JP7831554B2 - Zeolite, resin composition, liquid encapsulant, underfill material, method for manufacturing encapsulant, and electronic device - Google Patents

Description

This invention relates to zeolites, resin compositions, liquid encapsulants, underfill materials, methods for producing encapsulants, and electronic devices.

Liquid sealants used as underfill materials are required to have excellent injectability, adhesion, curing properties, and storage stability, and to be void-free. Furthermore, the areas sealed with the liquid sealant must exhibit excellent moisture resistance, thermal cycling resistance, reflow resistance, crack resistance, and warping resistance. To satisfy these requirements, epoxy resin-based liquid sealants are widely used as underfill materials.

Furthermore, to improve the moisture resistance and thermal cycling resistance, particularly thermal cycling resistance, of the parts sealed with liquid encapsulants, it is known that using fillers made of inorganic substances such as silica fillers (hereinafter sometimes referred to as "inorganic fillers") in the liquid encapsulant allows for control of the difference in thermal expansion coefficients between the substrate made of organic materials such as epoxy resin and semiconductor elements, and to reinforce the bump electrodes (see Patent Document 1).

Japanese Patent Publication No. 2007-56070

Liquid sealants (resin compositions) using inorganic fillers such as silica fillers do not have sufficiently low thermal expansion coefficients, and further reductions in the thermal expansion coefficient are required from the viewpoint of thermal cycling resistance. While zeolites are known as inorganic fillers with low thermal expansion coefficients, liquid sealants containing zeolites tend to have high viscosity, reducing their injectability (gap penetration) when used as underfill materials. Therefore, it is difficult to obtain a liquid sealant with good injectability while simultaneously having a low thermal expansion coefficient in the cured product.

Furthermore, while zeolites are known to be highly hygroscopic, the presence of water can reduce the dielectric constant and reliability of electronic materials. Therefore, zeolites used in this application require low hygroscopicity.

Therefore, the 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, low viscosity, and good gap penetration properties.

As a result of diligent research into the above-mentioned problems, the inventors of this invention discovered that the above-mentioned problems could be solved by using a zeolite with a specific configuration, and thus completed the present invention.
The gist of this 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, shows a weight loss rate of 1% or more at 800°C relative to the weight at 400°C, a roundness of 0.800 or more of the primary particles, and 40% or less of the particles with a particle size of 3 μm or larger obtained by volume-based particle size distribution measurement.
[2] The zeolite described in [1] above, having d6r as CBU.
[3] The zeolite described in [1] or [2] above, having a structure of an oxygen ring of 8 members or less.
[4] A zeolite described in any one of [1] to [3] above, having a CHA-type structure.
[5] A resin composition containing the zeolite and resin described in any one of [1] to [4] above.
[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 encapsulant comprising the resin composition described in any one of [5] to [7] above.
[9] An underfill material comprising the resin composition described in any one of [5] to [7] above.
[10] A method for manufacturing a sealing material, comprising the step of filling a gap with the resin composition described in any one of [5] to [7] above, and then curing it.
[11] An electronic device comprising a sealing material obtained by the manufacturing method described in [10] above.

According to the present invention, it is possible to provide a zeolite for obtaining a resin composition that has low hygroscopicity and low thermal expansion coefficient after curing, as well as low viscosity and high gap penetration properties.

[Zeolite]
Zeolites typically refer to a group of crystalline materials composed of silicon or aluminum and oxygen, with a three-dimensional network framework and pores derived from this framework structure. This characteristic structure is used in adsorbents and catalysts. Therefore, organic substances, such as organic structure-regulating agents, incorporated into the pores during zeolite synthesis can clog the pores and reduce the zeolite's adsorption and catalytic capabilities; these are generally removed by calcination or other methods. However, the zeolite of the present invention (hereinafter sometimes referred to as "this zeolite") is characterized by containing organic substances, preferably components derived from organic structure-regulating agents which are raw materials for zeolites, within its pores. Methods for producing zeolites containing organic substances, preferably components derived from organic structure-regulating agents, within their pores are not limited to this, but include, for example, omitting or partially performing the calcination process that is normally carried out during the zeolite manufacturing process. A characteristic of zeolites containing organic matter, preferably components derived from organic structural regulators, within their pores is that, as determined by thermogravimetric analysis (TGA), 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, the weight loss rate at 800°C is 1% or more, relative to the weight at 400°C. Zeolites containing organic matter, preferably components derived from organic structural regulators, within their pores are expected to exhibit a larger weight loss rate compared to conventionally calcined zeolites (hereinafter sometimes referred to as "calcined zeolites") during heat treatment in the high-temperature range of 400°C to 800°C, due to the desorption of adsorbed water and organic matter, preferably organic structural regulators, present within the pores of the zeolite.
The resin composition of the present invention (hereinafter sometimes referred to as "this resin composition") described later uses a zeolite containing organic matter, preferably components derived from an organic structure-regulating agent, within its pores, thereby resulting in a cured product exhibiting low hygroscopicity. The mechanism by which such zeolite exhibits low hygroscopicity is presumed to be as follows: Zeolites exhibit adsorption properties to water and other substances because they have a porous structure and possess acid sites, which are adsorption sites. The presence of organic matter, preferably components derived from an organic structure-regulating agent, within these pores prevents the zeolite from becoming completely porous, thereby reducing its adsorption properties to water and other substances, and consequently reducing its hygroscopicity. From the above perspective, the zeolite, 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, by thermogravimetric analysis (TGA), has a weight loss rate at 800°C (hereinafter sometimes simply referred to as "weight loss rate") of 1% or more, preferably 2% or more, and more preferably 3% or more, relative to the weight at 400°C. The weight loss rate may also be 5% or more, 10% or more, or 20% or more. There are no particular restrictions on the upper limit as long as the effects of the present invention are achieved, but for example, it may be 50% or less.

(Zeolite particle size distribution)
This zeolite is characterized in that, in its volume-based particle size distribution, 40% or less of the particles have a particle size of 3 μm or larger. Having 40% or less of particles with a particle size of 3 μm or larger in its volume-based particle size distribution allows the resin composition to be sufficiently filled even in narrow gaps. From this viewpoint, it is preferable that, in its volume-based particle size distribution, 40% or less of particles with a particle size of 3 μm or larger are present, more preferably 30% or less, even more preferably 20% or less, particularly preferably 10% or less, and most preferably 5% or less. Furthermore, the lower limit of particles with a particle size of 3 μm or larger in its volume-based particle size distribution is not particularly limited; it should be 0% or more.
The volume-based particle size distribution of this zeolite is obtained by measuring it using the laser diffraction scattering particle size distribution method. Specifically, it can be measured by the method described in the examples. Methods to satisfy the above particle size distribution include performing a classification treatment after hydrothermal synthesis, and adding seed crystals or alkali metals in arbitrary proportions during hydrothermal synthesis. These steps may be used individually or in combination.

(Zeolite particle size)
When adding zeolite to a resin, a larger particle size is preferable in that it does not easily increase the viscosity. Specifically, a particle size of 0.1 μm or larger is preferable, 0.2 μm or larger is more preferable, 0.3 μm or larger is even preferable, 0.4 μm or larger is preferable, 0.5 μm or larger is preferable, 0.6 μm or larger is preferable, 0.7 μm or larger is preferable, 0.8 μm or larger is particularly preferable, 0.9 μm or larger is especially preferable, and 1.0 μm or larger is most preferable. On the other hand, a smaller particle size is preferable in that it is easier to uniformly mix with other components such as resin and the surface smoothness is easier to achieve. Specifically, a particle size of 3.0 μm or less is preferred, 2.95 μm or less is more preferred, 2.9 μm or less is even more preferred, 2.8 μm or less is preferred, 2.7 μm or less is preferred, 2.5 μm or less is preferred, 2.4 μm or less is preferred, 2.3 μm or less is particularly preferred, 2.2 μm or less is particularly preferred, 2.1 μm or less is especially preferred, and 2.0 μm or less is most preferred.
The particle size of this zeolite refers to the median diameter obtained from the volume-based particle size distribution, which is obtained by measuring the particle size distribution using the laser diffraction scattering method.
Furthermore, this zeolite may be formed by the aggregation of multiple zeolite particles to create secondary particles, but in this case, the particle size of the zeolite is the same as the particle size of the primary particles.

(Structure of zeolite)
Zeolites are compounds composed of silicon or aluminum and oxygen, with _TO4 units (T elements being elements other than oxygen that make up the skeleton) as their basic units. Specifically, zeolites include crystalline porous aluminosilicates, crystalline porous aluminophosphates (ALPO), and crystalline porous silicoaluminophosphates (SAPO). While any of the above structures is acceptable for the zeolite, aluminosilicate is preferred.
Zeolites are composed of structural units called Composite Building Units (hereinafter sometimes referred to as "CBUs"), which are made up of several (several to several dozen) TO ₄ units linked together. As a result, they have regular channels (tubular pores) and cavities.
The crystal structure of this CBU and the zeolite described later can be indicated by the code that defines the structure of zeolites as defined by the International Zeolite Association (IZA). The structure of the zeolite can be determined based on the X-ray diffraction pattern obtained by an X-ray structural analyzer (for example, a BRUKER D2PHASER desktop X-ray diffractometer) using the 2018 Zeolite Structure Database (http://www.iza-structure.org/databases/).

(Zeolite skeleton)
The zeolite skeleton preferably has d6r as the CBU. Having d6r makes it easier to obtain a resin composition with a low coefficient of thermal expansion after curing.
Examples of zeolites containing d6r as CBU include AEI, AFT, AFV, AFX, AVL, CHA, EAB, EMT, ERI, FAU, GME, JSR, KFI, LEV, LTL, LTN, MOZ, MSO, MWW, OFF, SAS, SAT, SAV, SBS, SBT, SFW, SSF, SZR, TSC, and zeolites with a -WEN type structure.
Of these, zeolites with an oxygen ring of 8 members or less are particularly preferred from the viewpoint that water molecules do not easily penetrate into the pores. Examples of zeolites with an oxygen ring of 8 members or less include AEI, AFT, AFX, CHA, ERI, KFI, SAT, SAV, SFW, and TSC type zeolites. Among these, AEI, AFX, CHA, and ERI type zeolites are particularly preferred because their structure remains stable even when their shape is controlled, and CHA type zeolites are the most preferred. In this specification, an oxygen ring of 8 members refers to a structure in which the number of oxygen elements is 8 in the pores composed of oxygen and T elements (elements other than oxygen that constitute the skeleton), where the number of oxygen elements is highest.
Furthermore, the above-mentioned zeolite may be used individually or in combination of two or more types.

(Average thermal expansion coefficient of zeolite)
The average thermal expansion coefficient of this zeolite is preferably low because it is easy to reduce the average thermal expansion coefficient of the liquid composition described later with a small amount. It is also preferable that the various physical properties of the resin do not change easily due to the addition of zeolite because only a small amount is used. In particular, it is preferable that the viscosity increase of the liquid composition described later is suppressed. Specifically, the average thermal expansion coefficient of the zeolite is usually less than 0 ppm/K, preferably -2 ppm/K or less, more preferably -3 ppm/K or less, even more preferably -4 ppm/K or less, and particularly preferably -5 ppm/K or less.

On the other hand, considering that the zeolite will be used as a liquid composition containing zeolite and resin, as described later, it is preferable that the average thermal expansion coefficient of the zeolite be high, as this reduces the difference with the average thermal expansion coefficient of the resin and makes it difficult for the zeolite and resin to separate. Therefore, the average thermal expansion coefficient of the zeolite is usually -1000 ppm/K or higher, preferably -900 ppm/K or higher, more preferably -800 ppm/K or higher, even more preferably -700 ppm/K or higher, particularly preferably -500 ppm/K or higher, and most preferably -300 ppm/K or higher. In particular, when used as a sealing material, a high coefficient is preferable, specifically, usually -100 ppm/K or higher, preferably -50 ppm/K or higher, more preferably -40 ppm/K or higher, even more preferably -30 ppm/K or higher, particularly preferably -25 ppm/K or higher, and most preferably -20 ppm/K or higher.
The average thermal expansion coefficient of zeolite can be measured by calculating the lattice constant using a BRUKER D8 ADVANCE X-ray diffractometer and JADE X-ray diffraction analysis software. To eliminate the effects of water desorption, the zeolite is typically measured in a dry state.
The average thermal expansion coefficient of zeolite is typically measured in the range of 50 to 100°C. Specifically, it represents the displacement of the lattice constant per degree Celsius, calculated by comparing the average lattice constant at 50°C with the average lattice constant at 100°C. Here, the average lattice constant at each temperature is the average of the lattice constants along the a, b, and c axes. The measurement of the average thermal expansion coefficient is performed by gradually increasing the temperature after waiting for the lattice constant to stabilize.

Resins generally exhibit a high coefficient of thermal expansion at high temperatures. Therefore, it is preferable that the average coefficient of thermal expansion of zeolite be low, especially when heated to high temperatures. Specifically, the average coefficient of thermal expansion (high temperature range) in the 50-350°C range 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 coefficient of thermal expansion (high temperature range) of zeolite is a value representing the displacement of the lattice constant per degree Celsius, calculated from the average lattice constant at 50°C and the average lattice constant at 350°C when the zeolite is heated.

(Zeolite shape)
The zeolite is preferably spherical. The spherical shape of the zeolite helps to suppress an increase in the viscosity of the resin composition containing the zeolite. Specifically, the primary particles have the following degree of roundness.
A "primary particle" refers to a unit particle that does not contain grain boundaries within its structure. Furthermore, primary particles can be identified through observation using a scanning electron microscope (SEM).

<<Roundness>>
The roundness of the primary particles of this zeolite is 0.800 or higher, preferably 0.810 or higher, more preferably 0.820 or higher, even more preferably 0.830 or higher, and particularly preferably 0.835 or higher. Furthermore, there is no particular upper limit to the roundness of the primary particles, and it is sufficient if it is 1 or less. For reference, the roundness of the cubic shape, which is common in zeolites, is 0.785.
In this specification, "roundness" is defined as "4 × π × area / (circumference) ^² ". The area and circumference can be determined by observation using a scanning electron microscope (SEM). In this specification, "roundness" is the average value of 100 particles obtained by scanning electron microscopy (SEM).
Methods for achieving the above-mentioned range of roundness of the primary particles of this zeolite include performing classification after hydrothermal synthesis, and adding seed crystals, amino acids, surfactants, or organic structure-regulating agents in arbitrary proportions during hydrothermal synthesis.

(Zeolite framework density)
The framework density of the zeolite is not particularly limited, as long as the effects of the present invention are not impaired. A low framework density of the zeolite is preferable because it makes the zeolite more susceptible to structural vibration and tends to result in a lower average coefficient of thermal expansion. Therefore, the framework density of the zeolite is preferably 17.0 T/1000 ^ų or less, and more preferably 16.0 T/1000 ^ų or less.
On the other hand, a high framework density of zeolite is preferable because it tends to increase the structural stability of the zeolite. The framework density of zeolite is preferably 12.0 T/1000 ^ų or higher, more preferably 13.0 T/1000 ^ų or higher, and even more preferably 14.0 T/1000 ^ų or higher. When the framework density is within the above range, zeolite can be used as a stable filler.
Framework density refers to the number of T atoms present per unit volume of zeolite, and is a value determined by the structure of the zeolite. In this specification, the values listed in the IZA Zeolite Structure Database 2017 edition (http://www.iza-structure.org/databases/) may be used.

Examples of zeolites with a framework density greater than 16.0 T/1000 ^ų and less than or equal to 17.0 T/1000 ^ų include ERI, LTL, LTN, MOZ, OFF, SAT, SSF, and -WEN type zeolites.
Examples of zeolites with a framework density greater than 15.0 T/1000 ^ų and less than or equal to 16.0 T/1000 ^ų include AEI, AFT, AFV, AFX, AVL, EAB, GME, LEV, MWW, and SFW type zeolites.
Examples of zeolites with a framework density greater than 14.0 T/1000 ^ų and less than or equal to 15.0 T/1000 ^ų include CHA, KFI, SAS, and SAV-type zeolites.
Examples of zeolites with a framework density in the range of 14.0 T/1000 ^ų or less include EMT, FAU, JSR, SBS, SBT, and zeolites with TSC-type structures.

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

Furthermore, if elements such as gallium, iron, boron, titanium, zirconium, tin, zinc, or phosphorus are used instead of silicon or aluminum, the molar ratio of the oxide of the substituted element should be converted to the molar ratio of alumina or silica. Specifically, if gallium is used instead of aluminum, the molar ratio of gallium oxide should be converted to the molar ratio of alumina.

(Silica/alumina molar ratio (SAR) of zeolite)
The silica/alumina molar ratio of this zeolite (hereinafter sometimes referred to as "SAR", "Si/ _Al2 molar ratio", or "Si/ _Al2 ratio") is not particularly limited as long as the effects of the present invention are not impaired. A high SAR (Si/ _Al2 ratio) of the zeolite is preferable in that it improves the moisture resistance of the cured product and makes it easier to control the amount of countercations. Therefore, the SAR (Si/ _Al2 ratio) of the zeolite is usually 2 or more, preferably 5 or more, more preferably 10 or more, even more preferably 14 or more, among many more preferably 18 or more, among many more preferably 20 or more, among many more preferably 22 or more, among many more preferably 23 or more, among many more preferably 23.5 or more, particularly preferably 24 or more, especially preferably 24.5 or more, and most preferably 25 or more.
On the other hand, a low SAR (Si/ _Al2 ratio) of zeolite is preferable in terms of ease of inexpensive production. Therefore, the SAR (Si/ _Al2 ratio) of zeolite is usually 2000 or less, preferably 1000 or less, more preferably 500 or less, even more preferably 100 or less, most preferably 50 or less, most preferably 47.5 or less, most preferably 45 or less, most preferably 42.5 or less, most preferably 40 or less, most preferably 39 or less, most preferably 38 or less, particularly preferably 37 or less, especially preferably 36 or less, and most preferably 35 or less. When the Si/ _Al2 ratio is within the above range, it is easy to control the amount of countercations, and the manufacturing cost of the zeolite is also kept low.
The Si/ _Al2 ratio of zeolite can be adjusted by the type and ratio of silicon-containing and aluminum-containing compounds used as raw materials, the type and amount of structure-regulating agent, the use of seed crystals, and synthesis conditions such as temperature and time.

(Zeolite countercations)
The countercation of the zeolite is not particularly limited as long as it does not impair the effects of the present invention. The countercation of the zeolite is usually a component derived from an organic structure-regulating agent, a proton, an alkali metal ion, or an alkaline earth metal ion. Preferably, it is a component derived from an organic structure-regulating agent, a proton, or an alkali metal ion; more preferably, it is a component derived from an organic structure-regulating agent, a proton, a Li ion, a Na ion, or a K ion; and even more preferably, it is a component derived from an organic structure-regulating agent. When it is an alkali metal ion or an alkaline earth metal ion, the smaller its size, the more likely the zeolite is to exhibit an average thermal expansion coefficient of less than 0 ppm/K, which is preferable. When it is a component derived from an organic structure-regulating agent, it is preferable because it is more flexible than alkali metal ions or alkaline earth metal ions, which is preferable because the zeolite is more likely to exhibit an average thermal expansion coefficient of less than 0 ppm/K.
In other words, the zeolite is preferably a component type derived from an organic structure-determining agent (hereinafter sometimes referred to as "as-made"), a proton type, or an alkali metal type, more preferably as-made, a proton type, a Li type, a Na type, or a K type, and even more preferably as-made.

(Zeolite crystallinity)
The crystallinity of this zeolite is not particularly limited, as long as the effects of the present invention are not impaired. This is because the Composite Building Unit (CBU) is presumed to be a more influential factor than the structure defined by the code in IZA, due to its greater influence on the average thermal expansion coefficient of the cured product. The crystallinity of the zeolite can be determined by comparing it with the X-ray diffraction peak of the zeolite, using a reference X-ray diffraction peak obtained with an X-ray diffractometer (for example, a BRUKER D2PHASER desktop X-ray diffractometer). A specific example of calculation is the crystallinity of the LTA-type zeolite described in Scientific Reports 2016, 6, Article number: 29210.

(Surface treatment of zeolite)
This zeolite may be subjected to surface treatments such as silylation treatment or fluorination treatment, to the extent that the effects of the present invention are not impaired. Such surface treatments may be physical or chemical treatments.

(Zeolite content)
From the viewpoint of lowering the thermal expansion coefficient of the resin composition, the content of the zeolite in the resin composition is preferably 40% by mass or more, more preferably 45% by mass or more, and even more preferably 50% by mass or more, based on the total amount of the resin composition. On the other hand, from the viewpoint of suppressing the increase in viscosity of the resin composition, the content of the zeolite in the resin composition is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, based on the total amount of the resin composition.

<Inorganic fillers other than zeolite>
This resin composition may contain inorganic fillers other than the zeolite (hereinafter sometimes referred to as "other inorganic fillers"). The other inorganic fillers are not particularly limited as long as they do not impair the effects of the present invention, and examples 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, fullerene, and diamond. Examples of metal carbides include silicon carbide, titanium carbide, and tungsten carbide. Examples of metal oxides include magnesium oxide, aluminum oxide (alumina), silicon oxide such as silica, calcium oxide, zinc oxide, yttrium oxide, zirconium oxide, cerium oxide, ytterbium oxide, and SiAlON (ceramics composed of silicon, aluminum, oxygen, and nitrogen). Examples of metal nitrides include boron nitride, aluminum nitride, and silicon nitride.
Of these inorganic fillers, silica is preferred from the viewpoint of being able to reduce the viscosity of the resin composition.

The average particle size of the other inorganic fillers is not particularly limited as long as it is within the range that achieves the effects of the present invention, but it is preferably in the range of 0.1 μm to 5 μm. If it is above the lower limit, the viscosity of the resin composition can be reduced, and if it is below the upper limit, the filling ability into narrow gaps is good. From these viewpoints, the average particle size of the other inorganic fillers 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.

The content of this zeolite in the total inorganic filler is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, in order to fully exhibit the effect of this zeolite, i.e., low CTE.

<Total amount of inorganic filler>
The total content of all inorganic fillers (total inorganic fillers) in this resin composition is preferably high in terms of how easily the filler effect is exhibited. On the other hand, if the resin composition is liquid at room temperature, it is preferable that the total content be low in terms of high fluidity and ease of filling into narrow spaces. Specifically, the total content of all inorganic fillers is preferably 40% by mass or more, more preferably 45% by mass or more, and even more preferably 50% by mass or more, based on the total amount of the resin composition. On the other hand, it is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

<Dispersant>
This resin composition may contain a dispersant to enhance the dispersibility of inorganic fillers such as this zeolite. The dispersant contained in the liquid composition containing the resin and filler is mainly added to the liquid composition containing the resin and filler, which have a large difference in polarity, to improve the interface between the two and improve compatibility. This can be effective in reducing viscosity, improving the dispersibility of the filler, and preventing filler aggregation and sedimentation.

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 as the dispersant. There are no particular restrictions on the main chain skeleton of the polymeric dispersant, but examples include polyurethane skeleton, polyacrylic skeleton, polyester skeleton, polyamide skeleton, polyimide skeleton, and polyurea skeleton, with polyurethane skeleton, polyacrylic skeleton, and polyester skeleton being preferred in terms of storage stability. There are also no particular restrictions on the structure of the polymeric dispersant, but examples include random structure, block structure, comb structure, and star structure, with block structure or comb structure being preferred in terms of storage stability.
Furthermore, the dispersant is preferably a solvent-free type dispersant, particularly a solvent-free polymer dispersant. By not using a solvent, it is possible to prevent the dispersant from volatilizing and creating voids when the resin composition is heat-cured.
Commercially available dispersants can be used. Examples of commercially available dispersants include the following, and any dispersant having at least one of the functional groups of an amino group and/or an amine salt should be used.

Commercially available polymer-based dispersants include the DISPERBYK series of wetting dispersants from BIC-Chemie, specifically numbers 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, and 1. 83, 184, 185, 2000, 2001, 2008, 2020, 2050, 2070, 2096, 2150, 2152, 2155, and the EFKA series models 4008, 4009, 4010, 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4340, all commercially available from BASF Japan. 4400, 4401, 4402, 4403, 4406, 4800, 5010, 5044, 5054, 5055, 5063, 5064, 5065, 5066, 5070, 5244, and the Solsperse series 3000, 5000, 11200, 13240, 13650, 13940, 16000, 17000, which are commercially available from Lubrizol. , 18000, 20000, 21000, 24000SC, 24000GR, 26000, 28000, 31845, 32000, 32500, 32550, 32600, 3 3000, 34750, 35100, 35200, 36000, 36600, 37500, 38500, 39000, 53095, 54000, 55000, 56000, 71 000, Commercially available DISPARLON series from Kusumoto Kasei Co., Ltd.: 1210, 1220, 1831, 1850, 1860, 2100, 2150, 2200, 7004, KS-260, KS-273N, KS-860, KS-873N, PW-36, DN-900, DA-234, DA-325, DA-375, DA-550, DA-1200 DA-1401, DA-7301, PB-711, PB-821, PB-822, PN-411, PA-111 from the Ajisper series sold by Ajinomoto Co., Inc., and 104A, 104C, 104E, 104H, 104S, 104BC, 104DPM, 104PA, 104PG from the Surfinol series sold by Air Products Inc. Examples include 50, 420, 440, DF110D, DF110L, DF37, DF58, DF75, DF210, CT111, CT121, CT131, CT136, GA, TG, TGE, STG and E1004 from the Orphine series (commercially available from Nisshin Chemical Industry Co., Ltd.), 70, 2120, and 2190 from the SN Sparse series (manufactured by Sannopco Co., Ltd.), the Adekacol and Adekatol series (commercially available from ADEKA Corporation), and the Sannonic series, Naroacty CL series, Emulmin series, Newpol PE series, Ionet M series, Ionet D series, Ionet S series, Ionet T series, and Sansepara 100 (commercially available from Sanyo Chemical Industries, Ltd.).

The dispersant content is preferably high in order to facilitate uniform dispersion of inorganic fillers in the liquid composition. On the other hand, the dispersant content is preferably low in order to prevent an increase in the coefficient of thermal expansion due to phase separation between the inorganic filler and the resin such as epoxy resin. Therefore, in order to facilitate filling of the liquid composition into a narrow space and to achieve a low coefficient of thermal expansion after curing, the dispersant content 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.

<Method for manufacturing zeolite>
A known method can be applied to the manufacturing method of zeolite. For example, when manufacturing CHA-type zeolite, the method described in Japanese Patent Application Publication No. 2009-097856 can be used.
More specifically, an aqueous gel is prepared by mixing aluminum atom raw materials, silica atom raw materials, and organic structure-regulating agents. Typically, the mixing order is to mix the aluminum atom raw materials with water, and then mix in the silica atom raw materials and organic structure-regulating agents. Next, the prepared aqueous gel is subjected to hydrothermal synthesis, the product is separated, and any adhering raw material-derived components are removed by methods such as washing with water and drying to obtain a zeolite.

The particularly preferred zeolite described above can be produced by the following method (hereinafter sometimes referred to as "this manufacturing method").
This manufacturing method includes a step of hydrothermally synthesizing a raw material composition containing silicon atom raw materials, aluminum atom raw materials, an organic structure-regulating agent, and water. Furthermore, in this manufacturing method, as described above, it is preferable not to perform the usual calcination treatment, or to perform partial calcination as long as the zeolite after calcination treatment achieves the aforementioned weight loss rate of 1% or more. When partial calcination is performed, the calcination conditions described below are preferred.
In this manufacturing method, partial firing can be performed as described above, but it is preferable not to perform the firing treatment. In other words, it is preferable that the zeolite is not fired (unfired). By not performing the firing treatment, it is easier to achieve a weight loss rate of 1% or more, and consequently, it is possible to easily manufacture a zeolite for obtaining a resin composition that has low moisture absorption, a low coefficient of thermal expansion after curing, low viscosity, and good gap penetration properties.
Furthermore, if necessary, a preferred zeolite (hereinafter sometimes referred to as "seed crystal zeolite") may be used.

<<Silicon Atom Raw Materials>>
The silicon atom raw material 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 individually or in any combination and ratio of two or more types.

<<Aluminum atomic raw material>>
For the aluminum atom raw material, it is preferable to use a water-soluble raw material. Furthermore, aluminum hydroxide is preferred because it has a low alkali metal content.

<<Organic matter>>
As mentioned above, this zeolite contains organic matter within its pores.
The organic substance is not particularly limited as long as it does not impair the effects of the present invention, and examples include amines, amino acids, fatty acids, surfactants, polymers, and organic structure modifiers. 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 modifiers include those described later. Among these, organic structure modifiers are preferred because they fill the spaces within the zeolite skeleton, inhibiting the diffusion of water vapor into the pores and reducing hygroscopicity. In other words, it is preferable that the zeolite contains components derived from organic structure modifiers as organic substances.
When using organic materials, one type may be used alone, or two or more types may be used in any combination and ratio.

<<Organic structure directing agent>>
Various known substances can be used as organic structure-determining agents, such as tetramethylammonium hydroxide (TMAOH), tetraethylammonium hydroxide (TEAOH), tetrapropylammonium hydroxide (TPAOH), and N,N,N-trimethyl-1-adamantylammonium hydroxide (TMAdaOH). Of these, N,N,N-trimethyl-1-adamantylammonium hydroxide (TMAdaOH) is preferred from the viewpoint of easily retaining organic matter in the pores of the zeolite in the range of room temperature to 200°C and reducing the hygroscopicity of the zeolite. These can be used individually or in any combination and ratio of two or more.
The amount of organic structure-determining 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 molar ratio to silicon (Si) contained in the raw material composition. On the other hand, it is typically 1 or less, preferably 0.6 or less, more preferably 0.55 or less, even more preferably 0.5 or less, particularly preferably 0.45 or less, and most preferably 0.4 or less. It is believed that using within this range facilitates the growth of high-purity spherical zeolites with fewer by-products.

<<Water>>
When using seed crystal zeolite, as described later, the amount of water used should, from the viewpoint of facilitating crystal formation, be 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 of water to silicon (Si) contained in the raw material composition other than the seed crystal zeolite. Keeping it within this range is preferable as it facilitates crystal formation. Furthermore, when hydrothermally synthesizing zeolite under conditions where the raw material concentration is diluted by increasing the amount of water, it is easier to obtain zeolite with a large particle size. In addition, in terms of easily obtaining cost reduction effects for wastewater treatment, the molar ratio to silicon (Si) should typically be 50 or less, preferably 40 or less, more preferably 30 or less, and even more preferably 25 or less.

<<Alkali Metal Atom Raw Materials>>
Alkali metal atom raw materials may be used in the production of zeolites. When alkali metal atom raw materials are used, the alkali metal atoms are not particularly limited, and known alkali metals used in zeolite synthesis can be used, but at least one alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium is preferred. Multiple types of alkali metal atoms may also be used.

<<Seed crystal zeolite>>
In this manufacturing method, a seed crystal zeolite may be used. If a seed crystal zeolite is used, one type may be used alone, or two or more types may be used in any combination and ratio.

<<Mixing of raw materials (preparation of raw material composition before reaction)>>
The raw material composition can usually be obtained by mixing silicon atom raw materials, aluminum atom raw materials, an organic structure-regulating agent, and water, and then adding seed crystal zeolite if used.
In addition to the components mentioned above, other components such as acidic components to promote the reaction and metal stabilizers such as polyamines may be added as needed at any stage in the production of zeolite.

<<Aging>>
The raw material composition prepared as described above may be hydrothermally synthesized immediately after preparation, but in order to obtain a zeolite with higher crystallinity, it is preferable to age it for a certain period of time under predetermined temperature conditions. In particular when scaling up the reaction, it is preferable to age the raw materials while stirring them for a certain period of time, as this improves agitation and makes it easier to make the raw materials more uniform. The temperature during aging is usually 100°C or lower, preferably 95°C or lower, and more preferably 90°C or lower, and there is no particular lower limit, but the temperature during aging is usually 0°C or higher, preferably 10°C or higher. The aging temperature may be constant during aging, or it may be changed in stages or continuously. The aging time is not particularly limited, but is usually 2 hours or more, preferably 3 hours or more, and more preferably 5 hours or more, and on the other hand, is usually 30 days or less, preferably 10 days or less, and more preferably 4 days or less.

<<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 the aqueous gel obtained by maturing it, into a pressure-resistant container and maintaining a predetermined temperature under self-generated pressure or under gas pressure that does not inhibit crystallization, while stirring, rotating or oscillating the container, or while remaining still.
The reaction temperature during hydrothermal synthesis is usually 120°C or higher to increase the reaction rate, preferably 130°C or higher, more preferably 140°C or higher, and even more preferably 150°C or higher. On the other hand, it is usually 230°C or lower, preferably 220°C or lower, more preferably 200°C or lower, and even more preferably 190°C or lower. The reaction time is not particularly limited, but is usually 2 hours or more, preferably 3 hours or more, and more preferably 5 hours or more, and on the other hand, it is usually 30 days or less, preferably 10 days or less, more preferably 7 days or less, and even more preferably 5 days or less. The reaction temperature may be constant during the reaction, or it may be changed stepwise or continuously.

<<Drying process>>
After hydrothermal synthesis, the zeolite is separated from the resulting composition (hydrothermal synthesis reaction solution). While the separation method is not particularly limited, it is usually separated by washing with water followed by filtration, decantation, or direct drying. Even when separated by filtration or decantation, it is usually dried afterward.
The drying conditions are not particularly limited; for example, the drying temperature is preferably 50°C to 200°C, and more preferably 70°C to 150°C. The atmosphere during drying is not particularly limited, but it may be carried out in air or under an inert gas atmosphere such as nitrogen or argon.

<<Firing>>
The dried zeolite may be subjected to calcination or other processes to remove organic structural modifiers used during production in any proportion, to the extent that it contains organic matter, preferably components derived from organic structural modifiers, within its pores. By using a zeolite containing organic matter, preferably components derived from organic structural modifiers, within its pores in this resin composition, a resin composition that provides a cured product with low CTE and low hygroscopicity can be provided.
When firing is performed, the firing temperature is usually preferably 200 to 1000°C. Firing at 300°C or higher can remove organic structural regulators, while firing at 1000°C or lower does not impair the physical properties of the zeolite. From this viewpoint, the firing temperature is preferably 300°C or higher, more preferably 350°C or higher, even more preferably 400°C or higher, preferably 900°C or lower, more preferably 800°C or lower, and even more preferably 700°C or lower.
There are no particular limitations on the firing atmosphere; it may be carried out in air or under an inert gas atmosphere such as nitrogen or argon.
The calcination method is not particularly limited, and muffle furnaces, kilns, fluidized bed furnaces, etc., can be used, but the method of calcining by circulating the above-mentioned gas is preferable. The gas flow rate is not particularly limited, but the gas flow rate per gram of powder is usually preferably in the range of 0.1 ml/min to 100 ml/min, and more preferably calcined under a gas flow rate of 5 ml/min to 20 ml/min.

[Resin composition]
This resin composition contains zeolite and resin. This resin composition is preferably liquid at room temperature, and when this resin composition is liquid at room temperature (hereinafter sometimes referred to as "liquid composition"), it is preferably used as a liquid encapsulant and is particularly suitable as an underfill material.
The following details each constituent element, but when it is assumed that the resin composition is liquid at room temperature, it should be read as a liquid composition.
In this specification, "liquid at room temperature" means having fluidity between 10°C and 35°C.

<Resin>
The resin in this resin composition is not particularly limited as long as it achieves the effects of the present invention, and examples include thermosetting resins and thermoplastic resins. In particular, when considering liquid encapsulants such as underfill materials, it is preferable to include a thermosetting resin.

<<Thermosetting resin>>
The resin composition preferably contains a thermosetting resin. The thermosetting resin is not particularly limited and examples include epoxy resins, polyimide resins, maleimide resins, polyamide resins, phenolic resins, vinyl ester resins, unsaturated polyester resins, melamine resins, and the like. Of these thermosetting resins, the present invention preferably contains at least one selected from the group consisting of epoxy resins and polyimide resins, and more preferably contains an epoxy resin.

(Epoxy resin)
In the present invention, epoxy resins that can be used are preferably epoxy compounds having aromatic rings, such as bisphenol A type skeletons, bisphenol F type skeletons, and biphenyl skeletons, as these tend to have a low coefficient of thermal expansion after curing. Specifically, examples include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins, naphthalene ring-containing epoxy resins, epoxy resins having a dicyclopentadiene skeleton, phenol novolac type resins, cresol novolac type epoxy resins, triphenylmethane type epoxy resins, aminophenol type epoxy resins, aliphatic epoxy resins, and copolymer epoxy resins of aliphatic epoxy resins and aromatic epoxy resins. Among these, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins, and naphthalene ring-containing epoxy resins are preferred, and more preferably, bisphenol A type epoxy resins, bisphenol F type epoxy resins, naphthalene ring-containing epoxy resins, aminophenol type epoxy resins, and biphenyl type epoxy resins are used.

Furthermore, in this resin composition, it is preferable to use a polyfunctional epoxy resin because it tends to have a high glass transition temperature after thermal curing. Preferred polyfunctional epoxy resins include various phenols such as phenol novolac resins, cresol novolac resins, bisphenol A novolac resins, dicyclopentadienephenol resins, phenol aralkyl resins, naphthol novolac resins, biphenyl novolac resins, terpene phenol resins, and heavy oil-modified phenol resins, as well as glycidyl ether-type polyfunctional epoxy resins, such as epoxy resins produced from various phenol compounds (including polyhydric phenol resins obtained by condensation reactions of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, and glyoxal) and epihalohydrins.

Furthermore, from the viewpoint of fluidity, the epoxy resin preferably has a viscosity of 5 Pa·s or less at 23°C, and more preferably 0.1 to 3 Pa·s. The viscosity measurement method for 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 this invention at 23°C should 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.

From the viewpoint of viscosity control, the epoxy resin preferably has an epoxy equivalent of 50 g/equivalent to 500 g/equivalent, and more preferably 90 g/equivalent to 150 g/equivalent. 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 lowering the melting point and viscosity of the epoxy resin, which results in good filling properties of the resin composition and easier bonding through filling.
Epoxy resin may be used alone or mixed in any combination and ratio of two or more types, but in the case of a mixture, the epoxy equivalent shall be the equivalent of the mixture.

The epoxy resin content in this resin composition is preferably low because it allows for a relatively high content of inorganic fillers such as zeolite, which tends to lower the coefficient of thermal expansion. On the other hand, a high epoxy resin content is preferable because it helps maintain the excellent physical properties of the epoxy resin. Therefore, from the viewpoint of achieving both the maintenance of the resin's excellent physical properties and the heat resistance (resistance to thermal expansion) of the cured resin composition, it is preferably 5% by mass or more, and more preferably 10% by mass or more, relative to the total amount of the resin composition. Conversely, it is preferably 50% by mass or less, more preferably 35% by mass or less, and even more preferably 20% by mass or less.

(Hardening agent)
The resin composition preferably further contains a curing agent. A curing agent is a substance that contributes to the crosslinking reaction between crosslinking groups of a resin, particularly preferably an epoxy resin.
There are no particular restrictions on the curing agent; generally, resin curing agents, especially epoxy resin curing agents, can be used. Examples include phenolic curing agents, amine curing agents such as aliphatic amines, polyetheramines, alicyclic amines, and aromatic amines, acid anhydride curing agents, amide curing agents, tertiary amines, imidazoles and their derivatives, organophosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halogenated amine complexes, polymercaptan curing agents, isocyanate curing agents, blocked isocyanate curing agents, and dicyandiamine compounds. From the viewpoint of imparting fluidity and rapid curing, acid anhydride curing agents are preferred as the curing agent.

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, allyl or polyallylized derivatives of the above dihydroxynaphthalenes, allylated bisphenol A, allylated bisphenol F, allylated phenol novolac, allylated pyrogallol, and the like.

Specific examples of amine-based curing agents include aliphatic amines such as ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, and tetra(hydroxyethyl)ethylenediamine.
Examples of polyetheramines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propylamine), polyoxypropylenediamine, and polyoxypropylene triamines.
Examples of alicyclic amines include isophoronediamine, metacenediamine, 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-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylethane, 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.

Specific examples of acid anhydride-based curing agents include dodecenyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyl octadecanediic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenedicarboxylic acid anhydride, methylcyclohexenetetracarboxylic acid anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarbone. Examples include acid anhydrides, ethylene glycol bistrimellitate dianhydrides, hetic anhydrides, nadic anhydrides, methylnadic anhydrides, hydrogenated nadic acid, hydrogenated methylnadic 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-naphthalene succinic acid dianhydride, and 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride.

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.
Imidazoles and their 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 midazolyl-(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 isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resins with the above imidazoles or polymer-encapsulated imidazoles.

Examples of organophosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine. Examples of phosphonium salts include tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, and tetrabutylphosphonium tetrabutylborate. Examples of tetraphenylboron salts include 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate.
These hardening agents may be used individually, or two or more may be mixed in any combination and ratio.

When this resin composition contains a curing agent, the curing agent content is preferably such that the effect of unreacted epoxy groups or residual functional groups of the curing agent is minimized. Therefore, when the curing agent is a phenolic, amine, or acid anhydride-based curing agent, the equivalent ratio of epoxy groups in the epoxy resin to 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 an amide-based curing agent, tertiary amine, imidazole and its derivatives, organophosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron-halogenated amine complexes, polymercaptan-based curing agents, isocyanate-based curing agents, blocked isocyanate-based curing agents, etc., it is preferable to use 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more, per 100 parts by mass of epoxy resin. On the other hand, it is preferable to use 20 parts by mass or less, and more preferably 15 parts by mass or less.
In the case of dicyandiamine compounds, it is preferable to use 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more, per 100 parts by mass of epoxy resin. On the other hand, it is preferable to use 10 parts by mass or less, and more preferably 6 parts by mass or less.

<Reactive Diluent>
If the resin composition is in liquid form, it may contain a reactive diluent. The reactive diluent is not particularly limited as long as it contains at least one monofunctional epoxy compound. A monofunctional epoxy compound is an epoxy compound having one epoxy group and has been conventionally used as a reactive diluent to adjust the viscosity of epoxy resin compositions. Monofunctional epoxy compounds are broadly classified into aliphatic monofunctional epoxy compounds and aromatic monofunctional epoxy compounds, and from the viewpoint of viscosity, aromatic monofunctional epoxy compounds are preferred.

<Other additives>
In addition to the above, this resin composition may appropriately contain other additives selected from coupling agents, UV inhibitors, antioxidants, plasticizers, flame retardants, colorants, flow improvers, defoamers, ion trappers, etc.

Furthermore, when the resin composition is in liquid form, it is preferable that the resin composition be solvent-free. By being solvent-free, it is possible to prevent the generation of voids and other defects due to solvent volatilization when the liquid composition is heat-cured. Note that "solvent" refers to volatile components and, in this specification, includes water and organic solvents. A solvent-free liquid composition is one that substantially does not contain 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.

<Method for manufacturing this resin composition>
This resin composition can be obtained by mixing and kneading zeolite and resin, along with inorganic fillers other than zeolite, curing agents, dispersants, reactive diluents, and other additive components as needed, using a vacuum mixer, mixing rolls, planetary mixer, etc., and degassing as necessary. The order in which these components are added is arbitrary, as long as there are no particular problems such as the occurrence of reactions or precipitates. Two or three or more of the constituent components may be mixed in advance and then the remaining components may be mixed, or all components may be mixed at once.

<Physical properties of this resin composition>
(Average coefficient of thermal expansion (CTE))
When the resin composition is cured to a gel fraction of 80% or more, the average coefficient of thermal expansion (CTE) of the cured product at 25 to 100°C is preferably 0 ppm/K or more, more preferably 2 ppm/K or more, even more preferably 4 ppm/K or more, and particularly preferably 10 ppm/K or more. On the other hand, it is preferably 100 ppm/K or less, more preferably 50 ppm/K or less, and even more preferably 30 ppm/K or less.
Such resin compositions have a low average thermal expansion coefficient at temperatures below the glass transition temperature, making them useful as materials requiring various heat resistances, and are particularly effective for application in electronic devices.

The average thermal expansion coefficient mentioned above can be measured by thermomechanical analysis of a cured product obtained by curing the resin composition to a gel fraction of 80% or more. The specific measurement conditions are as described in the examples.

(viscosity)
The resin composition is preferably fluid at room temperature (23°C). A low viscosity is preferable for ease of filling even narrow spaces. On the other hand, a high viscosity is preferable for preventing dripping during filling. The viscosity of the resin composition at 23°C is preferably 0.1 Pa·s or higher, more preferably 1 Pa·s or higher, even more preferably 3 Pa·s or higher, and particularly preferably 5 Pa·s or higher. Conversely, it is preferably 250 Pa·s or lower, more preferably 150 Pa·s or lower, even more preferably 50 Pa·s or lower, and particularly preferably 20 Pa·s or lower.

Furthermore, the viscosity at 23°C mentioned above should be measured using a Type B rotational viscometer, which is one of the single-cylinder rotational viscometers. For example, the Type B rotational viscometer described in the examples can be used.

(Water absorption rate)
It is preferable that the water absorption rate of the cured resin composition is 5% or less when cured to a gel fraction of 80% or more. When the water absorption rate is 5% or less, problems caused by hygroscopicity are less likely to occur, even when used as part of an electronic component such as an underfill material. From this viewpoint, the lower the water absorption rate, the better; more preferably 4% or less, even more preferably 3% or less, and particularly preferably 2% or less.
The water absorption rate can be measured using the method described in the examples.

(Gap filling distance)
When this resin composition is held at 80°C for 10 minutes, the gap-filling distance into 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. When the gap-filling distance is this length or longer, it can penetrate narrow gaps well, for example, when used as part of an electronic component such as an underfill material.
The gap filling distance can be measured by the method described in the examples.

[Application]
This resin composition can be used, for example, in catalyst modules, molecular sieve membrane modules, optical components, moisture-absorbing components, food products, building materials, and components and packaging materials for electronic devices, with its use in electronic devices being particularly preferred.
An electronic device is a device having two or more electrodes that controls the current flowing between the electrodes or the voltage generated by electricity, light, magnetism, or chemical substances, or a device that generates light, an electric field, or a magnetic field by an applied voltage or current. Specifically, examples include resistors, rectifiers (diodes), switching elements (transistors, thyristors), amplifying elements (transistors), memory elements, or chemical sensors, or devices that combine or integrate these elements. Also, optical elements such as photodiodes or phototransistors that generate photocurrents, electroluminescent elements that emit light when an electric field is applied, and photoelectric conversion elements or solar cells that generate electromotive force from light can also be mentioned. Semiconductor devices are preferred among electronic devices. Semiconductor devices preferably have at least a semiconductor substrate, for example, a device on which a semiconductor chip is mounted on a substrate, or a device in which semiconductor chips or semiconductor substrates are stacked in multiple layers.

<Liquid sealant>
When the resin composition is in liquid form, it is preferable to use it as a liquid encapsulant, in which case the liquid composition is cured to become a encapsulant.
Liquid sealants are best used as sealants to fill gaps formed in constituent members, and then harden to fill those gaps. A method for manufacturing a sealant that involves filling a gap with a resin composition and then hardening it is also within the scope of the present invention.
Furthermore, the liquid sealant may be used as a sealant to fill gaps between components by, for example, applying it to various components, then placing another component on top of the liquid sealant, and then curing it as appropriate. In this case, the liquid sealant may be cured to a B-stage before the other component is placed on top.
Among these, the present resin composition, particularly the liquid composition in which the present resin composition is in liquid form, is preferred for use in applications where it is filled into gaps and then cured. That is, it is preferable to manufacture a sealing material by filling a gap with the present resin composition and then curing it.

This resin composition is preferably used as a liquid encapsulant, and particularly preferably as an underfill material. The underfill material is preferably used in the manufacture of electrical devices, especially semiconductor devices, and is preferably used to fill gaps formed between a substrate and a semiconductor chip, between substrates, or between semiconductor chips. The substrate can be a known substrate, and it is preferable to use an organic material substrate such as an epoxy resin substrate or a phenolic resin substrate. The semiconductor chip is preferably formed from a semiconductor substrate such as a silicon substrate.
This resin composition has a low coefficient of thermal expansion of its cured product. When used as an underfill material, the difference in coefficient of thermal expansion between the underfill material and semiconductor substrates is reduced, thereby improving thermal cycling resistance and other properties.

The underfill material is preferably used as a sealing material to seal the gap between the substrate and the semiconductor chip in a laminate in which a semiconductor chip is mounted on a substrate, and is then cured by heating. In this case, it is preferable that the semiconductor chip be bonded to the surface of the substrate, where the wiring pattern is formed via bumps, for example, by reflow soldering, before the underfill material is filled.

Underfill material may be used in the manufacturing of semiconductor devices using the pre-apply method. Specifically, underfill material is filled between multiple bumps on the surface of a semiconductor chip, where multiple bumps are formed, to form an underfill layer. The filled underfill material may be B-staged as needed. Afterward, the semiconductor chip with the underfill layer is placed on the surface of a substrate with the side containing the underfill layer facing the substrate. Then, the underfill layer is hardened by heating and pressing to become a encapsulant, and the semiconductor chip is bonded to the surface of the substrate with the wiring pattern formed on it via the bumps.

Furthermore, in the pre-apply method, an underfill layer may be formed by applying an underfill material to the surface of the substrate on which the wiring pattern is formed. The applied underfill layer may be B-staged as needed. Then, the semiconductor chip with the bumps formed on it should be placed on the substrate with the underfill layer so that the side with the bumps faces the surface of the substrate with the underfill layer. Subsequently, the underfill layer is hardened by heating and pressurizing, becoming a encapsulant, and the semiconductor chip is bonded to the surface of the substrate with the wiring pattern via the bumps.

In the above explanation, we described an example where underfill material is used as a sealing material to fill the gap between a substrate and a semiconductor chip. However, the applications of underfill material are not particularly limited; it may also be used to fill gaps between semiconductor chips, or as a sealing material to fill gaps between substrates. Furthermore, the substrate is not limited to an organic material substrate; it may also be a semiconductor substrate or the like.

The present invention will be described in further detail below using examples and comparative examples, but the present invention is not limited to the following examples and comparative examples without departing from its spirit.

(Evaluation of physical properties)
The physical properties were evaluated as follows:

(Gel fraction)
The gel fraction of the cured material was measured using the following procedure. After heat treatment at 80°C for 2 hours, the cured material was prepared under curing conditions of 120°C for 2 hours. A sample of 0.5 to 0.6 g of the cured material was cut out and placed on a wire mesh. The wire mesh was then immersed in acetone and left to stand for 24 hours. After that, the wire mesh was removed from the acetone and vacuum-dried. The gel fraction was defined as the ratio of the weight of the cured material after immersion to its weight before immersion.

(Weight reduction rate)
The weight loss rate of the zeolite was measured using the following procedure. Approximately 5 mg of zeolite was placed in a platinum cup and placed in a thermal analyzer (instrument name: TGA Q5000IR, manufactured by TA Instruments). The temperature was raised from room temperature to 800°C at an air atmosphere and a heating rate of 10°C/min, and held at 800°C for 10 minutes. The weight loss rate was defined as the percentage decrease in weight at 800°C relative to the weight at 400°C. Specifically, it was calculated as follows: "Weight loss rate of zeolite = 100 × {(weight at 400°C) - (weight after holding at 800°C for 10 minutes)} / (weight at 400°C)".

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

(particle size distribution)
The particle size distribution of zeolite was measured using the following procedure. Zeolite powder was added to pure water to make a slurry of approximately 0.2% by mass. This slurry was then placed in a laser diffraction/scattering particle size distribution analyzer (device name: Laser Diffraction/Scattering Particle Size Distribution Analyzer Partica mini LA-350, manufactured by HORIBA Corporation) through which pure water was flowing, and ultrasonically treated for 1 minute to obtain the volume-based particle size distribution. The refractive index of water was set to 1.33, and the refractive index of the zeolite powder was set to 1.50. In the obtained volume-based particle size distribution measurement, the percentage of particles with a particle size of 3 μm or larger relative to all particles detected by the device was calculated and expressed as the percentage of particles with a particle size of 3 μm or larger obtained from the volume-based particle size distribution measurement (%).

(particle size)
The particle size of the zeolite was measured using the following procedure. Zeolite powder was added to pure water to make a slurry of approximately 0.2% by mass. This slurry was then placed in a laser diffraction/scattering particle size distribution analyzer (device name: Laser Diffraction/Scattering Particle Size Distribution Analyzer Partica mini LA-350, manufactured by HORIBA Corporation) through which pure water was flowing, and ultrasonically treated for 1 minute to obtain the volume-based particle size distribution. The refractive index of water was set to 1.33, and the refractive index of the zeolite powder was set to 1.50. In the obtained volume-based particle size distribution measurement, the median diameter was calculated and used as the particle size of the zeolite.

(Average thermal expansion coefficient (CTE) of zeolite)
The average thermal expansion coefficient of zeolite was measured using the following procedure. Pre-dried zeolite was placed in an X-ray diffractometer (device name: D8 ADVANCE, manufactured by BRUKER) and X-ray diffraction measurements were performed in the range of 50 to 100°C. The obtained results were used to calculate the lattice constants of the a, b, and c axes at each temperature using X-ray diffraction analysis software (software name: JADE, manufactured by Materials Data). The average thermal expansion coefficient of zeolite was calculated using the following formula: "Average thermal expansion coefficient of zeolite = {(average lattice constant at 100°C) - (average lattice constant at 50°C)} / {(average lattice constant at 50°C) × (100°C - 50°C)}". Here, the average lattice constant at each temperature is the average value of the lattice constants of the a, b, and c axes.

(Average thermal expansion coefficient (CTE) of the cured material)
The average thermal expansion coefficient of the cured resin composition, when cured to a gel fraction of 80% or more, was measured by thermomechanical analysis using a method compliant with JIS K7197 (2012). The measurement was performed using a thermomechanical analyzer (device name: TMA SS7100, manufactured by SII Nanotechnology Co., Ltd.) and the compression method.
Specifically, when the resin composition was cured to a gel fraction of 80% or more, the cured material was cut into pieces measuring φ6 mm × 10 mm in size. Using a thermomechanical analyzer, the temperature was measured by compression from 200°C to 20°C at a rate of 5°C/min, and the temperature change of the change in sample length between 25 and 100°C was measured. The slope of the tangent line was defined as the mean thermal expansion coefficient (CTE).

(viscosity)
The viscosity of the resin composition at 23°C was measured using a B-type rotational viscometer. For viscosity between 0.1 and 100 Pa·s, the Brookfield LVDV-1 Pri with spindles S64 and S63 was used. For viscosity exceeding 100 Pa·s, the Brookfield HBDV-E with spindle S-07 was used. The values measured at 5 rpm were used as representative values for the viscosity of each sample.

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

(Gap filling distance)
A test specimen was prepared by creating a 7 μm gap on a 10 mm wide glass plate and then sandwiching it with another glass plate. This test specimen was placed on a horizontal hot plate heated to 80°C with one side of the glass plate in contact with the hot plate. A resin composition was applied to one end of the glass plate and left to stand for 10 minutes. After 10 minutes, the distance the resin composition had advanced within the gap was measured to evaluate the gap-filling distance.

First, examples of the zeolite of the present invention are shown.

Manufacturing Example 1
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, Kyowa Chemical Industry Co., Ltd.'s "Kyoward 200S" as aluminum hydroxide, and Nissan Chemical Industries Ltd.'s "Snowtex N-40" as silica were added to the container in sequence.
The composition and molar ratio of the obtained mixture were _SiO₂ : _Al₂O₃ : _TMAdaOH : _H₂O :surfactant = 1.0:0.025:0.3:25:0.02. Subsequently, 5% by mass of CHA-type zeolite was added to _SiO₂ as a seed crystal and thoroughly mixed. The resulting mixture was then placed in a pressure vessel and hydrothermally synthesized in an oven at 150°C for 48 hours. After suction filtration and washing, it was dried to obtain CHA-type zeolite.
The obtained zeolite contained particles of 3 μm or larger, representing 1% by volume. The particle size of the obtained zeolite was 1.21 μm. The roundness of the primary particles was 0.839. Furthermore, XRD measurement of the obtained powder confirmed that it was a CHA-type zeolite. The weight loss rate of the obtained zeolite, calculated using the above method, was 22.6%. The average thermal expansion coefficient of the zeolite at 50-100°C was -6.8 ppm/K.

Manufacturing Example 2
Zeolite was manufactured in the same manner as in Manufacturing Example 1. The manufactured zeolite was calcined at 600°C for 6 hours under air circulation to obtain calcined zeolite.
The obtained zeolite contained 15% of its particles by volume that were 3 μm or larger. The particle size of the obtained zeolite was 2.07 μm. The roundness of the primary particles was 0.845. Furthermore, when the XRD of the obtained powder was measured, it was confirmed to be a CHA-type zeolite. In addition, the weight loss rate of the obtained zeolite, calculated using the above method, was 0.40%. The average thermal expansion coefficient of the zeolite at 50-100°C was -9.4 ppm/K.

Manufacturing Example 3
The following were added to the container in sequence: 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.
The composition and molar ratio of the obtained mixture were _SiO₂ : _Al₂O₃ : _TMadaOH : _H₂O = 1.0:0.025:0.4:20. After thorough mixing, the mixture was placed in a pressure vessel and hydrothermally synthesized in an oven at 150°C for 48 hours. After suction filtration and washing, it was dried to obtain CHA-type zeolite.
The obtained zeolite had 50% of its particles larger than 3 μm by volume. The particle size of the obtained zeolite was 2.98 μm. The roundness of the primary particles was 0.840. Furthermore, XRD measurement of the obtained powder confirmed that it was a CHA-type zeolite. The weight loss rate of the obtained zeolite, calculated using the above method, was 24.2%. The average thermal expansion coefficient of the zeolite at 50-100°C was -5.0 ppm/K.

Next, examples of the resin composition of the present invention are shown.
<Ingredients>
The components used in the preparation of the resin composition are as follows:

<Epoxy resin>
(A) p-aminophenol type epoxy resin; manufactured by Mitsubishi Chemical Corporation, product name "jER630", epoxy equivalent: 97 g/equivalent <hardener>
(B) Acid anhydride curing agent; Acid anhydride (main component: methylnadic hydrogenated anhydride): Manufactured by Shin Nippon Rika Co., Ltd., product name "Ricacid HNA-100" (acid anhydride equivalent: 174-184)
(C) Imidazole-based curing agent; manufactured by Shikoku Chemicals Co., Ltd., product name "2E4MZ-CN"
<Filler>
(D) Zeolite filler 1; The zeolite produced in the above-mentioned production example 1 was used.
(E) Zeolite filler 2; The zeolite produced in the above-mentioned production example 2 was used.
(F) Zeolite filler 3; Zeolite produced in the above-mentioned production example 3 was used.
<Additives>
(G) Additive; manufactured by BIC Chemie Japan, wetting and dispersing agent, product name "DISPERBY K-2152" (amino group-containing ultramolecular weight polyester, comb-type, solvent-free)

Example 1
The fillers, resins, curing agents, and additives shown in Table 1 were mixed in the amounts shown in Table 1. Then, the mixture was mixed at 1500 rpm for 5 minutes using a vacuum mixer (V-mini 300, manufactured by EME Co., Ltd.) to prepare a resin composition (liquid composition). The viscosity of this liquid composition was evaluated using the method described above. The results are shown in Table 1.
Next, the gap-filling distance of 5 g of this liquid composition was evaluated using the method described above. The results are shown in Table 1.
Next, the 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 rate of this cured product were evaluated using the evaluation method described above. The results are shown in Table 1.

Comparative Examples 1-2
In Example 1, the zeolite filler was replaced with one shown in Table 1, and a resin composition (liquid composition) and cured product were obtained in the same manner as in Example 1. The results of the evaluation, in the same manner as in Example 1, are shown in Table 1.

From the results of Example 1 and Comparative Example 1, it was found that using zeolite containing components derived from an organic structure-regulating agent (Example 1) as a filler resulted in a decrease in viscosity and water absorption rate, and an increase in gap-filling distance compared to using calcined zeolite (Comparative Example 1). In Comparative Example 1, the proportion of primary particles with a particle size of 3 μm or larger on a volume basis was higher than that of the zeolite containing components derived from an organic structure-regulating agent obtained in Example 1. This is presumed to be due to the particles adhering to each other during the calcination process. Furthermore, the resin composition obtained in Comparative Example 1 had a higher viscosity compared to the resin composition obtained in Example 1. This is presumed to be because calcining the zeolite increases the number of isolated silanol groups on the particle surface, and these isolated silanol groups interact with the resin.
Furthermore, the results from Example 1 and Comparative Example 2 showed that using zeolite as a filler in which 40% or less of the primary particles have a particle size of 3 μm or larger on a volume basis increases the gap filling distance.
In other words, the zeolite of the present invention can be used to obtain a resin composition that has low hygroscopicity and low thermal expansion coefficient after curing, as well as low viscosity and high gap penetration properties.

According to the present invention, it is possible to provide a zeolite for obtaining a resin composition that has low hygroscopicity and low thermal expansion coefficient after curing, as well as low viscosity and high gap penetration properties. Such a resin composition is suitable as a liquid sealant and is particularly useful as an underfill material.

Claims (10)

A resin composition containing zeolite and resin, wherein the zeolite, 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, by thermogravimetric analysis (TGA), has a weight loss rate of 1% or more at 800°C relative to its weight at 400°C, a roundness of 0.800 or more of primary particles, and 40% or less of particles with a particle size of 3 μm or larger obtained by volume-based particle size distribution measurement . The resin composition according to claim 1 , wherein the zeolite has d6r as CBU. The resin composition according to claim 1, wherein the zeolite has a structure of an oxygen ring of 8 members or less. The resin composition according to claim 1, wherein the zeolite has a CHA-type structure. The resin composition according to any one of claims 1 to 4 , wherein the resin comprises at least one selected from the group consisting of epoxy resins and polyimide resins. The resin composition according to claim 5, wherein the resin comprises an epoxy resin. A liquid encapsulant comprising the resin composition according to any one of claims 1 to 4 . An underfill material comprising the resin composition according to any one of claims 1 to 4 . A method for producing a sealing material, comprising the step of filling a gap with a resin composition according to any one of claims 1 to 4 , and then curing it. An electronic device comprising a sealing material obtained by the manufacturing method described in claim 9 .