SII NanoTechnology, Inc.). Specifically, when the resin composition was cured to a gel fraction of 80% or more, the cured product was cut into a size of φ6 mm x 10 mm, and the temperature was decreased from 200°C to 20°C at a rate of 5°C / min using a thermomechanical analyzer by a compression method. The temperature change in the change in the sample length from 25 to 100°C was measured, and the slope of the tangent was taken as the average coefficient of thermal expansion (CTE).

[0144] (Viscosity) The viscosity of the resin composition at 23°C was measured using a Brookfield type rotational viscometer. When the viscosity was 0.1 to 100 Pa s, an "LVDV-1 Pri" manufactured by Brookfield, with spindles S64 and S63, was used as the Brookfield type rotational viscometer, and when the viscosity exceeded 100 Pa s, an "HBDV-E" manufactured by Brookfield, with spindle S-07, was used. The value measured at 5 rpm was used as the representative viscosity value for each sample.

[0145] (Water absorption rate) When the resin composition was cured to a gel fraction of 80% or more, the cured product was kept in a drying oven at 125°C for 3 hours, and then kept in a constant temperature and humidity chamber adjusted to 85°C and 85% humidity for 3 hours, after which the weight change rate (%) was evaluated.

[0146] First, examples of the zeolite according to the second aspect of the present invention will be shown.

[0147] Production Example 2-1 (Production of Uncalcined Zeolite) N,N,N-trimethyl-1-adamantylammonium hydroxide (TMadaOH) manufactured by Seichem Co., Ltd. as a structure directing agent (SDA), "Kyoward 200S" manufactured by Kyowa Chemical Industry Co., Ltd. as aluminum hydroxide, and "AEROSIL 200" manufactured by Nippon Aerosil Co., Ltd. as silica were sequentially added to a vessel. The composition and molar ratio of the resulting mixture were as follows: SiO ２ :Al ２ O ３ :TMadaOH:H ２ The ratio of the zeolite to the total mass was 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 resulting uncalcined zeolite had particle sizes ranging from 1.0 μm to 10 μm, and its average primary particle size was 3.1 μm. The average thermal expansion coefficient of the uncalcined zeolite at 50 to 100°C was -5.0 ppm / K, the sphericity was 0.84, and the roundness was 0.840.

[0148] Production Example 2-2 (Production of Calcined Zeolite) The uncalcined zeolite prepared in Production Example 2-1 was calcined at 600°C for 6 hours under air flow to obtain a calcined zeolite. The calcined zeolite obtained had a particle size of 1.0 μm or more and 10 μm or less, and an average primary particle size of 3.1 μm. The average thermal expansion coefficient of the calcined zeolite at 50 to 100°C was -9.0 ppm / K, the sphericity was 0.85, and the circularity was 0.845. Other physical properties were similar to those of the uncalcined zeolite.

[0149] Next, examples of the resin composition according to the second aspect of the present invention will be described. <Components> The components used in preparing the resin composition are as follows.

[0150] <Epoxy Resin> (A-2) p-Aminophenol Type Epoxy Resin: Mitsubishi Chemical Corporation, Product Name "jER630", Epoxy Equivalent: 97 g / equivalent <Curing Agent> (B-2) Acid Anhydride Curing Agent; Acid Anhydride (Main Component: Hydrogenated Methyl Nadic Anhydride): New Japan Chemical Co., Ltd., Product Name "RIKACID HNA-100" (Acid Anhydride Equivalent: 174-184) <Filler> (C-2) Zeolite Filler 2-1: Uncalcined zeolite, the zeolite produced in Production Example 2-1 described above, was used. The weight loss rate measured using a thermal analyzer (TGA Q5000IR, TA Instruments, Measurement Conditions: In air) was 22%. (D-2) Zeolite Filler 2-2: Calcined zeolite, the zeolite produced in Production Example 2-2 described above was used. The weight loss rate measured using a thermal analyzer (apparatus name: TGA Q5000IR, manufactured by TA Instruments, measurement conditions: in air) was 0.3%. (E-2) Silica filler: manufactured by Admatechs Co., Ltd., product name "SC4050-SX" (average particle size 1 μm) <Additives> (F-2) Additive: manufactured by BYK Japan, wetting and dispersing agent, product name "DISPERBYK-2152" (amino group-containing ultramolecular weight polyester, comb type, solvent-free)

[0151] Example 2-1 The filler, resin, curing agent, and additives shown in Table 2 were blended in the amounts shown in Table 2. A resin composition (liquid composition) was then prepared by mixing for 5 minutes at 1500 rpm using a vacuum mixer (EME Corporation, "V-mini 300"). The viscosity of this liquid composition was evaluated using the method described above. The results are shown in Table 2. Next, this liquid composition was poured into a mold and heated at 80°C for 2 hours, then heated at 120°C for 2 hours to cure to a gel fraction of 80% or more, and then demolded to obtain a cured product. The CTE and water absorption of this cured product were evaluated using the evaluation methods described above. The results are shown in Table 2.

[0152] Example 2-2 and Comparative Examples 2-1 to 2-5 In Example 2-1, a resin composition (liquid composition) and a cured product were obtained in the same manner as in Example 2-1, except that the components and amounts thereof were replaced with those shown in Table 2. The results of evaluation in the same manner as in Example 2-1 are shown in Table 2.

[0153]

[0154] The results of Examples 2-1 and 2-2 and Comparative Examples 2-4 and 2-5 demonstrate that using uncalcined zeolite as the zeolite results in a lower viscosity and lower water absorption rate compared to the case of using calcined zeolite, while maintaining the same CTE. According to the resin composition according to the second aspect of the present invention, it is possible to provide a resin composition that has a low coefficient of thermal expansion after curing, low moisture absorption, and low viscosity. Such a resin composition is suitable for use as a liquid sealant and is particularly useful as an underfill material.

[0155] 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 zeolite which, when heated in an air atmosphere at a heating rate of 10°C / min up to 800°C and held at 800°C for 10 minutes, has a weight loss at 800°C of 1% or more based on the weight at 400°C, a circularity of primary particles of 0.800 or more, and, when measured by volumetric particle size distribution, has a particle size distribution of 3 μm or more that accounts for 40% or less of the total.

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

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

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

5. A resin composition comprising the zeolite according to any one of claims 1 to 4 and a resin.

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

8. A liquid sealant comprising the resin composition according to claim 5.

9. An underfill material comprising the resin composition according to claim 5.

10. A method for producing a sealing material, comprising a step of filling a gap with the resin composition according to claim 5 and then curing the composition.

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

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