Zeolite, methods for manufacturing zeolite, compositions thereof, liquid compositions thereof, liquid sealants, resin composites, sealing materials, methods for manufacturing sealing materials, and apparatus thereof.

Abstract

This invention relates to a liquid composition containing resin and inorganic fillers. The inorganic fillers include zeolite with a particle size of 1.0 μm to 10 μm and inorganic fillers with a particle size of 0.1 μm or more but less than 1.0 μm. This invention provides a liquid composition that can reduce the coefficient of thermal expansion of the cured material while also reducing its viscosity.

Description

Technical Field

[0001] This invention relates to a zeolite, a method for manufacturing a zeolite, a composition, a liquid composition, a liquid sealant, a resin composite material, a sealing material, a method for manufacturing a sealing material, and an electronic device. Prior Technology

[0002] For liquid sealants used as underfill materials, the industry requires excellent injectability, adhesion, curing properties, and storage stability, as well as the absence of voids. Furthermore, for areas sealed with liquid sealants, excellent moisture resistance, thermal cycling resistance, reflow resistance, crack resistance, and warpage resistance are required. To meet these requirements, epoxy resin-based liquid sealants are widely used as underfill materials.

[0003] Furthermore, in order to improve the moisture resistance and thermal cycling resistance, especially the thermal cycling resistance, of the parts sealed by the liquid sealant, the following method is effective (see Patent Document 1): by adding a filler material containing inorganic substances, such as silica filler (hereinafter referred to as "inorganic filler"), to the liquid sealant, the difference in the coefficient of thermal expansion between the substrate made of organic materials such as epoxy resin and the semiconductor element is controlled; and the bump electrode is strengthened. [Previous Technical Documents] [Patent Literature]

[0004] Patent Document 1: Japanese Patent Application Publication No. 2007-56070 Summary of the Invention

[0005] [The problem the invention aims to solve]

[0006] Liquid sealants using inorganic fillers such as silica have insufficiently low coefficients of thermal expansion. Considering factors such as thermal cycling resistance, a further reduction in the coefficient of thermal expansion is required. Furthermore, zeolite is known to be an inorganic filler with a relatively low coefficient of thermal expansion; however, liquid compositions formulated with zeolite tend to have increased viscosity, reducing injectability when used as a bottom filler. Therefore, it is difficult to obtain a liquid sealant that simultaneously reduces the coefficient of thermal expansion of the hardened material and provides good injectability.

[0007] The purpose of this invention is to provide a liquid composition and an epoxy resin composite material obtained by curing the liquid composition, wherein the liquid composition can reduce the coefficient of thermal expansion of the cured material while also reducing its viscosity. Furthermore, another object of the present invention is to provide a liquid composition and an epoxy resin composite material obtained from the liquid composition, wherein the liquid composition can prevent the viscosity from increasing in a liquid composition containing zeolite. Furthermore, another object of the present invention is to provide a zeolite with a lower coefficient of thermal expansion, based on the consideration that if a zeolite with a lower coefficient of thermal expansion is used, the coefficient of thermal expansion of the resin composite material can be reduced in a smaller amount, and the increase in viscosity caused by the use of zeolite can be suppressed. Moreover, a further object of the present invention is to provide various applications for suppressing the thermal expansion of resin substrates and the like using zeolites with a lower coefficient of thermal expansion. [Technical means to solve the problem]

[0008] The gist of this invention is as follows. [1] A liquid composition containing resin and inorganic filler, wherein the inorganic filler contains zeolite with a particle size of 1.0 μm to 10 μm and inorganic filler with a particle size of 0.1 μm or more but less than 1.0 μm. [2] The liquid composition described in [1] above further contains a dispersant having at least one functional group having an amine group and an amine salt. [3] The liquid composition described in [1] or [2] above, wherein the zeolite has d6r (double six-membered rings) as CBU (Composite Building Unit). [4] The liquid composition described in any of [1] to [3] above, wherein the zeolite is an aluminum silicate. [5] The liquid composition described in any of [1] to [4] above, wherein the resin is an epoxy resin. [6] The liquid composition described in any one of [1] to [5] above, wherein the resin is an epoxy resin and the viscosity of the liquid composition at 23°C is 0.1 Pa·s or more and 250 Pa·s or less. [7] A liquid sealant comprising the liquid composition described in any one of [1] to [6] above. [8] A resin composite material, which is formed by hardening the liquid composition described in any one of [1] to [6] above to a gel fraction of 80% or more. [9] A resin composite material containing resin and inorganic filler, wherein the inorganic filler contains zeolite with a particle size of 1.0 μm to 10 μm and inorganic filler with a particle size of 0.1 μm or more but less than 1.0 μm.

[10] The resin composite material described above in [9] further contains a dispersant having at least one functional group, namely an amine group or an amine salt.

[11] The resin composite material as described in [9] or

[10] above, wherein the zeolite has d6r as CBU.

[12] The resin composite material described in any of [9] to

[11] above, wherein the zeolite is an aluminum silicate.

[13] The resin composite material described in any of [9] to

[12] above, wherein the resin is selected from at least one of the group consisting of epoxy resin and polyimide resin.

[14] The resin composite material described in any of [9] to

[13] above, wherein the resin is an epoxy resin, and the average coefficient of thermal expansion of the resin composite material, determined by the following method, is 0 ppm / K or more and 200 ppm / K or less. (Among them, the average coefficient of thermal expansion is based on JIS K7197 (2012), which is determined by measuring the temperature change of the sample length change at 25~100℃ using the compression method of thermomechanical analysis, and obtained from the slope of its tangent).

[15] A zeolite having a particle size of 1.0 μm to 10 μm, having d6r as CBU, and being spherical.

[16] A zeolite having a particle size of 1.0 μm to 10 μm, having d6r as CBU, and having a c-axis length of 14.80 Å or less in lattice constant.

[17] A composition comprising zeolite as described in

[15] or

[16] above, and resin.

[18] The composition described in

[17] above, wherein the resin is selected from at least one of the group consisting of epoxy resin and polyimide resin.

[19] The composition described in

[17] or

[18] above further contains inorganic fillers with a particle size of 0.1 μm or more but less than 1.0 μm.

[20] The composition described in any of

[17] to

[19] above further contains a dispersant having at least one functional group having an amino group and an amino salt.

[21] A liquid composition, which is the composition described in any one of

[17] to

[20] above, wherein the content of the zeolite is 40 to 70% by mass, the resin is an epoxy resin, and the viscosity of the liquid composition at 23°C is more than 1 Pa·s and less than 30 Pa·s.

[22] A resin composite material comprising the composition described in any one of

[17] to

[20] above, wherein the content of the zeolite is 40 to 70% by mass, the resin is an epoxy resin, and the average coefficient of thermal expansion of the resin composite material at 25 to 100°C is 10 to 30 ppm / K.

[23] A sealing material comprising a resin composite material as described in any one of [9] to

[14] and

[22] above.

[24] An electronic device comprising a resin composite material as described in any one of [9] to

[14] and

[22] above.

[25] A method for manufacturing a sealing material, wherein a liquid composition as described in any one of [1] to [6] and

[21] above is filled into a gap and then hardened.

[26] A method for manufacturing zeolite, characterized in that: the method includes a step of hydrothermal synthesis of a raw material composition comprising silicon atom raw material, water-soluble aluminum atom raw material, organic structure preservative and water, and a subsequent calcination step, wherein the content of alkali metal atoms in the raw material composition other than the organic structure preservative is 0.05 moles or less per mol of Si atoms. [Effects of the Invention]

[0009] In this invention, a liquid composition and a resin composite material obtained by hardening the liquid composition to reduce the coefficient of thermal expansion are provided. The liquid composition does not easily increase viscosity by combining zeolite with a specific particle size and inorganic filler. Furthermore, the present invention may also provide a liquid composition and a resin composite material obtained from the liquid composition, wherein the viscosity of the liquid composition can be prevented from increasing in the liquid composition containing zeolite by using a specific dispersant. Furthermore, in this invention, a zeolite with a low coefficient of thermal expansion can also be provided, which is suitable for suppressing the thermal expansion of resins. Simple Explanation of the Diagram

[0010] Figure 1 is a graph showing the particle size distribution of the zeolite in Example 1. Figure 2 is a graph showing the particle size distribution of the zeolite in Example 2. Figure 3 is a graph showing the particle size distribution of the zeolite in Comparative Example 2. Implementation

[0011] The present invention will now be described with reference to embodiments. [First Implementation] Zeolite The zeolite system of the first embodiment of the present invention is an aluminosilicate with a particle size of 1.0 μm to 10 μm and containing d6r as CBU. One of the characteristics of the zeolite of the present invention is that its particle size is larger than that of ordinary zeolite, with a particle size of more than 1.0 μm and less than 10 μm. The zeolite of the first embodiment of the present invention will be described in detail below. Furthermore, zeolites with a particle size of 1.0 μm to 10 μm are sometimes referred to as "large-particle-size zeolites".

[0012] (Particle size of zeolite) The particle size of the zeolite in the first embodiment of the present invention refers to the diameter (circle equivalent diameter) of the largest circle with an area equal to the projected area of ​​the particle when observed using a scanning electron microscope (SEM). Regarding the zeolite of the first embodiment of the present invention, multiple zeolite particles can aggregate to form secondary particles. In this case, the particle size of the zeolite is the particle size of the primary particles. Considering that the viscosity of the zeolite does not easily increase when added to the resin, the particle size of the zeolite in the first embodiment of the present invention is preferably larger. On the other hand, considering that it is easier to mix uniformly with other components such as resin and that surface smoothness is easily improved, the particle size of the zeolite in the first embodiment of the present invention is preferably smaller. Specifically, it is preferably 1.5 μm or more, more preferably 2.0 μm or more. Furthermore, it is preferably 8 μm or less, more preferably 5 μm or less. When using zeolite, it is usually not used as a single zeolite particle, but rather as a group of multiple zeolite particles. That is, in one embodiment of the present invention, it is preferable to use a group of zeolite comprising at least the zeolite particles of the first embodiment of the present invention. For this type of zeolite comprising multiple zeolite particles, the average primary particle size is preferably in the range of 1.1 to 4.0 μm, more preferably 1.5 to 3.8 μm, and even more preferably 2.0 to 3.5 μm. The average primary particle size of the zeolite is obtained by randomly selecting 50 zeolite particles (particles in powder, the liquid composition described below, or resin composite materials), measuring their particle size, and taking the average value. Furthermore, regarding the volume-based particle size distribution of zeolite, the median particle size (d50) is preferably in the range of 0.5 to 5.0 μm, more preferably in the range of 1.5 to 5.0 μm, and even more preferably in the range of 2.0 to 4.0 μm. By having the median particle size within this range, the proportion of zeolite that exerts the effects of the present invention increases, making it easier to obtain the effects of the present invention with a smaller quantity.

[0013] (Structure of zeolite) Zeolites are compounds composed of silicon or aluminum and oxygen, and are based on TO 4 units (T elements are elements other than oxygen that form the framework). Specifically, examples of zeolites include crystalline porous aluminosilicates, crystalline porous aluminum phosphates (ALPO), or crystalline porous silica aluminum phosphates (SAPO). The zeolite of the first embodiment of the present invention is an aluminosilicate. Zeolites are composed of structural units called composite building units (CBUs), which are formed by connecting several (to dozens) TO 4 units. Therefore, zeolites have regular channels (tubular pores) and cavities (hollows). The crystal structure of CBU or the following zeolites can be represented by the coding system established by the International Zeolite Association (IZA). Alternatively, the zeolite structure can be identified using the 2018 version of the Zeolite Structure Database (http: / / www.iza-structure.org / databases / ) based on X-ray diffraction patterns obtained using an X-ray structure analysis device (e.g., the D2PHASER desktop X-ray diffraction device manufactured by BRUKER).

[0014] (The skeleton of zeolite) The zeolite skeleton of the first embodiment of the present invention includes d6r as a CBU. By including d6r, it is easy to obtain a resin composite material with a low coefficient of thermal expansion, as detailed below. Examples of zeolites with d6r as a 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 -WEN type structures. Among these, zeolites with an oxygen octet or smaller structure are preferred, especially considering ease of particle size control. Examples of zeolites with an oxygen octet or smaller structure include AEI, AFT, AFX, CHA, ERI, KFI, SAT, SAV, SFW, and TSC type structures. Among these, zeolites with AEI, AFX, CHA, and ERI type structures are preferred, especially those with a CHA structure, considering structural stability even with shape control. Furthermore, in this specification, an oxygen octet structure means a structure in which the number of oxygen elements is 8, where the pores formed by oxygen and T elements (elements other than oxygen constituting the framework) that make up the zeolite framework are at most composed of oxygen and T elements.

[0015] (Average thermal expansion coefficient of zeolite) Based on the consideration that a small amount can easily reduce the average coefficient of thermal expansion of the following liquid composition and resin composite material, the zeolite of the first embodiment of the present invention preferably has a low average coefficient of thermal expansion. Furthermore, since the amount is small, the various physical properties of the resin are less likely to be altered by the addition of zeolite; based on this consideration, the average coefficient of thermal expansion of the zeolite of the first embodiment of the present invention is also preferably low. In particular, based on the consideration of suppressing the increase in viscosity of the following liquid composition, the average coefficient of thermal expansion of the zeolite of the first embodiment of the present invention is also preferably low. Specifically, the average coefficient of thermal expansion of the zeolite is generally less than 0 ppm / K, preferably -2 ppm / K or less, more preferably -3 ppm / K or less, further preferably -5 ppm / K or less, particularly preferably -6 ppm / K or less, and most preferably -8 ppm / K or less.

[0016] On the other hand, taking into account the liquid composition and resin composite material containing zeolite and resin described below, the average thermal expansion coefficient of zeolite is preferably higher due to the smaller difference between the average thermal expansion coefficients of the two materials and the ease with which zeolite and resin are separated. Therefore, the average thermal expansion coefficient of zeolite is typically -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 especially preferably -300 ppm / K or higher. Furthermore, especially when used in applications where the zeolite comes into contact with other materials such as sealing materials or substrates, the average coefficient of thermal expansion is preferably higher, specifically, preferably -100 ppm / K or higher, more preferably -50 ppm / K or higher, even more preferably -40 ppm / K or higher, particularly preferably -30 ppm / K or higher, especially preferably -25 ppm / K or higher, and most preferably -20 ppm / K or higher. Furthermore, the average thermal expansion coefficient of zeolite can be determined by calculating the lattice constant using the "D8ADVANCE" X-ray diffraction apparatus manufactured by BRUKER and the X-ray diffraction analysis software "JADE". Moreover, to eliminate the influence of moisture loss, the zeolite was measured in a dry state. The determination of the average thermal expansion coefficient of zeolite is usually carried out within the range of 50–100 °C. That is, the average thermal expansion coefficient of zeolite represents the displacement of the lattice constant per 1 °C when the zeolite is heated, relative to the average lattice constant at 50 °C and 100 °C. The average lattice constant at each temperature is the average of the lattice constants along the a-axis, b-axis, and c-axis. Furthermore, the determination of the average thermal expansion coefficient is performed by slowly increasing the temperature after the lattice constant has stabilized.

[0017] Generally, the coefficient of thermal expansion of resins tends to increase in the high-temperature region. Therefore, the average coefficient of thermal expansion of zeolite is preferably lower during the process of heating to the high-temperature region. Specifically, the average coefficient of thermal expansion (high-temperature region) in the range of 50~350℃ is preferably below -9.5 ppm / K, more preferably below -10.0 ppm / K, and even more preferably below -12.5 ppm / K. Furthermore, the average coefficient of thermal expansion (high-temperature region) of zeolite here represents the numerical value of the displacement of the lattice constant per 1℃ of heating of zeolite relative to the average lattice constant at 50℃ and the average lattice constant at 350℃.

[0018] (The shape of zeolite) The zeolite of the first embodiment of the present invention is preferably spherical, taking into account the aspect of easily suppressing the increase of viscosity. Specifically, it is preferably spherical and round.

[0019] True Ball Degree The sphericity of zeolite is preferably 0.6 or higher, more preferably 0.65 or higher, and especially preferably 0.70 or higher. However, there is no particular upper limit to the sphericity; it can be below 1. Furthermore, zeolite is usually cubic in shape, in which case the sphericity is 0.58. In this specification, "true sphericity" is defined as "the ratio of the minimum diameter of a particle to its maximum diameter." The maximum and minimum diameters can be determined by observation using a scanning electron microscope (SEM).

[0020] <<True Roundness>> The sphericity of the zeolite according to the first embodiment of the present invention is preferably 0.786 or higher, more preferably 0.790 or higher, even more preferably 0.795 or higher, even more preferably 0.800 or higher, even more preferably 0.805 or higher, particularly preferably 0.810 or higher, especially preferably 0.815 or higher, and most preferably 0.820 or higher. Furthermore, there is no particular limitation on the upper limit of sphericity; it can be 1 or less. Moreover, zeolite is usually cubic in shape, in which case the sphericity 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).

[0021] (c-axis length of zeolite) The c-axis length of the lattice constant of the zeolite in the first embodiment of the present invention is preferably short. Because the c-axis length is short, the transverse lattice vibrations are larger, resulting in negative expansion, and the average coefficient of thermal expansion is more easily reduced. Specifically, the c-axis length is preferably 14.80 Å or less, more preferably 14.78 Å or less, further preferably 14.76 Å or less, particularly preferably 14.74 Å or less, especially preferably 14.72 Å or less, and most preferably 14.70 Å or less. Furthermore, in this specification, the c-axis length refers to the length of the c-axis at room temperature (23°C). The lattice constant of zeolite can be determined using the "D8 ADVANCE" X-ray diffraction apparatus manufactured by BRUKER Corporation, and calculated using the least squares method with the X-ray diffraction analysis software "JADE".

[0022] (Zeolite structure density) The zeolite's structure density in the first embodiment of the present invention is not particularly limited as long as it does not impair the effects of the present invention. Considering the ease with which zeolite structural vibrations occur and the ease with which the average coefficient of thermal expansion can be reduced, the zeolite's structure density is preferably low. Therefore, the zeolite's structure density is preferably 17.0 T / 1000 ų or less, and more preferably 16.0 T / 1000 ų or less. On the other hand, considering the ease with which zeolite can increase structural stability, a relatively high zeolite structure density is preferable. A zeolite structure density of 12.0 T / 1000 ų or higher is preferred, more preferably 13.0 T / 1000 ų or higher, and even more preferably 14.0 T / 1000 ų or higher is also preferred. If the structure density is within the above range, zeolite can be used as a stabilizing filler. Furthermore, the structure density represents 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, values ​​from the 2017 edition of the IZA Zeolite Structure Database (http: / / www.iza-structure.org / databases / ) may be used.

[0023] Examples of zeolites with a structure density greater than 16.0 T / 1000 Å3 and less than 17.0 T / 1000 Å3 include zeolites with ERI, LTL, LTN, MOZ, OFF, SAT, SSF, and -WEN type structures. Examples of zeolites with a structure density greater than 15.0 T / 1000 Å3 and less than 16.0 T / 1000 Å3 include zeolites with structures of the AEI, AFT, AFV, AFX, AVL, EAB, GME, LEV, MWW, and SFW types. Examples of zeolites with a structure density greater than 14.0 T / 1000 Å3 and less than 15.0 T / 1000 Å3 include zeolites with CHA, KFI, SAS, and SAV structures. Examples of zeolites with a structure density below 14.0 T / 1000 Å3 include zeolites with EMT, FAU, JSR, SBS, SBT, and TSC structures.

[0024] (Silicon dioxide of zeolite / Mohr's ratio of alumina (SAR)) The molar ratio of silicon dioxide to aluminum oxide (sometimes referred to as "SAR", "Si / Al2 molar ratio", or "Si / Al2 ratio") of the zeolite in the first embodiment of the present invention is not particularly limited as long as it does not impair the effects of the present invention. Considering the improved moisture resistance of the resin composite material and the ease of controlling the amount of counteracting cations, the SAR (Si / Al2 ratio) of the zeolite is preferably higher. Therefore, the SAR (Si / Al2 ratio) of the zeolite is generally 2 or higher, preferably 3 or higher, more preferably 3.5 or higher, further preferably 4 or higher, particularly preferably 4.5 or higher, and most preferably 5 or higher. On the other hand, considering the ease of manufacturing at a low cost, the SAR (Si / Al2 ratio) of zeolite is preferably low. Therefore, the SAR (Si / Al2 ratio) of zeolite is typically below 2000, preferably below 1000, more preferably below 500, and even more preferably below 100. If the Si / Al2 ratio is within the above range, it is easier to control the amount of counteracting cations, and the manufacturing cost of zeolite can also be lower.

[0025] (Countercations of zeolite) The countercation of the zeolite in the first embodiment of the present invention is not particularly limited as long as it does not impair the effects of the present invention. The countercation of the zeolite is typically a proton, an alkali metal ion, or an alkaline earth metal ion. Preferably, it is a proton or an alkali metal ion, and more preferably, a proton, a Li ion, a Na ion, or a K ion. The smaller the size of the alkali metal ion or alkaline earth metal ion, the easier it is for the zeolite to exhibit an average coefficient of thermal expansion below 0 ppm / K, which is therefore preferred. In particular, when the countercation of the zeolite is a proton, it is easier to reduce the average coefficient of thermal expansion of the resin composite material, which is also preferred. That is, as a zeolite, it is preferably a proton-type or an alkali metal-type, more preferably a proton-type, a Li-type, a Na-type, or a K-type, and especially preferably a proton-type.

[0026] (Crystallization degree of zeolite) The crystallinity of the zeolite in the first embodiment of this invention is not particularly limited as long as it does not impair the effects of this invention. This is presumably because, compared to the structure determined by coding in IZA, the Composite Building Unit (CBU) has a greater impact on the average coefficient of thermal expansion of epoxy resin composites. Furthermore, the crystallinity of the zeolite can be determined by comparing it with the X-ray diffraction peak of a zeolite based on a certain X-ray diffraction peak, obtained using an X-ray diffraction apparatus (e.g., the "D2PHASER" benchtop X-ray diffraction apparatus manufactured by BRUKER). As a specific example of calculation, the crystallinity of LTA-type zeolite can be cited in Scientific Reports 2016, 6, Article number: 29210.

[0027] (Surface treatment of zeolite) Zeolite can undergo surface treatments such as silanization without compromising the effectiveness of this invention. Such surface treatments are not limited to physical or chemical treatments.

[0028] (Method for manufacturing zeolite) The manufacturing method of zeolite can be any known method. For example, in the case of manufacturing CHA-type zeolite, the method described in Japanese Patent Application Publication No. 2009-097856 can be used. In the case of manufacturing zeolite with larger particle size, hydrothermal synthesis can be carried out by appropriately controlling the type and ratio of raw materials, synthesis time, or temperature. Specifically, for example, zeolite with larger particle size can be manufactured by increasing the amount of water used in synthesis and diluting the concentration of raw materials, as described in Microporous and Mesoporous Materials 21 (1998) 24.

[0029] Furthermore, the aforementioned superior zeolite can be manufactured by the following method (hereinafter sometimes referred to as "the method for manufacturing the zeolite of the present invention"). The method for manufacturing zeolite of the present invention comprises: a step of hydrothermal synthesis of a raw material composition containing silicon atom raw material, water-soluble aluminum atom raw material, organic structure prescribing agent and water, and a subsequent calcination step. In this context, the content of alkali metal atoms in the above-mentioned raw material composition, excluding the organic structure prescribing agent, is set to 0.05 moles or less per mole of Si atoms. Furthermore, the required zeolite (hereinafter sometimes referred to as "seed zeolite") may be used as needed.

[0030] <<Silicon Atom Raw Materials>> The silicon atom raw material used in this invention is not particularly limited, and various known substances can be used. For example, colloidal silicon dioxide, amorphous silicon dioxide, sodium silicate, trimethylethoxysilane, tetraethyl orthosilicate, aluminosilicate gel, and zeolite can be used. Among these, amorphous silicon dioxide is preferred due to its lower alkali metal content. One of these can be used alone, or two or more can be used in any combination and ratio.

[0031] <<Aluminum Atom Raw Materials>> The aluminum atom raw material is water-soluble. Furthermore, considering the lower content of alkali metals, aluminum hydroxide is preferred. Water-soluble amorphous aluminum hydroxide is particularly advantageous because it allows zeolite to grow into spherical shapes without calcination.

[0032] <<Alkali Metal Atomic Raw Materials>> Alkali metal atoms may not be used. When used, the content of alkali metal atoms, excluding organic structure prescribing agents, is set to 0.05 moles or less per mole of Si atoms. There are no particular limitations on the alkali metal atoms used when using alkali metal atoms; those known for their use in zeolite synthesis can be used, preferably at least one alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium. The amount of alkali metal used, in mole ratio to the silicon (Si) content of the raw material composition, is preferably 0.045 or less, more preferably 0.04 or less, further preferably 0.035 or less, and particularly preferably 0.03 or less. Because the amount of alkali metal atoms is relatively small, zeolite is more likely to grow into a spherical shape, with a shorter c-axis length in the crystal lattice, and the average coefficient of thermal expansion tends to increase in the negative direction.

[0033] <<Organic Structure Regulators>> As an organic structure prescribing agent, various known substances such as tetraethylammonium hydroxide (TEAOH) and tetrapropylammonium hydroxide (TPAOH) can be used. Among these, N,N,N-trimethyl-1-adamantane ammonium hydroxide (TMAdaOH) is preferred. The amount of the organic structure prestressing agent used, calculated relative to the molar ratio of silicon (Si) contained in the raw material composition, is typically 0.01 or more, preferably 0.02 or more, even more preferably 0.03 or more, particularly preferably 0.04 or more, and most preferably 0.05 or more. On the other hand, it is typically 1 or less, preferably 0.6 or less, even more preferably 0.55 or less, and even more preferably 0.5 or less. With the amount of the organic structure prestressing agent used within this range, it is easier to grow high-purity spherical zeolite with fewer byproducts.

[0034] <<Seed Zeolite>> In the manufacturing method of the present invention, zeolite can be used as seed crystals. When using seed zeolite, one type can be used alone, or two or more types can be used together in any combination and ratio.

[0035] <<Water>> The amount of water used is determined based on the consideration of facilitating crystal formation. When using seed zeolite, the molar ratio relative to the silicon (Si) content of the raw material composition excluding the seed zeolite is typically 5 or more, preferably 7 or more, more preferably 9 or more, and even more preferably 10 or more. By setting it within this range, crystal formation is easier and better. Furthermore, by synthesizing under conditions where the raw material concentration is diluted by increasing the amount of water, it is easier to produce zeolite with a larger particle size. In order to fully obtain the effect of reducing the cost of wastewater treatment, the amount of water used, relative to the silicon (Si) molar ratio, is typically 50 or less, preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0036] <<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, organic structure prestating agents and water, and then adding seed zeolite as needed. Furthermore, in this invention, in addition to the above-mentioned components, acidic components that promote the reaction or metal stabilizers such as polyamines may be added in any step as needed.

[0037] <<Mature>> The raw material composition prepared as described above can be subjected to hydrothermal synthesis immediately after preparation. To obtain zeolite with higher crystallinity, it is preferable to mature it for a certain period of time under specified temperature conditions. Especially when the reaction scales up, considering the improved agitation and ease of achieving a more homogeneous state of the raw materials, it is preferable to mature the raw materials while stirring for a certain period of time. The maturation temperature is usually below 100°C, preferably below 95°C, and more preferably below 90°C. The lower limit is not specifically set, but it is usually above 0°C, and more preferably above 10°C. The maturation temperature can be fixed during the maturation process, or it can be varied in stages or continuously. The maturation time is not particularly limited, but it is usually above 2 hours, preferably above 3 hours, and more preferably above 5 hours. On the other hand, it is usually below 30 days, preferably below 10 days, and even more preferably below 4 days.

[0038] <<Hydrothermal Synthesis>> Subsequently, the obtained raw material composition was subjected to hydrothermal synthesis. Hydrothermal synthesis is usually 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 stirring, rotating or shaking the container under its own pressure or under gas pressure that does not hinder crystallization, or maintaining a specified temperature in a static state. To accelerate the reaction rate, the reaction temperature during hydrothermal synthesis is typically above 120°C, preferably above 130°C, more preferably above 140°C, and particularly preferably above 150°C. Alternatively, it is typically below 230°C, preferably below 220°C, more preferably below 200°C, and even more preferably below 190°C. The reaction time is not particularly limited, but is typically above 2 hours, preferably above 3 hours, and even more preferably above 5 hours. Alternatively, it is typically below 30 days, preferably below 10 days, even more preferably below 7 days, and even more preferably below 5 days. The reaction temperature can be fixed during the reaction process, or it can vary in stages or continuously. The reason why the zeolite manufacturing method of the present invention can produce superior zeolite is presumed as follows. In the manufacture of zeolite, alkali metals are generally used to dissolve the raw material components. In contrast, when using the zeolite manufacturing method of the present invention, alkali metals are not used, or even if they are used, the amount is less than a certain amount. As a result, in the raw material composition, crystals readily grow from an organic structure-defining agent as a starting point, and the crystals readily grow into spherical shapes from that starting point. Furthermore, it is presumed that during the process of crystal growth into spherical shapes, the crystal lattice undergoes strain, which is fixed by calcination. The fact that the c-axis length of the crystal lattice in Examples 1-3 (manufactured by the zeolite manufacturing method of the present invention) is shorter than that in Comparative Examples 1 (without calcination) and 2 (using sodium hydroxide) also supports this presumption. Furthermore, it is presumed that due to the strain generated by the crystal lattice, the average coefficient of thermal expansion of the zeolite of the first embodiment of the present invention is more likely to be lower. That is, due to the strain generated by the crystal lattice, the strain is eliminated upon heating, resulting in shrinkage. Also, it is presumed that for the same reason, the average coefficient of thermal expansion of the zeolite of the first embodiment of the present invention is more likely to be lower in the high-temperature region (range of 50~350°C). This presumption is also supported by the fact that the average coefficient of thermal expansion of Examples 1~3, which have shorter c-axis lengths of the crystal lattice, is lower than that of Comparative Examples 1 and 2 in the comparison of Examples 1~3 and Comparative Examples 1~2 described below.

[0039] [Second Implementation] <Composition> The composition of the second embodiment of the present invention is a composition containing the zeolite and resin of the first embodiment described above. As described below, the average coefficient of thermal expansion of the zeolite of the first embodiment is easily made extremely low. Therefore, by containing this zeolite, the thermal expansion of the composite material containing the composition of the second embodiment can be suppressed. The content of zeolite of the first embodiment contained in the resin composition is preferably 25% by mass or more, more preferably 30% by mass or more, further preferably 35% by mass or more, further preferably 40% by mass or more, particularly preferably 45% by mass or more, and especially preferably 50% by mass or more, relative to the total amount of the composition. On the other hand, it is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 75% by mass or less, and especially preferably 70% by mass or less. Furthermore, when the resin composition contains fillers other than the zeolite of the first embodiment, the zeolite content of the present invention among all fillers is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, further preferably 70% by mass or more, and most preferably 90% by mass or more, taking into account the smaller increase in viscosity of the resin compound and the ease of reducing the coefficient of thermal expansion of the cured product.

[0040] (resin) The resin used in the composition of the second embodiment of the present invention is not particularly limited within the scope of the effects of the present invention. However, considering the further enhancement of its effects as a composite material, it is preferably selected from at least one of the group consisting of epoxy resin and polyimide resin. In particular, when used as a liquid composition that can be used as a sealant, epoxy resin is preferred. Furthermore, when used as a composition that can be used as a substrate, polyimide resin is preferred. The amount of resin contained in the composition of the present invention is preferably 5% by mass or more, and more preferably 10% by mass or more, relative to the total amount of the composition, taking into account both the maintenance of the excellent physical properties of the resin and the heat resistance (non-instability of thermal expansion) of the cured resin composition. On the other hand, it is preferably 50% by mass or less, more preferably 25% by mass or less, and particularly preferably 15% by mass or less.

[0041] <<Epoxy Resin>> The epoxy resin used in this invention will be described in detail in the fifth embodiment of this invention below.

[0042] <<Polyimide Resin>> As for the polyimide resin used in this invention, considering that the coefficient of thermal expansion of the resin composite material is easy to reduce, and that it has excellent properties such as heat resistance, mechanical strength, electrical properties, and solvent resistance, it is preferred to use polyimide obtained from tetracarboxylic dianhydride and diamine, especially aromatic polyimide obtained from aromatic tetracarboxylic dianhydride and aromatic diamine. More specifically, it is preferable to spray a polyimide precursor solution onto the polyimide resin powder obtained by polymerizing and acetylation aromatic tetracarboxylic acid components and p-phenylenediamine to granulate it, thereby obtaining polyimide powder, and then use the obtained polyimide powder to composite with fillers to prepare a resin composite material. Furthermore, the polyimide powder is formed by granulating polyimide powder particles together using a polyimide precursor, in which the polyimide precursor acts as a binder. For example, polyamide is used as a polyimide precursor. The polyimide precursor solution used as a raw material is produced by reacting tetracarboxylic dianhydride with a diamine in the presence of a basic compound with a pKa (Acid dissociation constant) of 7.5 or higher, using water and / or alcohol-based solvents as the reaction solvent.

[0043] As a preferred embodiment of the second embodiment, an example is a liquid resin composition that uses epoxy resin as the resin and contains the zeolite of the first embodiment, having a viscosity of 1 Pa·s or more and 30 Pa·s or less, and a zeolite content of 40 to 70% by mass. This liquid resin composition can be used as a bottom filler (hereinafter sometimes referred to as "liquid sealant"), and its average coefficient of thermal expansion decreases after curing, making it suitable as a sealant.

[0044] Furthermore, as another preferred embodiment of the second embodiment, an example is a composite material that uses epoxy resin as the resin and contains zeolite of the first embodiment, wherein the zeolite content is 40 to 70% by mass, and the average coefficient of thermal expansion of the composite material at 25 to 100°C is 10 to 30 ppm / K. This composite material has a low average coefficient of thermal expansion at temperatures below the glass transition temperature, making it suitable for use in various materials, especially electronic devices.

[0045] [Third Implementation] <Composition> The composition of the third embodiment of the present invention is a composition containing the zeolite, resin and inorganic filler with a particle size of 0.1 μm or more and 1.0 μm (hereinafter also referred to as small particle size inorganic filler) of the first embodiment.

[0046] (Inorganic packing) Considering the ease with which the liquid composition can be filled even in confined spaces, the inorganic filler preferably has a smaller particle size. On the other hand, considering the likelihood that the viscosity of the liquid composition will not increase, the inorganic filler preferably has a larger particle size. When fillers with smaller and larger specific surface areas are used together, a larger specific surface area increases the interaction between the filler and the resin, making it easier for the viscosity of the liquid composition to increase. Therefore, to reduce the viscosity of the liquid composition, it is preferable that the filler has a smaller specific surface area. Regarding specific surface area, the smaller the particle size, the easier it is to increase. Furthermore, specific surface area also varies depending on the shape of the filler; a spherical filler has the smallest specific surface area. Therefore, considering the reduction of viscosity, the inorganic filler preferably has a near-spherical shape and a larger particle size. Therefore, particularly for large-particle-size zeolites, the specific surface area is preferably 1×10⁻⁶ ( / m) or less, and more preferably 0.8×10⁻⁶ ( / m) or less. In this invention, by using both small-particle-size and large-particle-size fillers, the small particles enter the gaps between the large particles, allowing for a higher filler content, which reduces the coefficient of thermal expansion and also suppresses viscosity increase. Therefore, considering the ease with which the coefficient of thermal expansion can be reduced, the composition of this invention preferably contains large-particle-size zeolite and small-particle-size inorganic fillers. The particle size of the inorganic filler was measured in the same manner as that of the zeolite in the first embodiment described above. That is, the particle size of the inorganic filler refers to the diameter (circle equivalent diameter) of the largest circle with an area equal to the projected area of ​​the particle when observed using a scanning electron microscope (SEM). Furthermore, the particle size refers to the particle size of the primary particles. Examples of inorganic fillers used in the compositions of this invention include zeolite and inorganic fillers other than zeolite.

[0047] Zeolite is an inorganic filler with a low coefficient of thermal expansion, which can reduce the coefficient of thermal expansion of the epoxy resin composite material, which is one of the preferred forms of the present invention and serves as a hardened liquid composition. However, because zeolite has a porous structure, it has a large specific surface area, and if a large quantity is prepared, the viscosity of the liquid composition is prone to increase. In the present invention, various studies were conducted, and it was found that by including small-particle-size inorganic fillers in the liquid composition in addition to large-particle-size zeolite such as that described in the first embodiment, for example, the coefficient of thermal expansion of the liquid epoxy resin composite material can be reduced while preventing the viscosity from increasing, thus achieving a low viscosity liquid composition. Examples of inorganic fillers other than zeolites include at least one 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, silicon dioxide, calcium oxide, zinc oxide, yttrium oxide, zirconium oxide, cerium oxide, ytterbium oxide, and silane (ceramics containing silicon, aluminum, oxygen, and nitrogen). Examples of metal nitrides include boron nitride, aluminum nitride, and silicon nitride.

[0048] (Content of large-particle-size zeolite) In the composition of the third embodiment of the present invention, when the resin composition is a liquid composition, the content of zeolite in the composition according to the first embodiment is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and most preferably 45% by mass or more, relative to the total amount of the liquid composition, based on the consideration of suppressing viscosity increase and reducing the coefficient of thermal expansion. Furthermore, on the other hand, it is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 75% by mass or less, and particularly preferably 70% by mass or less. Furthermore, the content of zeolite (large particle size zeolite) in all fillers is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, even more preferably 70% by mass or more, and most preferably 90% by mass or more, taking into account the smaller viscosity increase during resin mixing and the ease of reducing the coefficient of thermal expansion of the hardened product.

[0049] (Small-diameter inorganic fillers) Small-particle-size inorganic fillers can be zeolite or other inorganic fillers. Specific examples of inorganic fillers other than zeolite are described above. Small-particle-size inorganic fillers, based on the consideration of reducing the coefficient of thermal expansion, are preferably zeolites, metal nitrides, metal oxides, etc.

[0050] From the perspective of easily demonstrating the full effect of the filler, the content of small-particle-size inorganic fillers is preferably higher. On the other hand, from the perspective of improving the fluidity of the liquid composition and facilitating its filling in narrow spaces, the content of small-particle-size inorganic fillers is preferably lower. In particular, because small-particle-size inorganic fillers have a larger specific surface area, their viscosity tends to increase easily; therefore, by reducing the amount used, fluidity can be easily improved. In the composition of the third embodiment of the present invention, the content of small-particle-size inorganic filler is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more, relative to the total amount of the composition. On the other hand, it is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less.

[0051] (Shape of small-particle-size inorganic packings) The shape of small-particle-size inorganic fillers is not particularly limited within the range that the composition and resin composite material can exhibit better performance. They can be spherical, whisker-like, fibrous, plate-like, or aggregates of such materials. Considering the aspect of suppressing the increase of viscosity, spherical shape is preferred. The sphericity of small-particle-size inorganic fillers is preferably 0.6 or higher, more preferably 0.65 or higher, and especially preferably 0.70 or higher. Furthermore, there is no particular upper limit to the sphericity; it can be below 1. Therefore, in the third embodiment of the present invention, the sphericity of both the large-diameter zeolite and the small-diameter inorganic filler is preferably 0.6 or more, more preferably 0.65 or more, and particularly preferably 0.70 or more. Furthermore, it is preferable that the sphericity of the small-diameter inorganic filler is higher than that of the large-diameter zeolite. Furthermore, the roundness of small-particle-size inorganic fillers is preferably 0.786 or higher, more preferably 0.790 or higher, even more preferably 0.795 or higher, even more preferably 0.800 or higher, even more preferably 0.805 or higher, particularly preferably 0.810 or higher, especially preferably 0.815 or higher, and most preferably 0.820 or higher. There is no particular upper limit to the roundness; it can be below 1. Moreover, the methods for determining sphericity and roundness are as described above.

[0052] (Total inorganic filler content) From the perspective of easily demonstrating its effect as a filling material, the total content of all inorganic fillers (all inorganic fillers) contained in the composition is preferably more. On the other hand, from the perspective of the high fluidity of the liquid composition and its ease of filling even in narrow spaces, the total content of all inorganic fillers (all inorganic fillers) contained in the composition is preferably less. Specifically, in the composition of the third embodiment of the present invention, the total content of all inorganic fillers relative to the total amount of the composition is preferably 30% by mass or more, more preferably 35% by mass or more, and particularly preferably 40% by mass or more. On the other hand, it is preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0053] [Fourth Implementation] <Composition> The composition of the fourth embodiment of the present invention contains a resin, a zeolite, and a dispersant having at least one functional group, namely an amine group or an amine salt. Preferably, the zeolite is the zeolite (large particle size zeolite) of the first embodiment described above. The inventors have discovered that when the composition containing epoxy resin and zeolite filler is in a liquid state, dispersants having at least an amine group or an amine salt are superior in terms of viscosity reduction. Therefore, considering the ease of viscosity reduction, the composition of the present invention preferably contains a dispersant having at least an amine group or an amine salt. That is, the dispersant used in the fourth embodiment of the present invention is a dispersant having at least one functional group, either an amine group or an amine salt. Furthermore, considering the viscosity reduction when the composition is in a liquid state, the dispersant preferably has an amine group at the end. The amine salt can be modified by an acid group such as phosphoric acid. In the fourth embodiment of the present invention, by using a specific dispersant, zeolite can be used as an inorganic filler while preventing the viscosity of the liquid composition from increasing.

[0054] (Dispersant) To improve the dispersibility of inorganic fillers such as zeolites, the composition of the fourth embodiment of the present invention contains a dispersant. The dispersant used in the composition containing resin and filler primarily improves the interfacial state and compatibility of the two by adding it to a liquid composition containing resin and filler with significant polarity differences. This results in effects such as reduced viscosity, improved filler dispersibility, filler agglomeration, and prevention of sedimentation.

[0055] As the dispersant in the fourth embodiment, examples include acrylic dispersants and polymeric dispersants. Here, "polymeric dispersant" refers to a dispersant with a weight average molecular weight of 1,000 or higher. Furthermore, the main chain backbone of the polymeric dispersant is not particularly limited; examples include polyurethane backbone, polyacrylic acid backbone, polyester backbone, polyamide backbone, polyimide backbone, and polyurea backbone. For storage stability considerations, polyurethane backbone, polyacrylic acid backbone, and polyester backbone are preferred. Also, the structure of the polymeric dispersant is not particularly limited; examples include random structures, block structures, comb structures, and star structures. Again, for storage stability considerations, block structures or comb structures are preferred.

[0056] Polymer dispersants have structures with polar groups at the ends or within the molecule, and their effectiveness varies depending on the surface polarity of the inorganic filler. Examples of terminal polar groups include carboxyl, amino, phosphate, and hydroxyl groups, while examples of intramolecular structures include esters and aliphatic amides.

[0057] Furthermore, the dispersant is preferably a solvent-free dispersant, especially a solvent-free polymeric dispersant. By ensuring that the dispersant does not contain a solvent, it is possible to prevent the dispersant from evaporating and creating voids during the heat curing of the composition. In this embodiment, considering the reduction of viscosity, the dispersant is preferably a dispersant having at least an amine group or an amine salt. Furthermore, details of the dispersant having at least an amine group or an amine salt are described in Embodiment 6 below.

[0058] Commercially available products can also be used as dispersants. Examples of commercially available polymeric dispersants include: the DISPERBYK series of wetting and dispersing agents sold by BYK-Chemie, namely 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; and those sold by BASF. The EFKA series sold by the Japanese company includes the following models: 4008, 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, and 506. 6. 5070, 5244; Solsperse series sold by Lubrizol, including models 3000, 5000, 11200, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000SC, 24000GR, 26000, 28000, 31845, 32000, 32500, 32550, 32 600, 33000, 34750, 35100, 35200, 36000, 36600, 37500, 38500, 39000, 53095, 54000, 55000, 56000, 71000; DISPARLON series sold by Kusumoto Kasei (Co., Ltd.) including models 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; and Ajisper series PB-711, PB-821, PB-822, PN-411, PA-111 sold by Ajinomoto (stock).The following products are sold by Air Products: Surfynol series (104A, 104C, 104E, 104H, 104S, 104BC, 104DPM, 104PA, 104PG-50, 420, 440, DF110D, DF110L, DF37, DF58, DF75, DF210, CT111, CT121, CT131, CT136, GA, TG, TGE); Olfine series (STG, E1004) sold by Nissin Chemical Industries, Ltd.; SN-SPERSE series (70, 2120, 2190) manufactured by San Nopco, Ltd.; ADEKA NOL and ADEKA TOL series sold by ADEKA, Ltd.; and Sannonic series, NAROACTY CL series, Emulmin series, NEWPOL PE series, IONET M series, and IONET products sold by Sanyo Chemical Industries, Ltd. D series, IONET S series, IONET T series, Sanseparator 100, etc.

[0059] In the fourth embodiment, for example, considering the ease with which the inorganic filler can be uniformly dispersed when the composition is liquid, the content of the dispersant is preferably higher. On the other hand, considering the reduced likelihood of an increase in the coefficient of thermal expansion due to phase separation between the inorganic filler and resins such as epoxy resin, the content of the dispersant is preferably lower. Considering the ease with which the liquid composition can be filled into narrow spaces and the ease with which it can be cured to have a low coefficient of thermal expansion, the content of the dispersant relative to the total amount of the composition is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.1% by mass or more and 25% by mass or less.

[0060] In the above embodiments, when the composition is a liquid composition, the viscosity of the liquid composition is preferably low, considering that it is easy to fill the composition even in narrow spaces. On the other hand, the viscosity of the liquid composition is preferably high, considering that it is less likely to drip when filling the composition. The viscosity of the liquid composition at 23°C is preferably 0.1 Pa·s or more, more preferably 1 Pa·s or more, further 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 200 Pa·s or less, further preferably 150 Pa·s or less, and particularly preferably 30 Pa·s or less.

[0061] As a preferred form of the above composition, it is preferably a liquid composition using epoxy resin as the resin and zeolite of the first embodiment as the zeolite. The viscosity of the liquid composition is preferably 1 Pa·s or more and 30 Pa·s or less. Furthermore, the zeolite content is preferably 40 to 70% by mass. This liquid composition can be used as a bottom filler material and is suitable as a sealant because it can reduce the average coefficient of thermal expansion after hardening.

[0062] When the compositions of embodiments 2 to 4 above are in liquid form, they can be hardened to form resin composite materials. For example, when the resin is epoxy resin, the resin composite material is an epoxy resin composite material. Details of the epoxy resin composite material are described below. Furthermore, when the resin is polyimide resin, the resin composite material is a polyimide resin composite material.

[0063] The average coefficient of thermal expansion of the resin composite material at 25~100°C is preferably 0 ppm / K or higher, more preferably 2 ppm / K or higher, further preferably 4 ppm / K or higher, and especially preferably 10 ppm / K or higher. On the other hand, it is preferably 200 ppm / K or lower, further preferably 100 ppm / K or lower, and especially preferably 30 ppm / K or lower.

[0064] In particular, when epoxy resin is used as the resin and zeolite of the first embodiment is used as the zeolite in the composition of the second embodiment, the content of the zeolite is preferably 40 to 70% by mass, and the average coefficient of thermal expansion of the resin composite material at 25 to 100°C is preferably 10 to 30 ppm / K. This type of resin composite material has a low average coefficient of thermal expansion at temperatures below the glass transition temperature, making it suitable for use in various heat-resistant materials, especially in electronic devices.

[0065] <Resin Composite Materials> In one embodiment of the present invention, the resin composite material can be obtained by curing the above-described composition (the compositions of embodiments 2 to 4). For example, when the resin is epoxy resin, an epoxy resin composite material can be obtained. When the resin is epoxy resin, the composition is preferably a liquid composition. The method for manufacturing the epoxy resin composition and the epoxy resin composite material will be described in detail in the fifth embodiment of the invention described below. Furthermore, when the resin is a polyimide resin, a polyimide resin composite material can be obtained. The manufacturing method of the polyimide resin composite material can be, for example, by the method described below.

[0066] (Manufacturing method of polyimide resin composite material) Polyimide resin composites can be molded using various known thermoplastic resin molding presses. The heating temperature during molding is also affected by the properties of the resin used and is not particularly limited, but is generally above 250°C, preferably above 300°C, more preferably above 350°C, and even more preferably above 390°C. Furthermore, considering the reduced likelihood of resin degradation during the heating and pressing process, it is preferable to use a vacuum pressing device that can reduce the oxygen content in the press during heating, or a pressing device equipped with a nitrogen purging device.

[0067] [Fifth Implementation] <Liquid composition> The liquid composition of the fifth embodiment of the present invention contains epoxy resin and inorganic filler.

[0068] (Inorganic packing) In the liquid composition of the fifth embodiment, zeolite and inorganic fillers other than zeolite are used as inorganic fillers. As inorganic fillers other than zeolite, it is preferable to use the same inorganic fillers as those used in the third embodiment, and the preferred range is also the same as described above, preferably the range described above.

[0069] The liquid composition of the fifth embodiment of the present invention contains inorganic fillers including zeolite with a particle size of 1.0 μm to 10 μm (large particle size zeolite) and inorganic fillers with a particle size of 0.1 μm or more but less than 1.0 μm (small particle size inorganic fillers). Zeolite is an inorganic filler with a low coefficient of thermal expansion, which can reduce the coefficient of thermal expansion of epoxy resin composites, which are hardened components of liquid compositions. However, its specific surface area is large, and if a large quantity is prepared, the viscosity of the liquid composition tends to increase. In this invention, various studies were conducted, and it was found that by including small-particle-size inorganic fillers in addition to large-particle-size zeolite in the liquid composition, the coefficient of thermal expansion of the epoxy resin composite can be reduced while preventing the viscosity from increasing, thus achieving a low-viscosity liquid composition.

[0070] Considering the ease with which liquid compositions can be filled even in confined spaces, the particle size of inorganic fillers is preferably small. On the other hand, considering the likelihood that the viscosity of the liquid composition will not increase, the particle size of inorganic fillers is preferably large. When fillers with smaller and larger specific surface areas are used together, a larger specific surface area increases the interaction between the filler and the resin, making it easier for the viscosity of the liquid composition to increase. Therefore, to reduce the viscosity of the liquid composition, it is preferable that the specific surface area of ​​the filler is small. Regarding specific surface area, the smaller the particle size, the easier it is to increase. Furthermore, the specific surface area also varies depending on the shape of the filler; a spherical filler has the smallest specific surface area. Therefore, considering the reduction of viscosity, inorganic fillers are preferably nearly spherical in shape and have the largest particle size. Therefore, particularly for large-particle-size zeolites, the specific surface area is preferably 1×10⁻⁶ ( / m) or less, and more preferably 0.8×10⁻⁶ ( / m) or less. In this invention, by using both small-particle-size and large-particle-size fillers, small particles can enter the gaps between large particles, the filling amount can be increased, the coefficient of thermal expansion can be reduced, and the increase in viscosity can also be reduced. The particle size of inorganic fillers such as zeolites refers to the particle size of each individual particle, meaning the diameter of the largest circle (circle equivalent diameter) with an area equal to the projected area of ​​the particle when observed using a scanning electron microscope (SEM). Furthermore, the particle size refers to the diameter of the primary particles.

[0071] (Content of large-particle-size zeolite) In the liquid composition of the fifth embodiment of the present invention, the content of large-particle-size zeolite is preferably more, considering that it is easier to exhibit the effect of reducing the average coefficient of thermal expansion. On the other hand, the content of large-particle-size zeolite is preferably less, considering that it improves the fluidity of the liquid composition and makes it easier to fill even in narrow spaces. Specifically, the content of large-particle-size zeolite relative to the total amount of the liquid composition is preferably 20% by mass or more, more preferably 25% by mass or more, and particularly preferably 30% by mass or more. Furthermore, the content of large-particle-size zeolite is preferably 80% by mass or less, more preferably 75% by mass or less, and particularly preferably 70% by mass or less.

[0072] (Small-diameter inorganic fillers) Small-particle-size inorganic fillers can be zeolite or other inorganic fillers. Specific examples of inorganic fillers other than zeolite are as described above. Considering the reduction of the coefficient of thermal expansion, small-particle-size inorganic fillers are preferably zeolites, metal nitrides, metal oxides, etc.

[0073] Considering the ease with which the filler's performance can be fully demonstrated, a higher content of small-particle-size inorganic fillers is preferable. On the other hand, considering the improvement of the fluidity of the liquid composition and its ease of filling narrow spaces, a lower content of small-particle-size inorganic fillers is preferable. In particular, because small-particle-size inorganic fillers have a larger specific surface area, their viscosity tends to increase easily; therefore, by reducing the amount used, fluidity can be improved more readily. In the liquid composition of the fifth embodiment of the present invention, the content of small-particle-size inorganic filler is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more, relative to the total amount of the liquid composition. On the other hand, it is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less.

[0074] (Zeolite) The zeolite used in this invention will be described in more detail below. Furthermore, unless otherwise specified, the following description pertains to large-particle-size zeolite. When using zeolite other than large-particle-size zeolite as an inorganic filler, the features other than particle size are preferably as described below. For example, when using zeolite as a small-particle-size inorganic filler, the zeolite used as a small-particle-size inorganic filler also preferably has the features described below. The same applies to the zeolite in embodiments 6 and 7 described below. Furthermore, the zeolite of the first embodiment described above is preferred as a large-particle-size zeolite.

[0075] (Structure of zeolite) Zeolites are compounds composed of silicon or aluminum and oxygen, and are based on the TO 4 unit (T is the element that forms the framework other than oxygen). Specifically, examples of zeolites include crystalline porous aluminosilicate, crystalline porous aluminum phosphate (ALPO), or crystalline porous silica aluminum phosphate (SAPO). Zeolites are composed of structural units called composite building units (CBUs), which are formed by connecting several (to dozens) TO 4 units. Therefore, zeolites have regular channels (tubular pores) and cavities (hollows). The crystal structure of CBU or the following zeolites can be represented by the coding system established by the International Zeolite Association (IZA). Alternatively, the zeolite structure can be identified using the 2018 version of the Zeolite Structure Database (http: / / www.iza-structure.org / databases / ) based on X-ray diffraction patterns obtained using an X-ray structure analysis device (e.g., the D2PHASER desktop X-ray diffraction device manufactured by BRUKER).

[0076] (Composition of zeolite) The zeolite of this invention is not particularly limited in form as long as it does not impair the effects of this invention. However, considering its suitability for use as a filler, it is preferably an aluminum silicate with a framework structure containing at least aluminum and silicon atoms. A single type of zeolite may be used alone, or two or more types may be used in any combination and ratio.

[0077] (The skeleton of zeolite) The zeolite framework is not particularly limited to the range of properties that are preferred in the liquid composition and the epoxy resin composite material obtained by curing the liquid composition described below. Considering the ease of obtaining an epoxy resin composite material with a low coefficient of thermal expansion by curing the liquid composition, the zeolite framework is preferably a CBU containing at least one of d6r and mtw (Mobil TWelve) structures, and more preferably has d6r. Specifically, the liquid composition and epoxy resin composite material preferably contain zeolite with the aforementioned preferred structure at least 1% by mass and epoxy resin as a (CBU).

[0078] Examples of zeolites with d6r as a 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 -WEN type structures. Examples of zeolites with mtw as CBU include *BEA, BEC, CSV, GON, ISV, ITG, *-ITN, IWS, MSE, MTW, SFH, SFN, SSF, *-SSO, UOS, and UOV type structures. To achieve a three-dimensional interaction with a portion of the epoxy groups contained in the epoxy resin, zeolites with three-dimensional channels are preferred. Examples include zeolites with structures such as AEI, AFT, AFX, *BEA, BEC, CHA, EMT, ERI, FAU, GME, ISV, ITG, *-ITN, IWS, JSR, KFI, MOZ, MSE, OFF, SAT, SAV, SBS, SBT, SFW, SZR, TSC, UOS, UOV, and -WEN. Among these, zeolites with an oxygen octet or smaller structure are preferred, especially considering ease of particle size control. Examples of zeolites with an oxygen octet or smaller structure include AEI, AFT, AFX, CHA, ERI, KFI, SAT, SAV, SFW, and TSC type structures. Among these, zeolites with AEI, AFX, CHA, and ERI type structures are preferred, especially those with a CHA structure, considering structural stability even with shape control. Furthermore, in this specification, an oxygen octet structure means a structure in which the number of oxygen elements is 8, where the pores formed by oxygen and T elements (elements other than oxygen constituting the framework) that make up the zeolite framework are at most composed of oxygen and T elements.

[0079] (Average thermal expansion coefficient of zeolite) The average coefficient of thermal expansion of zeolite is not particularly limited to a range within which the liquid composition and the epoxy resin composite material obtained by curing the liquid composition exhibit better performance. Considering that a small amount can easily reduce the average coefficient of thermal expansion of the liquid composition and the epoxy resin composite material, the average coefficient of thermal expansion of zeolite is preferably low. Furthermore, considering that a smaller amount can better suppress the increase in viscosity of the liquid composition caused by the addition of fillers, the average coefficient of thermal expansion of zeolite is also preferably low. Therefore, the average coefficient of thermal expansion of zeolite is typically less than 0 ppm / K, preferably less than -2 ppm / K, more preferably less than -3 ppm / K, further preferably less than -5 ppm / K, particularly preferably less than -6 ppm / K, and most preferably less than -8 ppm / K.

[0080] On the other hand, considering the smaller difference in average thermal expansion coefficient between zeolite and resin, and the less likely zeolite and resin to separate, the average thermal expansion coefficient of zeolite is preferably higher. Therefore, the average thermal expansion coefficient of zeolite is typically -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. That is, if the average coefficient of thermal expansion of zeolite is within the above-mentioned range, the viscosity increase of the liquid composition can be suppressed, making it easier to fill the gaps between various constituent components, and the average coefficient of thermal expansion of the cured epoxy resin composite material can be reduced. Furthermore, the average coefficient of thermal expansion of zeolite can be determined by calculating the lattice constant using the "D8ADVANCE" X-ray diffraction device manufactured by BRUKER Corporation and the X-ray diffraction analysis software "JADE".

[0081] (The shape of zeolite) The shape of the zeolite is not particularly limited within the range where it exhibits better performance in liquid compositions and epoxy resin composites. It can be spherical, whisker-like, fibrous, plate-like, or aggregates of such materials. Spherical is preferred, considering the ease of suppressing viscosity increase. The ideal sphericity of zeolite is 0.6 or higher, even better is 0.65 or higher, and exceptionally good is 0.70 or higher. However, there is no specific upper limit to the sphericity; it can be below 1. Furthermore, in this specification, "true sphericity" is defined as "the ratio of the smallest diameter to the largest diameter of a particle." Fifty zeolites contained in a liquid composition or epoxy resin composite were randomly selected, and their true sphericity was measured, with the average value taken. The largest and smallest diameters can be determined by observation using a scanning electron microscope (SEM). Furthermore, as described in the first embodiment above, the true sphericity of large-diameter zeolites can be within the aforementioned range.

[0082] (Zeolite structure density) The zeolite's structure density is not particularly limited as long as it does not impair the effects of the present invention. Considering the ease with which zeolite structural vibrations occur and the tendency for its average coefficient of thermal expansion to decrease, the zeolite's structure density is preferably low. Therefore, the zeolite's structure density is preferably 17.0 T / 1000 ų or less, and more preferably 16.0 T / 1000 ų or less. On the other hand, considering the ease with which zeolite can increase structural stability, a relatively high zeolite structure density is preferable. A zeolite structure density of 12.0 T / 1000 ų or higher is preferred, more preferably 13.0 T / 1000 ų or higher, and even more preferably 14.0 T / 1000 ų or higher is also preferred. If the structure density is within the above range, zeolite can be used as a stabilizing filler. Furthermore, the structure density represents 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, values ​​from the 2017 edition of the IZA Zeolite Structure Database (http: / / www.iza-structure.org / databases / ) may be used.

[0083] Examples of zeolites with a structure density greater than 16.0 T / 1000 Å3 and less than 17.0 T / 1000 Å3 include zeolites with structures of the CSV, ERI, ITG, LTL, LTN, MOZ, MSE, OFF, SAT, SFH, SFN, SSF, *-SSO, and -WEN types. Examples of zeolites with a structure density greater than 15.0 T / 1000 Å3 and less than 16.0 T / 1000 Å3 include zeolites with structures of the AEI, AFT, AFV, AFX, AVL, *BEA, BEC, EAB, GME, *-ITN, LEV, MWW, and SFW types. Examples of zeolites with a structure density greater than 14.0 T / 1000 Å3 and less than 15.0 T / 1000 Å3 include zeolites with CHA, ISV, IWS, KFI, SAS, and SAV structures. Examples of zeolites with a structure density below 14.0 T / 1000 Å3 include zeolites with EMT, FAU, JSR, SBS, SBT, and TSC structures.

[0084] (Silicon dioxide of zeolite / Mohr's ratio of alumina (SAR)) The molar ratio of silicon dioxide to aluminum oxide in zeolite (sometimes referred to as "SAR", "Si / Al2 molar ratio", or "Si / Al2 ratio") is not particularly limited as long as it does not impair the effects of the present invention. Considering the improved moisture resistance of epoxy resin composites and the ease of controlling the amount of counteracting cations, a higher SAR (Si / Al2 ratio) for zeolite is preferred. Therefore, the SAR (Si / Al2 ratio) of zeolite is typically 2 or higher, preferably 3 or higher, more preferably 3.5 or higher, even more preferably 4 or higher, particularly preferably 4.5 or higher, and most preferably 5 or higher. On the other hand, considering the ease of manufacturing at a low cost, the SAR (Si / Al2 ratio) of zeolite is preferably low. Therefore, the SAR (Si / Al2 ratio) of zeolite is typically below 2000, preferably below 1000, more preferably below 500, and even more preferably below 100. If the Si / Al2 ratio is within the above range, it is easier to control the amount of counteracting cations, and the manufacturing cost of zeolite can also be lower.

[0085] Furthermore, when using elements such as gallium, iron, boron, titanium, zirconium, tin, zinc, and phosphorus to replace silicon and aluminum, the molar ratio of the oxide of the substituted element can be converted to the molar ratio of aluminum oxide or silicon dioxide. Specifically, when using gallium to replace aluminum, the molar ratio of gallium oxide can be converted to the molar ratio of aluminum oxide. The Si / Al2 ratio of zeolite can be adjusted according to the type and ratio of silicon-containing and aluminum-containing compounds in the raw materials, the type and amount of structure-defining agents, the use of seed crystals, and synthesis conditions such as temperature or time.

[0086] (Countercations of zeolite) The countercation of zeolite is not particularly limited as long as it does not impair the effects of the present invention. The countercation of zeolite is typically a structural prestressing agent, a proton, an alkali metal ion, or an alkaline earth metal ion; preferably, a structural prestressing agent, a proton, or an alkali metal ion; and more preferably, a structural prestressing agent, a proton, a Li ion, a Na ion, or a K ion. When the countercation of zeolite is a structural prestressing agent, it is more flexible than alkali metal ions or alkaline earth metal ions, thus making it easier for zeolite to exhibit an average coefficient of thermal expansion below 0 ppm / K, which is preferable. Furthermore, the smaller the size of the alkali metal ions or alkaline earth metal ions, the easier it is for zeolite to exhibit an average coefficient of thermal expansion below 0 ppm / K, which is also preferable. In particular, when the countercation of zeolite is a proton, it is easier to reduce the average coefficient of thermal expansion of the resin composite material, which is also preferable. That is, as a zeolite, it is preferable to be as-made (including structurally defined formulations), proton-type, or alkali metal-type, and more preferably as-made, proton-type, Li-type, Na-type, or K-type. Furthermore, the structurally defined agent refers to the template used in the manufacture of the zeolite.

[0087] (Crystallization degree of zeolite) The crystallinity of the zeolite is not particularly limited as long as it does not impair the effects of this invention. This is presumably because, compared to the structure determined by coding in IZA, the Composite Building Unit (CBU) has a greater impact on the average coefficient of thermal expansion of epoxy resin composites. Furthermore, the crystallinity of the zeolite can be determined by comparing it with the X-ray diffraction peak of a zeolite based on a specific X-ray diffraction peak, obtained using an X-ray diffraction apparatus (e.g., the D2PHASER desktop X-ray diffraction apparatus manufactured by BRUKER). As a concrete example of calculation, the crystallinity of LTA-type zeolite can be cited in Scientific Reports 2016, 6, Article number: 29210.

[0088] (Surface treatment of zeolite) Zeolite can undergo surface treatments such as silanization without compromising the effectiveness of this invention. Such surface treatments are not limited to physical or chemical treatments.

[0089] (Method for manufacturing zeolite) The manufacturing method of zeolite can be any known method. For example, in the case of manufacturing CHA-type zeolite, the method described in Japanese Patent Application Publication No. 2009-097856 can be used. In the case of manufacturing zeolite with larger particle size, hydrothermal synthesis can be carried out by appropriately controlling the type and ratio of raw materials, synthesis time, or temperature. Specifically, for example, zeolite with larger particle size can be manufactured by increasing the amount of water used in synthesis and diluting the concentration of raw materials, as described in Microporous and Mesoporous Materials 21 (1998) 24.

[0090] (Shape of small-particle-size inorganic packings) The shape of small-particle-size inorganic fillers is not particularly limited within the range where liquid compositions and resin composites exhibit better performance. They can be spherical, whisker-like, fibrous, plate-like, or aggregates of the like. Spherical is preferred, considering the aspect of suppressing viscosity increase. The sphericity of small-particle-size inorganic fillers is preferably 0.6 or higher, more preferably 0.65 or higher, and especially preferably 0.70 or higher. Furthermore, there is no particular upper limit to the sphericity; it can be below 1. Therefore, in the fifth embodiment of the present invention, the sphericity of both the large-diameter zeolite and the small-diameter inorganic filler is preferably 0.6 or more, more preferably 0.65 or more, and particularly preferably 0.70 or more. Furthermore, it is preferable that the sphericity of small-particle-size inorganic fillers is higher than that of large-particle-size zeolites.

[0091] (Total inorganic filler content) Considering the ease with which it can demonstrate its effect as a filler material, the total content of all inorganic fillers (all inorganic fillers) contained in the liquid composition is preferably more. On the other hand, considering the high fluidity of the liquid composition and its ease of filling even in narrow spaces, the total content of all inorganic fillers (all inorganic fillers) contained in the liquid composition is preferably less. Specifically, in the liquid composition of the fifth embodiment of the present invention, the total content of all inorganic fillers relative to the total amount of the composition is preferably 30% by mass or more, more preferably 35% by mass or more, and particularly preferably 40% by mass or more. On the other hand, it is preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0092] (Epoxy resin) As the epoxy resin used in this invention, considering that the coefficient of thermal expansion of the epoxy resin composite material obtained by curing the liquid composition is easily reduced, it is preferable to use an epoxy compound having an aromatic ring such as a bisphenol A backbone, a bisphenol F backbone, or a biphenyl backbone. Specifically, examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, epoxy resin containing a naphthalene ring, epoxy resin having a dicyclopentadiene skeleton, phenolic varnish type epoxy resin, cresol phenolic varnish type epoxy resin, triphenylmethane type epoxy resin, aminophenol type epoxy resin, aliphatic epoxy resin, and copolymer epoxy resin of aliphatic epoxy resin and aromatic epoxy resin. Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, epoxy resin containing a naphthalene ring, and aminophenol type epoxy resin are preferred. More preferably, bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy resin containing a naphthalene ring, aminophenol type epoxy resin, and biphenyl type epoxy resin are used.

[0093] Considering the ease with which the glass transition temperature of the epoxy resin composite material obtained by thermosetting the liquid composition can be increased, it is preferable to use a multifunctional epoxy resin. As a multifunctional epoxy resin, glycidyl ether-type multifunctional epoxy resins, such as epoxy resins made from various phenols or various phenolic compounds and epihaloalcohols, are preferred. The various phenols include phenolic varnish resins, cresol varnish resins, bisphenol A varnish resins, dicyclopentadiene phenol resins, phenol aralkyl resins, naphthol varnish resins, biphenyl varnish resins, terpene phenol resins, heavy oil-modified phenol resins, etc. The various phenolic compounds are polyphenol resins obtained by the condensation reaction of various phenols with aldehydes such as hydroxybenzaldehyde, crotonaldehyde, and glyoxal.

[0094] The epoxy resin used in this invention preferably has a viscosity of less than 5 Pa·s at 23°C, and more preferably 0.1 to 3 Pa·s, considering its flowability. The viscosity determination method for epoxy resin is specified in JIS K 7233 (1986), with the single-cylinder rotational viscometer method being more suitable. The viscosity of the epoxy resin used in this invention at 23°C can be measured using a Type B rotational viscometer ("LVDV-1 Pri", manufactured by Brookfield Company, shaft: S62), which is one method of the single-cylinder rotational viscometer method.

[0095] From a viscosity control perspective, the epoxy equivalent of the epoxy resin is preferably 50 g / equivalent to 500 g / equivalent or less, and more preferably 90 g / equivalent to 150 g / equivalent or less. From an excellent heat resistance perspective, a higher epoxy equivalent is preferred. On the other hand, from the perspective that a lower melting point or lower viscosity of the epoxy resin leads to better filling properties in the liquid composition and easier attainment of better bonding through filling, a lower epoxy equivalent is preferred. Epoxy resins can be used alone, or two or more can be mixed in any combination and ratio. In the case of mixing, the epoxy equivalent refers to the equivalent of the mixture.

[0096] Considering the relatively higher content of inorganic fillers and the ease with which the coefficient of thermal expansion is reduced, the epoxy resin content in the liquid composition of the present invention is preferably low. On the other hand, considering the ease with which the excellent physical properties of epoxy resin are maintained, the epoxy resin content in the liquid composition of the present invention is preferably high. Specifically, relative to the total amount of the composition, it is preferably 5% by mass or more, and more preferably 10% by mass or more. On the other hand, it is preferably 50% by mass or less, more preferably 25% by mass or less, and particularly preferably 15% by mass or less.

[0097] (hardener) The liquid composition of the present invention preferably further comprises a curing agent. A curing agent refers to a substance that facilitates the crosslinking reaction between the crosslinking groups of the epoxy resin. There are no particular limitations on the type of curing agent used; those commonly known as epoxy resin curing agents can be used. Examples include phenolic curing agents, aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and other amine-based curing agents, acid anhydride curing agents, amide-based curing agents, tertiary amines, imidazoles and their derivatives, organophosphorus compounds, phosphonium salts, tetraphenylborates, organic acid diacetylhydrazine, boron halide amine complexes, polythiol curing agents, isocyanate curing agents, end-capped isocyanate curing agents, and dicyandiamine compounds. Considering the imparting of flowability and rapid curing properties, acid anhydride curing agents are preferred.

[0098] 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 ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenolic varnishes, bisphenol A phenolic varnishes, o-cresol phenolic varnishes, m-cresol phenolic varnishes, p-cresol phenolic varnishes, xylenol phenolic varnishes, poly(p-hydroxystyrene), hydroquinone, resorcinol, catechol, and tert-hydroxystyrene. Butylcatechol, tert-butylhydroquinone, phloroglucinol, phloroglucinol, tert-butylcatechol, allylated phloroglucinol, polyallylated phloroglucinol, 1,2,4-phenylpyroglucinol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allylated or polyallylated forms of the above-mentioned dihydroxynaphthalenes, allylated bisphenol A, allylated bisphenol F, allylated phenolic varnishes, allylated phloroglucinol, etc.

[0099] Specific examples of amine-based curing agents, as aliphatic amines, include ethylenediamine, 1,3-propanediamine, 1,4-propanediamine, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethyltriamine, iminodipropylamine, bis(hexamethylene)triamine, triethyltetramine, tetraethylpentamine, pentaethylhexamine, N-hydroxyethylethylenediamine, tetra(hydroxyethyl)ethylenediamine, etc. Examples of polyetheramines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propylamine), polyoxypropylene diamine, and polyoxypropylene triamine. Examples of alicyclic amines include isophorone diamine, montanane diamine, 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 norcamphene diamine. Examples of aromatic amines include tetrachloro-p-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 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-diaminodiphenylamine, 4,4'-diaminodiphenylamine, m-aminophenol, m-aminobenzylamine, dimethylbenzylamine, 2-dimethylaminomethylphenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl)ethylamine, diaminodiethyldimethyldiphenylmethane, α,α'-bis(4-aminophenyl)-p-diisopropylbenzene, etc.

[0100] Specific examples of anhydride-based curing agents include dodecenyl succinic anhydride, polyadipic anhydride, polyazelic anhydride, polydecanediic anhydride, poly(ethyl octadecanoic acid) anhydride, poly(phenyl hexadecanoic acid) anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl dicycloheptenyl dicarboxylic anhydride, tetrahydrophthalic anhydride, trialkyl tetrahydrophthalic anhydride, methyl cyclohexene dicarboxylic anhydride, methyl cyclohexene tetracarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and diphenyl sulfide. Benzene tetracarboxylic anhydride, ethylene glycol bis(p-phenylenetriol) dianhydride, chlorobrittle anhydride, terpenoid anhydride, methylterpenoid anhydride, 5-(2,5-dioxytetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dimethyl-6-(2-methyl-1-propenyl)-4-cyclohexene-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthous succinic anhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthous succinic anhydride, etc.

[0101] Examples of amide-based curing agents include dicyandiamide and polyamide resins. Examples of tertiary amines include 1,8-diazabicyclo(5,4,0)undecene-7, triethyldiamine, dimethylbenzylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, etc. Examples of imidazoles and their derivatives include 1-cyanoethyl-2-phenylimidazolium, 2-phenylimidazolium, 2-ethyl-4(5)-methylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyano-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium ontyl trimellitate, and 2,4-diamino-6-[2'-methylimidazolium-(1 [1']-Ethyl-symmetric triazole, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-symmetric triazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-symmetric triazole isocyanate adduct, 2-phenylimidazolyl isocyanate adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, and epoxy resin adducts of the above imidazoles or polymeric encapsulated imidazoles, etc.

[0102] Examples of organophosphorus compounds include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine. Examples of phosphonium salts include tetraphenylphosphine tetraphenylboronic acid, tetraphenylphosphine tetraethyltriphenylboronic acid, and tetrabutylphosphine tetrabutylboronic acid. Examples of tetraphenylborates include 2-ethyl-4-methylimidazolium tetraphenylborate and N-methylmorpholine tetraphenylborate. These hardeners can be used alone, or two or more can be mixed in any combination and ratio.

[0103] Regarding the content of the hardener in the case where the liquid composition of the present invention contains a hardener, considering that it is less likely to produce effects caused by the residue of unreacted epoxy groups or functional groups of the hardener, when the hardener is a phenolic hardener, an amine hardener, or an anhydride hardener, the content of the hardener is preferably in the range of 0.8 to 2.0, and more preferably in the range of 0.8 to 1.5, based on the equivalent ratio of epoxy groups in the epoxy resin to functional groups in the hardener (functional groups in the hardener / epoxy groups in the epoxy resin).

[0104] When the curing agent is an amide-based curing agent, a tertiary amine, imidazole and its derivatives, organophosphorus compounds, phosphonium salts, tetraphenylborates, organic acid diazonium, boron halide amine complexes, polythiol-based curing agents, isocyanate-based curing agents, or end-capped isocyanate curing agents, the amount of curing agent relative to 100 parts by weight of epoxy resin is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more. On the other hand, it is preferable to use 20 parts by weight or less, more preferably 10 parts by weight or less. When the curing agent is a dicyandiamine compound, the amount of curing agent relative to 100 parts by weight of epoxy resin is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more. On the other hand, it is preferable to use 10 parts by weight or less, more preferably 6 parts by weight or less.

[0105] (Dispersant) To improve the dispersibility of inorganic fillers, the liquid composition of the fifth embodiment of the present invention may contain a dispersant. The dispersant used in the liquid composition containing resin and filler primarily improves the interfacial state and compatibility of the two components by adding it to the liquid composition containing resin and filler with a large polarity difference. This results in effects such as reduced viscosity, improved filler dispersibility, filler agglomeration, and prevention of sedimentation.

[0106] As a dispersant, the same dispersant used in the composition of embodiment 4 can be used, preferably commercially available products as well.

[0107] In the fifth embodiment, the content of the dispersant is preferably more abundant, considering that it facilitates the uniform dispersion of the inorganic filler in the liquid composition. On the other hand, the content of the dispersant is preferably less abundant, considering that it is less likely to cause an increase in the coefficient of thermal expansion due to phase separation between the inorganic filler and the epoxy resin. Considering that it is easy to fill narrow spaces with the liquid composition and easy to harden it to have a low coefficient of thermal expansion, the content of the dispersant relative to the total amount of the liquid composition is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.1% by mass or more and 25% by mass or less.

[0108] (Reactive diluent) The liquid composition of this invention may contain a reactive diluent. There are no particular limitations on the reactive diluent, 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 used previously as a reactive diluent for adjusting the viscosity of epoxy resin compositions. Monofunctional epoxy compounds are broadly classified into aliphatic monofunctional epoxy compounds and aromatic monofunctional epoxy compounds; for viscosity considerations, aromatic monofunctional epoxy compounds are preferred.

[0109] (Other additives) In addition to the above, the liquid composition may also contain other additives selected from coupling agents, ultraviolet light inhibitors, antioxidants, plasticizers, flame retardants, colorants, flow improvers, defoamers, ion scavengers, etc.

[0110] Furthermore, in this embodiment, the liquid composition is preferably solvent-free. By being solvent-free, it is possible to prevent the formation of voids due to solvent evaporation during heat curing of the liquid composition. Moreover, the term "solvent-based volatile components" 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 relative to the total amount of the liquid composition is preferably less than 3% by mass, more preferably less than 1% by mass, and most preferably 0% by mass.

[0111] (Viscosity of the liquid composition) The liquid composition is a composition that is fluid at room temperature (23°C). Considering the ease with which the composition can be filled even in confined spaces, the viscosity of the liquid composition of the fifth embodiment of the present invention is preferably low. On the other hand, considering the reduced likelihood of dripping during filling, the viscosity of the liquid composition of the fifth embodiment of the present invention is preferably high. The viscosity of the liquid composition at 23°C is preferably 0.1 Pa·s or more, more preferably 1 Pa·s or more, further 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 200 Pa·s or less, further preferably 150 Pa·s or less, and particularly preferably 30 Pa·s or less. The viscosity of the liquid composition can be measured using the same method as that used for measuring the viscosity of epoxy resin described above. The viscosity of the liquid composition used in this invention at 23°C can be measured using a Type B rotational viscometer, which is one method of single-cylinder rotational viscometer measurement. For example, the Type B rotational viscometer described in the examples can be used.

[0112] (Average coefficient of thermal expansion) Considering that epoxy resin composite materials are less prone to deformation due to ambient temperature or heat generation, the average coefficient of thermal expansion (CTE1) of the liquid composition of the fifth embodiment of the present invention, when formed into a hardened product, is preferably low. On the other hand, considering that it is less likely to cause damage due to the difference in average thermal expansion with surrounding components, it is preferably close to the average coefficient of thermal expansion of the surrounding components. Therefore, when the liquid composition is used as an underfill material in the manufacture of semiconductor devices, it is preferably close to the average coefficient of thermal expansion of the semiconductor substrate (e.g., 3~4 ppm / K). Based on the above considerations, when the liquid composition of the fifth embodiment of the present invention is made into a hardened product, the average coefficient of thermal expansion (CTE1) is preferably 0 ppm / K or more, more preferably 2 ppm / K or more, further preferably 4 ppm / K or more, and especially preferably 10 ppm / K or more. On the other hand, it is preferably 200 ppm / K or less, further preferably 100 ppm / K or less, and especially preferably 30 ppm / K or less.

[0113] Furthermore, regarding the average coefficient of thermal expansion (CTE1) and the glass transition temperature (Tg) of the cured product obtained by curing the liquid composition, the average CTE1 can be determined for epoxy resin composite materials (cured products) obtained by curing the liquid composition to a gel content of 80% or more. The average CTE1 is determined according to JIS K7197 (2012) by measuring the temperature change of the sample length change at 25~100°C using the compression method of thermomechanical analysis, and obtaining the CTE1 from the slope of its tangent. The specific measurement conditions for the average CTE1 are as described in the examples.

[0114] (Glass transfer temperature) There is no particular limitation on the glass transition temperature (Tg) of the epoxy resin composite material obtained by curing the liquid composition of the fifth embodiment of the present invention. For example, when the Tg of the underfill material is high, the protection of the bumps at high temperatures by the sealing part of the underfill material is higher, and the thermal cycling resistance is excellent, which is better (for example, see Japanese Patent Application Publication No. 2017-110146). Based on this consideration, the glass transition temperature (Tg) of the cured product obtained by curing the liquid composition of the fifth embodiment is preferably 50°C or higher, and more preferably 80°C or higher. Furthermore, if the glass transition temperature is below 150°C, the warpage at room temperature (23°C) tends to be less pronounced. Therefore, the glass transition temperature (Tg) is preferably 50~150°C, and more preferably 80~150°C. Moreover, the glass transition temperature (Tg) can be measured using a thermomechanical analysis (TMA) apparatus. Specifically, it can be measured using the method described in the examples.

[0115] (Method for manufacturing liquid composition) The liquid composition of the fifth embodiment of the present invention can generally be obtained by mixing and kneading epoxy resin, inorganic filler, hardener, dispersant, reactive diluent, and other additives as needed using a vacuum mixer, mixing roller, planetary mixer, etc., and defoaming as needed. The order of mixing these components is arbitrary, as long as there are no special problems such as reaction or precipitation. Any two or three or more components can be mixed in advance, and then the remaining components can be mixed, or all components can be mixed at once. Furthermore, for example, by using zeolite with a particle size of 1.0 μm to 10 μm and inorganic filler with a particle size of 0.1 μm to 1.0 μm as raw materials for manufacturing a liquid composition, the liquid composition can contain large-particle-size zeolite and small-particle-size inorganic filler produced by the above method, or it can contain large-particle-size zeolite and small-particle-size inorganic filler produced by other methods.

[0116] <Epoxy Resin Composite Materials> The epoxy resin composite material of the fifth embodiment of the present invention can be obtained by curing the above-mentioned liquid composition. The epoxy resin composite material of the fifth embodiment contains epoxy resin and inorganic fillers. The inorganic fillers include zeolite with a particle size of 1.0 μm to 10 μm (large-particle-size zeolite) and inorganic fillers with a particle size of 0.1 μm or more but less than 1.0 μm (small-particle-size inorganic fillers). The epoxy resin composite material of the fifth embodiment can be manufactured from a liquid composition containing large-particle-size zeolite and small-particle-size inorganic fillers, resulting in a lower coefficient of thermal expansion and lower viscosity.

[0117] In the epoxy resin composite material of the fifth embodiment of the present invention, the epoxy resin and inorganic filler are as described above. Furthermore, in addition to the epoxy resin and inorganic filler, the epoxy resin composite material may also appropriately contain components contained in the liquid composition. Moreover, except that the total amount of the epoxy resin composite material is used as a basis instead of the total amount of the liquid composition, the content of each component in the epoxy resin composite material is as described above. Furthermore, the epoxy resin composite material preferably has a curing gel fraction of 80% or more, and preferably is cured by the curing agent contained in the aforementioned liquid composition.

[0118] The average coefficient of thermal expansion (CTE1) and glass transition temperature of the epoxy resin composite material according to the fifth embodiment of the present invention are within the same range as those described above, based on the same considerations. Furthermore, the average coefficient of thermal expansion and glass transition temperature can be measured on the epoxy resin composite material using the methods described above.

[0119] (Manufacturing method of epoxy resin composite material) Epoxy resin composites can be obtained by curing a liquid composition. Curing is preferably achieved by heating. There are no particular limitations on the manufacturing method of epoxy resin composites within the range where the epoxy resin composite exhibits superior properties; known methods can be used appropriately based on the formulation and composition of the liquid composition.

[0120] For example, epoxy resin composite materials are preferably formed by filling the gaps between the constituent components of various articles such as electronic devices with a liquid composition and then curing the liquid composition to form a shape. Alternatively, epoxy resin composite materials can also be formed by coating the liquid composition onto the constituent components of various articles and then curing the liquid composition to form a shape. Furthermore, the liquid composition can also be molded by hardening it into a desired shape, for example, by being contained in a mold. In the manufacture of such molded articles, injection molding, injection compression molding, extrusion molding, or compression molding can be used. Furthermore, the molding and hardening of epoxy resin composites can be carried out under the hardening temperature conditions of each method. Also, epoxy resin composites can be obtained by cutting the hardened liquid composition into the desired shape. The heating temperature during thermosetting is also affected by the hardener used and is not particularly limited, but is generally above 30°C, preferably above 50°C, more preferably above 60°C, and even more preferably above 80°C. On the other hand, the heating temperature is generally below 400°C, preferably below 350°C, more preferably below 300°C, and even more preferably below 250°C. If the curing temperature is within the above range, high-quality resin composite materials can be easily obtained in a short time.

[0121] [Sixth Implementation] Next, the sixth embodiment of the present invention will be described. The liquid composition of the sixth embodiment of the present invention contains epoxy resin, inorganic filler, and dispersant, and at least contains zeolite as the inorganic filler. The components contained in the liquid composition of the sixth embodiment of the present invention, except for epoxy resin, inorganic filler, zeolite, and dispersant, are the same as those in the composition of the fifth embodiment of the present invention. In this embodiment, a dispersant having at least one functional group, either an amine group or an amine salt, is used as the dispersant.

[0122] (Dispersant) The inventors have discovered that dispersants having at least an amine group or an amine salt are superior in reducing viscosity in liquid compositions containing epoxy resin and zeolite filler. Therefore, the dispersant used in the sixth embodiment of the present invention is a dispersant having at least one functional group, either an amine group or an amine salt. Furthermore, considering the reduction in viscosity of the liquid composition, the dispersant preferably has an amine group at the end. The amine salt can be modified with an acid group such as phosphoric acid. In the sixth embodiment of the present invention, by using a specific dispersant, zeolite can be used as an inorganic filler while preventing the viscosity of the liquid composition from increasing.

[0123] The dispersant is preferably a polymeric dispersant, the details of which are described above. For storage stability considerations, a block or comb structure is particularly preferred. Furthermore, the dispersant is preferably a solvent-free, solvent-free dispersant, especially a solvent-free polymeric dispersant. In the sixth embodiment, commercially available products can also be used as dispersants. As commercially available products, dispersants exemplified in the fifth embodiment above, which have at least one functional group, such as an amine group or an amine salt, can be used.

[0124] The content of the dispersant is the same as in embodiment 5.

[0125] Except for particle size and content, the zeolite in the liquid composition of the sixth embodiment is the same as the zeolite contained in the liquid composition of the fifth embodiment. The zeolite contained in the liquid composition is not particularly limited, but its particle size is preferably 0.1 μm to 10 μm, and more preferably 1 μm to 10 μm. By increasing the particle size of the zeolite contained in the liquid composition, the increase in viscosity of the liquid composition can be further suppressed. The zeolite content in the liquid composition of the sixth embodiment is preferably 20% by mass or more, more preferably 25% by mass or more, more preferably 30% by mass or more, particularly preferably 40% by mass or more, especially preferably 45% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, more preferably 75% by mass or less, and especially preferably 70% by mass or less, based on the consideration of suppressing viscosity increase and reducing the coefficient of thermal expansion.

[0126] Furthermore, the details of the epoxy resin and zeolite, except for the content and particle size mentioned above, are as described in Embodiment 5. Furthermore, the zeolite in Embodiment 6, as described above, preferably contains large-particle-size zeolite. The content and other details of the large-particle-size zeolite are the same as in Embodiment 5, therefore, their detailed description is omitted. In this embodiment, by containing a predetermined amount or more of large-particle-size zeolite, it is easy to prevent the viscosity of the liquid composition from increasing. Furthermore, the inorganic filler in the liquid composition may contain inorganic fillers other than zeolite. Details of the inorganic fillers other than zeolite are the same as in Embodiment 5. Furthermore, in the sixth embodiment, the inorganic filler is the same as in the fifth embodiment, preferably containing both large-particle-size zeolite and small-particle-size inorganic filler. Details of the large-particle-size zeolite and small-particle-size inorganic filler in this case are as described in the fifth embodiment.

[0127] Furthermore, the liquid composition of the sixth embodiment, like that of the fifth embodiment, preferably contains a hardening agent, and may also contain a reactive diluent or other additives, as described above. Also, the liquid composition of the sixth embodiment is preferably solvent-free, as detailed above.

[0128] The epoxy resin composite material of the sixth embodiment of the present invention is obtained by curing the above-mentioned liquid composition to a gel content of 80% or more. More specifically, the epoxy resin composite material contains epoxy resin, zeolite, and a dispersant having at least one functional group, namely an amine group or an amine salt. As described above, the epoxy resin composite material of this embodiment, by containing a dispersant, prevents the viscosity from increasing in the liquid composition used to obtain the epoxy resin composite material. In the epoxy resin composite material of the sixth embodiment of the present invention, the epoxy resin, zeolite, and dispersant are as described above. Furthermore, in addition to the epoxy resin, zeolite, and dispersant, the epoxy resin composite material may also appropriately contain the components contained in the liquid composition of the sixth embodiment. Moreover, except that the total amount of the epoxy resin composite material is used as a basis instead of the total amount of the liquid composition, the content of each component in the epoxy resin composite material is as described above. Furthermore, the epoxy resin in the epoxy resin composite material can be cured to a gel fraction of 80% or more, preferably cured by the curing agent contained in the aforementioned liquid composition.

[0129] In the sixth embodiment, the various physical properties of the liquid composition and the epoxy resin composite material, as well as the manufacturing methods thereof, are as described in the fifth embodiment above. Therefore, the viscosity of the liquid composition of the sixth embodiment, the average coefficient of thermal expansion and glass transition temperature when the liquid composition is made into a hardened material, and the average coefficient of thermal expansion and glass transition temperature of the epoxy resin composite material of the sixth embodiment are as described in the fifth embodiment above.

[0130] [Seventh Implementation] The seventh embodiment of the present invention relates to an epoxy resin composite material containing zeolite as an inorganic filler and having a low average coefficient of thermal expansion. The seventh embodiment of the present invention will be described below. Specifically, the epoxy resin composite material of the seventh embodiment contains epoxy resin and inorganic filler. The average coefficient of thermal expansion of the epoxy resin composite material is 0 ppm / K or more and 200 ppm / K or less. The inorganic filler contains zeolite. As explained above, the average coefficient of thermal expansion is preferably 2 ppm / K or more, particularly preferably 4 ppm / K or more, and even more preferably 100 ppm / K or less, particularly preferably 30 ppm / K or less.

[0131] In the seventh embodiment of the present invention, by including zeolite in the inorganic filler, the average coefficient of thermal expansion can be reduced as described above. Based on this consideration, the zeolite content relative to the total amount of the epoxy resin composite material in the seventh embodiment is preferably 20% by mass or more, more preferably 25% by mass or more, further preferably 30% by mass or more, further preferably 40% by mass or more, and most preferably 45% by mass or more. Furthermore, based on the consideration of suppressing the viscosity increase of the liquid composition used to obtain the epoxy resin composite material, the above-mentioned content is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 75% by mass or less, and particularly preferably 70% by mass or less.

[0132] Furthermore, in the epoxy resin composite material of the seventh embodiment, considering the ease of reducing the coefficient of thermal expansion and thus the ease of maintaining the excellent physical properties of the epoxy resin, the epoxy resin content is preferably 5% by mass or more, and more preferably 10% by mass or more, relative to the total amount of the epoxy resin composite material. On the other hand, it is preferably 50% by mass or less, more preferably 25% by mass or less, and particularly preferably 15% by mass or less.

[0133] Furthermore, in the seventh embodiment of the present invention, a liquid composition for obtaining the above-mentioned epoxy resin composite material is also provided. Specifically, the liquid composition of the seventh embodiment contains epoxy resin and inorganic filler, and the average coefficient of thermal expansion when the composition is made into a cured product with a gel fraction of 80% or more is 0 ppm / K or more and 200 ppm / K or less. The inorganic filler contains zeolite. The method for measuring the average coefficient of thermal expansion and the preferred range are the same as those for the above-mentioned epoxy resin composite material. Furthermore, the viscosity of the liquid composition in the seventh embodiment at 23°C is preferably 0.1 Pa·s or more and 250 Pa·s or less. This reduces the coefficient of thermal expansion of the hardened material while simultaneously achieving low viscosity. The preferred range of viscosity of the liquid composition at 23°C is as described in the first embodiment above.

[0134] Furthermore, in the seventh embodiment, details other than the content of epoxy resin and zeolite are as described in the fifth embodiment. Moreover, the inorganic filler in the seventh embodiment, as described above, preferably contains large-particle-size zeolite. The content of the large-particle-size zeolite and other details are the same as in the fifth embodiment, and their description is omitted. Furthermore, the inorganic packing may contain inorganic packing other than zeolite. Details of the inorganic packing other than zeolite are the same as in embodiment 5. Furthermore, the liquid composition of the seventh embodiment, like that of the fifth embodiment, preferably contains a hardening agent, and may also contain a reactive diluent or other additives, as described above. Also, the liquid composition of the seventh embodiment is preferably solvent-free, as detailed above.

[0135] Furthermore, in the seventh embodiment, the inorganic filler is the same as in the fifth embodiment, preferably containing both large-particle-size zeolite and small-particle-size inorganic filler. Also, in the seventh embodiment, as in the sixth embodiment, the liquid composition or epoxy resin composite material preferably contains a specific dispersant (a dispersant having at least one functional group, either an amine group or an amine salt). These properties are as described in the fifth and sixth embodiments above.

[0136] (use) The compositions and resin composites of the present invention can be used, for example, in catalyst modules, molecular sieve membrane modules, optical components, moisture-absorbing components, food and building components, and components or packaging components of electronic devices, etc., with electronic devices being more preferred. Therefore, the present invention provides an electronic device containing a resin composite material as a preferred form, and provides an electronic device containing an epoxy resin composite material as a more preferred form. An electronic device is a device having two or more electrodes, controlling the current flowing between these electrodes or generating voltage through electricity, light, magnetism, or chemical substances, or generating light or electric and magnetic fields through applied voltage or current. Specifically, examples include resistors, rectifiers (diodes), switching elements (transistors, thyristors), amplifying elements (transistors), memory elements, or chemical sensors, or devices obtained by combining or integrating these elements. Examples also include photodiodes or photocrystals that generate photocurrent, electroluminescent elements that emit light through an applied electric field, and photoelectric conversion elements or solar cells that generate electromotive force through light. Electronic devices are preferably semiconductor devices. A semiconductor device needs to have at least a semiconductor substrate; for example, a device with a semiconductor chip mounted on a substrate, or a device with multiple layers of semiconductor chips or semiconductor substrates, etc.

[0137] The liquid composition of the present invention is preferably used as a liquid sealant. In this case, the epoxy resin composite material formed by hardening the liquid composition is preferably used as a sealing material. Liquid sealants can be used as sealing materials to fill gaps by filling them into the gaps formed between constituent components and then hardening. Furthermore, liquid sealant can be applied to various constituent components, and then another constituent component can be overlapped on top of the liquid sealant, followed by appropriate hardening, to serve as a sealing material for filling the gaps between the constituent components. In this case, the liquid sealant can be appropriately hardened before overlapping another constituent component and is staged. Of these, the liquid composition of the present invention is preferably used for filling gaps and hardening. That is, it is preferably used to manufacture a sealing material by filling the gaps with the liquid composition of the present invention and then hardening the liquid composition. The liquid composition of the present invention achieves low viscosity, so it can fill even narrow gaps without creating voids.

[0138] The liquid composition of this invention is preferably used as a liquid sealing material, and particularly preferably as an underfill material. The underfill material is preferably used in the manufacture of electrical devices, especially semiconductor devices, for example, for filling gaps formed between a substrate and a semiconductor wafer, between substrates, or between semiconductor wafers. The substrate can be a known substrate, such as a substrate made of organic materials like epoxy resin or phenolic resin. Furthermore, the semiconductor wafer can be formed from a semiconductor substrate such as a silicon substrate. Regarding the liquid composition of the present invention, the coefficient of thermal expansion of its hardened form is reduced. By using it as a bottom filler material, the difference in the coefficient of thermal expansion between it and the semiconductor substrate is reduced, thereby improving thermal cycling resistance and other properties.

[0139] The underfill material is preferably a multilayer material in which a semiconductor wafer is mounted on a substrate, filling the gap between the substrate and the semiconductor wafer, and then hardened by heating, thereby serving as a sealing material to seal between the substrate and the wafer. In this case, the semiconductor wafer can be bonded to the surface of the substrate with wiring patterns by bump bonding, for example by reflow soldering, before the underfill material is filled.

[0140] Underfill materials can be used in the manufacture of semiconductor devices using a pre-coating method. Specifically, underfill material is filled between the bumps on the surface of a semiconductor wafer with a plurality of bumps to form an underfill layer. Here, the underfill material can be B-staged as needed. Subsequently, the semiconductor wafer with the underfill layer formed can be placed on the surface of the substrate with the side with the underfill layer formed facing the substrate. Then, the underfill layer can be hardened into a sealing material by heating and pressurizing, etc., and the semiconductor wafer can be bonded to the surface of the substrate with wiring patterns formed by bumps.

[0141] Furthermore, in the pre-coating method, an underfill material can be coated onto the surface of a substrate with a wiring pattern to form an underfill layer. Here, the coated underfill layer can be staged in B-stage as needed. Subsequently, a semiconductor wafer with bumps formed can be placed on the substrate with the underfill layer formed, with the bump-formed side facing the surface of the substrate with the underfill layer formed. Subsequently, the underfill layer can be hardened into a sealing material by heating and pressurizing, and the semiconductor wafer can be bonded to the surface of the substrate with the wiring pattern formed via bumps.

[0142] Furthermore, the above description illustrates the use of underfill material as a sealing material to fill the gap between the substrate and the semiconductor wafer. However, the application of underfill material is not particularly limited; it can fill the gap between semiconductor wafers or be used as a sealing material to fill the gap between substrates. Also, the substrate is not limited to substrates made of organic materials; it can be a semiconductor substrate, etc. [Example]

[0143] The present invention will now be described in more detail using examples, comparative examples, and reference examples. However, the present invention is not limited to the following examples, comparative examples, and reference examples without departing from its spirit.

[0144] <Synthesis of Zeolites> [Example 1] (Manufacturing of zeolite packing A1) N,N,N-trimethyl-1-adamantane ammonium hydroxide (TMAdaOH) manufactured by Sachem Co., Ltd. was added sequentially as a structure directing agent (SDA); "KYOWAAD 200S" manufactured by Kyowa Chemical Industry Co., Ltd. was added as aluminum hydroxide; and "AEROSIL200" manufactured by Aerosil Co., Ltd. of Japan was added as silicon dioxide. The composition and molar ratio of the resulting mixture were SiO2:Al2O3:TMAdaOH:H2O = 1.0:0.025:0.4:20. After homogeneous 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 degassing filtration, washing, and drying, the resulting powder was calcined at 600°C under air circulation for 6 hours to remove TMAdaOH, the structure directing agent (SDA), thereby obtaining CHA-type zeolite. The resulting zeolite system has particles with the particle size distribution shown in Figure 1, with each particle ranging from 1.0 μm to 10 μm in diameter, and an average primary particle size of 3.1 μm. Furthermore, the average primary particle size is set as the average of the particle sizes of 50 randomly selected primary particles. Additionally, the average coefficient of thermal expansion at 50–100 °C is -9.0 ppm / K, the average coefficient of thermal expansion at 50–350 °C is -17.0 ppm / K, the Si / Al²⁺ ratio is 27.8, the sphericity is 0.85, the roundness is 0.845, the c-axis length is 14.67 Å, ​​and the counter cation is proton-type.

[0145] [Example 2] (Manufacturing of zeolite packing A2) In Example 1, hydrothermal synthesis was performed while rotating a heat-resistant container during the hydrothermal synthesis step. Otherwise, the procedure was the same as in Example 1 to obtain CHA-type zeolite. The resulting zeolite had particles with the particle size distribution shown in Figure 2, with 99% of the particles having a particle size between 1.0 μm and 10 μm based on a volume basis. Its average primary particle size was 2.4 μm. Furthermore, the average primary particle size was measured in the same manner as in Example 1. Additionally, the average coefficient of thermal expansion at 50–100 °C was -9.0 ppm / K, the average coefficient of thermal expansion at 50–350 °C was -12.1 ppm / K, the Si / Al²⁺ ratio was 27.8, the sphericity was 0.82, the roundness was 0.829, the c-axis length was 14.59 Å, and the counter cation was proton-type.

[0146] [Example 3] (Manufacturing of zeolite packing A3) In Example 2, the composition and molar ratio of the raw material mixture were set as SiO2:Al2O3:TMAdaOH:H2O = 1.0:0.020:0.4:20. Otherwise, the hydrothermal synthesis, drying, and calcination were performed in the same manner as in Example 2 to obtain CHA-type zeolite. Regarding the obtained zeolite, 81% of the particles, based on a volume basis, had a particle size in the range of 1.0 μm to 10 μm. Its average primary particle size was 1.2 μm. Furthermore, the determination of the average primary particle size was performed in the same manner as in Example 1. Furthermore, the average coefficient of thermal expansion at 50~100℃ is -13.7 ppm / K, the average coefficient of thermal expansion at 50~350℃ is -12.9 ppm / K, the Si / Al2 ratio is 28.2, the sphericity is 0.84, the roundness is 0.835, the c-axis length is 14.59 Å, and the counter cation is proton-type.

[0147] [Comparative Example 1] (Manufacturing of zeolite packing A4) N,N,N-trimethyl-1-adamantane ammonium hydroxide (TMAdaOH) manufactured by Sachem Corporation, used as a structure directing agent (SDA), and aluminum hydroxide manufactured by Fujifilm and Koujun Pharmaceutical Co., Ltd. were added sequentially to a container. After curing at 80°C for 12 hours, "CAB-O-SIL M-5" manufactured by Cabot Corporation, used as silicon dioxide, was added. The composition and molar ratio of the resulting mixture were SiO2:Al2O3:TMAdaOH:H2O = 1.0:0.025:0.4:20. After homogenization, 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 degassing, filtration, and washing, CHA-type zeolite was obtained. The obtained zeolite consisted of particles with a particle size ranging from 1.0 μm to 10 μm, with an average primary particle size of 3.1 μm. Furthermore, the average primary particle size was measured in the same manner as in Example 1. Also, the average coefficient of thermal expansion at 50–100°C was -5.0 ppm / K. Since TMAdaOH decomposes when heated above 300°C, the average coefficient of thermal expansion at 50–350°C could not be determined. The Si / Al2 ratio was 27.8, the sphericity was 0.84, the roundness was 0.840, and the c-axis length was 14.87 Å.

[0148] [Comparative Example 2] (Manufacturing of zeolite packing A5) In a container, N,N,N-trimethyl-1-adamantane ammonium hydroxide (TMAdaOH) manufactured by Sachem (Structure Directing Agent), sodium hydroxide manufactured by Kishida Chemical, potassium hydroxide manufactured by Kishida Chemical, aluminum hydroxide manufactured by Aldrich, and "Snowtex 40" manufactured by Nissan Chemical Corporation (silicon dioxide) were added sequentially. The composition and molar ratio of the resulting mixture were SiO2:Al2O3:NaOH:KOH:TMAdaOH:H2O = 1.0:0.033:0.1:0.06:0.07:20. After adding 2% by mass of CHA-type zeolite relative to SiO2 as seed crystals and mixing uniformly, the resulting mixture was placed in a pressure vessel and subjected to hydrothermal synthesis for 48 hours in an oven at 160°C while rotating the heat-resistant vessel. The powder obtained by vacuum filtration and washing was calcined at 600°C under air circulation for 6 hours to remove the structural prestressing agent, thus obtaining CHA-type zeolite. The obtained zeolite has particles with the particle size distribution shown in Figure 3, with 17% of the particles having a particle size in the range of 1.0 μm to 10 μm based on a volume basis. Its average primary particle size is 0.5 μm. Furthermore, the average primary particle size was measured in the same manner as in Example 1. In addition, the average coefficient of thermal expansion at 50~100°C is -4.9 ppm / K, the average coefficient of thermal expansion at 50~350°C is -5.87 ppm / K, the Si / Al2 ratio is 20.0, and the zeolite is cubic in shape. The sphericity is 0.59, the roundness is 0.785, the c-axis length is 14.83 Å, and the counter cations are sodium and potassium type. The results of Examples 1-3 and Comparative Examples 1 and 2 are summarized in Table 1.

[0149] [Table 1] Table 1 Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 zeolite A1 A2 A3 A4 A5 Particle size (μm) 1.0~10 1.0~10 1.0~10 1.0~10 - Average primary particle size (μm) 3.1 2.4 1.2 3.1 0.5 coefficient of thermal expansion (ppm) 50~100℃ -9.0 -9.0 -13.7 -5.0 -4.9 50~350℃ -17.0 -12.1 -12.9 - -5.87 Si / Al 2 ratio 27.8 27.8 28.2 27.8 20.0 True sphere 0.85 0.82 0.84 0.84 0.59 Roundness 0.845 0.829 0.835 0.840 0.785 c-axis length (A) 14.67 14.59 14.59 14.87 14.83

[0150] According to the results in Table 1, the zeolite of the first embodiment of the present invention has a larger average primary particle size, and the results of true sphericity and true roundness indicate that the zeolite is spherical. Furthermore, based on the fact that the coefficient of thermal expansion is larger in the negative direction, it is known that the thermal shrinkage rate is larger. Therefore, it is believed that by using this zeolite in combination with resin, a resin composite material with suppressed thermal expansion can be obtained. Furthermore, the c-axis length of the zeolite in Comparative Example 1, which was synthesized hydrothermally without calcination, was similar to that of the zeolite in Comparative Example 2, which was manufactured using the previous method. In contrast, the c-axis length of the zeolite in Example 1, which was synthesized hydrothermally and then calcined, was shorter. Therefore, it is speculated that the zeolite of the present invention has a lower coefficient of thermal expansion due to its shorter c-axis length.

[0151] The following are examples of the compositions and resin composites of the present invention. <Formulation Ingredients> The formulation components used in the preparation of liquid compositions and resin composites are as follows. <Inorganic packing> The zeolite packings A1, A3, and A4 manufactured in the above embodiments are used as zeolite packings A1, A3, and A4.

[0152] The inorganic packings other than zeolite packings A1~A5 are as follows. Silica filler A: Manufactured by Longsen Co., Ltd., product name "HL-3100" (silica filler with an average particle size of 45 μm and true spherical shape). Silica filler B: Manufactured by Admatechs Co., Ltd., product name "SC2053-SQ" (silica with an average particle size of 0.5 μm, individual particle sizes ranging from 0.1 μm to 1.0 μm, and a sphericity of 0.95). Zeolite filler B: (CHA zeolite with particle sizes all within the range of less than 1.0 μm, with an average primary particle size of 0.1~0.2 μm and a sphericity of 0.58)

[0153] <Epoxy Resin> Manufactured by Mitsubishi Chemical Co., Ltd., product name "jER630" (p-aminophenol type epoxy resin, epoxy equivalent: 97 g / equivalent). <Polyimide powder> Manufactured by Ube Industries, Inc., product name "UIP-R" (polyimide, average particle size: 7 μm, specific gravity 1.39). Hardening agent Anhydride-based hardener: Manufactured by Hitachi Chemical Co., Ltd., product name "HN-2200" (methyltetrahydrophthalic anhydride, amine equivalent 83 g / equivalent). <Dispersant> Dispersant A: Manufactured by BYK-Chemie Japan, wetting and dispersing agent, product name "DISPERBYK-2152" (containing amino-based ultramolecular polyester, comb type, solvent-free). Dispersant B: Manufactured by BYK-Chemie Japan, wetting and dispersing agent, product name "DISPERBYK-145" (comb-type polymer polyester end-phosphate modified amine salt, solvent-free). Dispersant C: Manufactured by BYK-Chemie Japan, a wetting and dispersing agent, product name "BYK-W9010" (phosphate polyester, solvent-free).

[0154] (Physical property evaluation) The physical property evaluation is conducted as follows. (Gel fraction) The gel fraction of the resin composite material was determined according to the following steps: Resin composite material samples prepared under curing conditions of 80°C for 2 hours followed by 120°C for 2 hours were cut into portions ranging from 0.5 to 0.6 g and placed on a wire mesh. The wire mesh was then immersed in acetone and allowed to stand for 24 hours. Afterward, the wire mesh was removed from the acetone and vacuum dried. The ratio of the weight of the sample after immersion to its weight before immersion was defined as the gel fraction. (Viscosity of the liquid composition) The viscosity of the liquid composition at 23°C was measured using a Type B rotational viscometer. For viscosity ranges from 0.1 to 100 Pa·s, the "LVDV-1 Pri" (manufactured by Brookfield, shaft: S64, S63) was used; for viscosity exceeding 100 Pa·s, the "HBDV-E" (manufactured by Brookfield, shaft: S-07) was used. Furthermore, the value measured at 20 rpm was taken as the representative viscosity for each sample.

[0155] (Average coefficient of thermal expansion (CTE1) of epoxy resin and epoxy resin composites) The average coefficient of thermal expansion (CTE1) of epoxy resin composites obtained by curing the liquid composition into a gel state with a gel content of 80% or more was determined by thermomechanical analysis according to JIS K7197 (2012). A thermomechanical analysis apparatus (TMA SS7100, manufactured by SII Nano Technology) was used, and the measurement was performed by compression. Specifically, epoxy resin composites were cut into ϕ6 mm × 10 mm pieces, and the temperature was measured by cooling from 200 °C to 20 °C at a rate of 5 °C / min using the thermomechanical analysis apparatus. The temperature change in the sample length between 25 and 100 °C was measured, and the slope of the tangent was taken as the average coefficient of thermal expansion (CTE1).

[0156] (Average coefficient of thermal expansion (CTE1) of polyimide resin and polyimide resin composites) The average coefficient of thermal expansion (CTE1) of polyimide resin composites obtained by curing to a gel fraction of 80% or more was determined by thermomechanical analysis according to JIS K7197 (2012). A thermomechanical analysis apparatus (TMA SS7100, manufactured by SII Nano Technology) was used, and the measurement was performed by compression. Specifically, polyimide resin composites were cut into pieces 10 mm wide, 6 mm thick, and 10 mm high. Using the thermomechanical analysis apparatus, the sample was cooled from 200°C to 20°C at a rate of 5°C / min via compression. The temperature change in the sample length between 25 and 100°C was measured, and the slope of the tangent was taken as the average coefficient of thermal expansion (CTE1).

[0157] (Glass transition temperature of epoxy resin composites) The glass transition temperature (Tg) of the epoxy resin composite material obtained by curing the liquid composition into a gel content of 80% or more was determined by a thermomechanical analysis (TMA) apparatus. Specifically, the measurement was performed under the same apparatus and conditions as those used for evaluating the coefficient of thermal expansion, and a graph was plotted with temperature as the X-axis and the coefficient of linear expansion as the Y-axis. The slope of the tangent line in the graph from 15 to 75°C was used to determine CTE'1, and the slope of the tangent line from 150 to 200°C was used to determine CTE'2. The intersection of CTE'1 and CTE'2 was used to determine the glass transition temperature Tg (°C).

[0158] [Example 4] As shown in Table 2, 13 g of epoxy resin, 17 g of hardener, 59 g of zeolite filler A1, 10 g of silica filler B, and 1 g of dispersant A were weighed into a cup and mixed. Then, a liquid composition was prepared by mixing at 1500 rpm for 5 minutes using a vacuum mixer (manufactured by EME Corporation, "V-mini 300"). The viscosity of the liquid composition at 23°C was measured using a rotational viscometer. Subsequently, it was cast into a molding die, heated at 80°C for 2 hours, and then heated at 120°C for 2 hours to harden to a gel content of over 80%. The mixture was then demolded to obtain the epoxy resin composite material.

[0159] [Comparative Example 3] Weigh 21 g of epoxy resin, 29 g of hardener, and 50 g of silica filler A into a cup in the manner shown in Table 2, and mix by hand. Except for the mixing ratio, proceed in the same manner as in Example 4 to obtain a liquid composition and a resin composite material.

[0160] [Comparative Example 4] Weigh 17 g of epoxy resin, 23 g of hardener, and 60 g of zeolite filler B into a cup in the manner shown in Table 2, and mix by hand. Except for the mixing ratio, proceed in the same manner as in Example 4 to obtain a liquid composition and a resin composite material.

[0161] [Example 5] Weigh 21 g of epoxy resin, 29 g of hardener, and 50 g of zeolite filler A1 into a cup in the manner shown in Table 2, and mix by hand. Except for the mixing ratio, proceed in the same manner as in Example 4 to obtain a liquid composition and a resin composite material.

[0162] [Example 6] As shown in Table 2, 17.2 g of epoxy resin, 23.2 g of hardener, and 59.6 g of zeolite filler A1 were weighed into a cup and mixed by hand. Except for the mixing ratio, the process was the same as in Example 4 to obtain a liquid composition and a resin composite material.

[0163] [Example 7] Weigh 17 g of resin, 23 g of hardener, 59 g of zeolite filler A1, and 1 g of dispersant C into a cup and mix them, as shown in Table 2. Except for the mixing ratio, proceed in the same manner as in Example 4 to obtain a liquid composition and a resin composite material.

[0164] [Example 8] Weigh 17 g of epoxy resin, 23 g of hardener, 59 g of zeolite filler A1, and 1 g of dispersant A into a cup in the manner shown in Table 2, and mix them. Except for the mixing ratio, proceed in the same manner as in Example 4 to obtain a liquid composition and a resin composite material.

[0165] [Example 9] Weigh 17 g of epoxy resin, 23 g of hardener, 59 g of zeolite filler A1, and 1 g of dispersant B into a cup in the manner shown in Table 2, and mix them. Except for the mixing ratio, proceed in the same manner as in Example 4 to obtain a liquid composition and a resin composite material.

[0166] [Example 10] As shown in Table 2, 9.9 g of epoxy resin, 14.9 g of hardener, 49.5 g of zeolite filler A1, 24.7 g of silica filler B, and 1 g of dispersant A were weighed into a cup and mixed by hand. Except for the mixing ratio, the same procedure as in Example 4 was followed to obtain a liquid composition and a resin composite material.

[0167] The viscosity of the liquid compositions in Examples 4-10 and Comparative Examples 3-4 was measured, and the average coefficient of thermal expansion (CTE1) and glass transition temperature (Tg) of the epoxy resin composites were measured. The results are shown in Table 2.

[0168] [Table 2] Table 2 Comparative Example 3 Comparative Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 4 Example 10 Composition of the liquid composition (mass %) Silica filler A 50.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Zeolite packing A1 0.0 0.0 50.0 59.6 59.0 59.0 59.0 59.0 49.5 Zeolite packing B 0.0 60.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Silica filler B 0.0 0.0 0.0 0.0 0.0 0.0 0.0 10.0 24.7 Epoxy resin 21.0 17.0 21.0 17.2 17.0 17.0 17.0 13.0 9.9 hardener 29.0 23.0 29.0 23.2 23.0 23.0 23.0 17.0 14.9 Dispersant A 0.0 0.0 0.0 0.0 0.0 1.0 0.0 1.0 1.0 Dispersant B 0.0 0.0 0.0 0.0 0.0 0.0 1.0 0.0 0.0 Dispersant C 0.0 0.0 0.0 0.0 1.0 0.0 0.0 0.0 0.0 physical properties CTE1 (ppm / K) 44 19 25 19 twenty one 27 25 17 15 Viscosity (Pa·s) 1 450 5 90 95 13 19 20 26 Tg (°C) 150 150 155 150 125 115 115 110 110

[0169] [Comparative Example 5] In Example 6, zeolite filler was not used; otherwise, the procedure was the same as in Example 6 to obtain a liquid composition and a resin composite material. The viscosity of the liquid composition was 0.4 Pa·s, and the average coefficient of thermal expansion (CTE1) of the epoxy resin composite material was 64 ppm / K. [Example 11] In Example 6, zeolite filler A3 was used instead of zeolite filler A1. Otherwise, the procedure was the same as in Example 6 to obtain the liquid composition and resin composite material. The average coefficient of thermal expansion (CTE1) of the epoxy resin composite material was 20 ppm / K. [Reference Example 1] In Example 6, zeolite filler A4 was used instead of zeolite filler A1. Otherwise, the procedure was the same as in Example 6 to obtain the liquid composition and resin composite material. The average coefficient of thermal expansion (CTE1) of the epoxy resin composite material was 30 ppm / K.

[0170] As can be seen from Examples 5 to 11, by using the zeolite containing the present invention, a low-viscosity liquid composition can be obtained, and the coefficient of thermal expansion of the resin composite material obtained by hardening the liquid composition can be reduced. In particular, by comparing Examples 5 and 11, which contain the zeolite of Examples 1 or 3, with Reference Example 1, which contains the zeolite of Comparative Example 1, it can be seen that by using the zeolite containing the present invention, a resin composite material with a lower coefficient of thermal expansion can be obtained. First, as shown in Table 2, the resin composites of Examples 5 and 6 containing the zeolite of the present invention have a lower coefficient of thermal expansion compared to the resin composite of Comparative Example 3, which contains large-particle-size silica filler. Furthermore, the liquid compositions of Examples 5 and 6 containing the zeolite of the present invention have lower viscosity compared to the liquid composition of Comparative Example 4, which contains small-particle-size zeolite. That is, it can be seen that by using the zeolite of the present invention, a low-viscosity liquid composition can be obtained, and the coefficient of thermal expansion of the resin composite obtained by hardening the liquid composition can be reduced. In Examples 4 and 10, large-particle-size zeolite was used in combination with small-particle-size inorganic fillers, thereby reducing the coefficient of thermal expansion of the epoxy resin composite material obtained by curing the liquid composition, and successfully reducing the viscosity of the liquid composition. In contrast, Comparative Example 3 contained large-particle-size silica filler, and its content was set to be the same as that of the large-particle-size zeolite in Example 10. As a result, the viscosity of the liquid composition was lower, however, the average coefficient of thermal expansion (CTE1) was higher. Furthermore, although Examples 5 and 10 contain the same amount of large-particle zeolite, both Examples 5 and 10 show a certain degree of reduction in the average coefficient of thermal expansion (CTE1), and the viscosity is also successfully reduced. In particular, in Example 10, the average coefficient of thermal expansion (CTE1) is even lower than that in Example 5. In Comparative Examples 4 and 6, zeolite filler was included, and its content was further increased compared to Comparative Examples 3 and 5. As a result, the average coefficient of thermal expansion (CTE1) decreased. Here, compared with Comparative Example 4, the viscosity of the liquid composition in Example 6 did not increase, so it is considered suitable as a bottom filler material for use in gaps. That is, it can be seen that by using the large-particle-size zeolite of the present invention, a low-viscosity liquid composition can be obtained, and by hardening the liquid composition, a resin composite material with a low coefficient of thermal expansion can be obtained.

[0171] As shown in Table 2, comparing Examples 8 and 9 with Examples 6 and 7, the results show that the addition of dispersant A or B resulted in a viscosity reduction effect. This indicates that dispersants A and B, containing amine groups or amine salts, are effective in reducing viscosity. Furthermore, it is evident that by adding dispersants, the resin composites of Examples 8 and 9 exhibit very high glass transition temperatures (Tg), excellent thermal cycling resistance, and suitable average coefficients of thermal expansion for bottom filler materials.

[0172] [Example 12] 21 g of polyimide powder and 9 g of zeolite filler A1 prepared in Example 1 were weighed into a cup and mixed. The mixture was then densely spread into a pressing mold. The mold was placed in a high-temperature vacuum pressing device (manufactured by Kitagawa Seiki Co., Ltd.) and pressed at a pressing temperature of 390°C and a surface pressure of 8 MPa for 30 minutes. Demolding was then performed to obtain a shaped body with a length of 11 cm, a width of 2.5 cm, and a thickness of 6 mm. The body was cut 10 mm from the end, and the average coefficient of thermal expansion was measured. The results are shown in Table 3.

[0173] [Comparative Example 6] In Example 12, the zeolite filler A4 manufactured in Comparative Example 1 was used as the zeolite. Otherwise, the same procedure as in Example 12 was followed to manufacture the molded article, and its average coefficient of thermal expansion was measured. The results are shown in Table 3.

[0174] [Comparative Example 7] In Example 12, zeolite filler was not used; otherwise, the same procedure as in Example 12 was followed to manufacture the molded article, and its average coefficient of thermal expansion was measured. The results are shown in Table 3.

[0175] [Table 3] Table 3 Example Comparative example 12 6 7 Composition of the resin composition (mass %) Zeolite packing A1 30 0 0 Zeolite packing A4 0 30 0 Polyimide resin 70 70 100 physical properties CTE1 (ppm / K) 29 33 41

[0176] As shown in Table 3, when using polyimide resin, a resin composite material with a lower coefficient of thermal expansion can also be obtained by using the large-particle-size zeolite of the present invention. [Industrial Applicability]

[0177] According to the present invention, a low-viscosity liquid composition can be provided. Furthermore, by hardening the liquid composition, a resin composite material with a low coefficient of thermal expansion can be provided. That is, the composition of the present invention provides a sealing material with excellent injectability and heat resistance, particularly suitable for use as a bottom filler material. Furthermore, the resin composite material with a low coefficient of thermal expansion of the present invention can also be used as a sealing material manufactured by means of pressure molding, etc.

Claims

1. A liquid composition comprising a resin and an inorganic filler, wherein the inorganic filler comprises zeolite with a particle size of 1.0 μm to 10 μm and an inorganic filler with a particle size of 0.1 μm to 1.0 μm, wherein the zeolite has a sphericity of 0.6 or higher and a roundness of 0.786 or higher, wherein the sphericity is the ratio of the minimum diameter to the maximum diameter of the particles, and the maximum diameter and the minimum diameter can be determined by observation using a scanning electron microscope (SEM), and the roundness is 4 × π × area / (circumference)², wherein the area and the circumference can be determined by observation using a scanning electron microscope (SEM).

2. The liquid composition of claim 1, further comprising a dispersant having at least one functional group having an amine group and an amine salt.

3. The liquid composition of claim 1 or 2, wherein the zeolite has d6r as CBU.

4. The liquid composition of claim 1 or 2, wherein the zeolite is an aluminosilicate.

5. The liquid composition of claim 1 or 2, wherein the resin is an epoxy resin.

6. The liquid composition of claim 1 or 2, wherein the resin is an epoxy resin, and the viscosity of the liquid composition at 23°C is 0.1 Pa·s or more and 250 Pa·s or less.

7. A liquid sealant comprising a liquid composition as claimed in any one of claims 1 to 6.

8. A resin composite material formed by curing a liquid composition of any one of claims 1 to 6 to a gel content of 80% or more.

9. A resin composite material comprising a resin and an inorganic filler, wherein the inorganic filler comprises zeolite with a particle size of 1.0 μm to 10 μm and an inorganic filler with a particle size of 0.1 μm to 1.0 μm, wherein the zeolite has a sphericity of 0.6 or higher and a roundness of 0.786 or higher, wherein the sphericity is the ratio of the minimum diameter to the maximum diameter of the particles, and the maximum diameter and the minimum diameter can be determined by observation using a scanning electron microscope (SEM), and the roundness is 4 × π × area / (circumference)², wherein the area and the circumference can be determined by observation using a scanning electron microscope (SEM).

10. The resin composite material of claim 9, further comprising a dispersant having at least one functional group having an amine group and an amine salt.

11. The resin composite material of claim 9 or 10, wherein the zeolite has d6r as CBU.

12. The resin composite material of claim 9 or 10, wherein the above-mentioned zeolite-based aluminosilicate.

13. The resin composite material of claim 9 or 10, wherein the resin is selected from at least one of the group consisting of epoxy resin and polyimide resin.

14. The resin composite material of claim 9 or 10, wherein the resin is an epoxy resin, and the average coefficient of thermal expansion of the resin composite material, determined by the following method, is 0 ppm / K or more and 200 ppm / K or less, (wherein, The average coefficient of thermal expansion is determined according to JIS K7197 (2012) by using the compression method of thermomechanical analysis to measure the temperature change of the sample length change at 25-100℃, and then by the slope of the tangent.

15. A zeolite comprising an aluminosilicate having a particle size of 1.0 μm to 10 μm, having d6r as a CBU, being spherical, having a sphericity of 0.6 or higher, and a roundness of 0.786 or higher, wherein the sphericity is the ratio of the minimum diameter to the maximum diameter of the particles, and the maximum diameter and the minimum diameter are respectively determined by observation using a scanning electron microscope (SEM), and the roundness is 4 × π × area / (circumference)², wherein the area and the circumference are respectively determined by observation using a scanning electron microscope (SEM).

16. A composition comprising the zeolite as claimed in claim 15 and a resin.

17. The composition of claim 16, wherein the resin is selected from at least one of the group consisting of epoxy resins and polyimide resins.

18. The composition of claim 16 or 17 further comprises inorganic filler having a particle size of 0.1 μm or more but less than 1.0 μm.

19. The composition of claim 16 or 17 further comprises a dispersant having at least one functional group having an amino group and an amino salt.

20. A liquid composition comprising any one of claims 16 to 19, wherein the content of the zeolite is 40 to 70% by mass, the resin is an epoxy resin, and the viscosity of the liquid composition at 23°C is 1 Pa·s or more and 30 Pa·s or less.

21. A resin composite material comprising a composition according to any one of claims 16 to 19, wherein the zeolite content is 40 to 70% by mass, the resin is an epoxy resin, and the resin composite material has an average coefficient of thermal expansion of 10 to 30 ppm / K at 25 to 100°C.

22. A sealing material comprising a resin composite material as claimed in any one of claims 9 to 14 and 21.

23. An electronic device comprising a resin composite material as claimed in any one of claims 9 to 14 and 21.

24. A method for manufacturing a sealing material, wherein a liquid composition of any one of claims 1 to 6 and 20 is filled into a gap and then hardened.

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