Zeolite, method for producing zeolite, and composition

Abstract

The objective is to provide a zeolite with a lower coefficient of thermal expansion. [Solution] The zeolite has a particle size of 1.0 μm or more and 10 μm or less, contains d6r as CBU, and is an aluminosilicate.

Description

[Technical Field]

[0001] This invention relates to zeolites, methods for producing zeolites, and compositions. [Background technology]

[0002] Liquid sealants used as underfill materials are required to have excellent injectability, adhesion, curing properties, and storage stability, and to be void-free. Furthermore, the areas sealed with the liquid sealant must have excellent moisture resistance, thermal cycling resistance, reflow resistance, crack resistance, and warping resistance. To satisfy the above 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 of the parts sealed with liquid encapsulants, particularly thermal cycling resistance, it is known that adding an inorganic filler such as silica filler (hereinafter referred to as "inorganic filler") to the liquid encapsulant is effective in controlling the difference in thermal expansion coefficients between the substrate made of organic material such as epoxy resin and the semiconductor element, and in reinforcing the bump electrodes (see Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2007-56070 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Liquid sealants using inorganic fillers such as silica fillers do not have sufficiently low thermal expansion coefficients, and there is a need to further reduce the thermal expansion coefficient from the standpoint of thermal cycling resistance. Zeolites are known as inorganic fillers with low thermal expansion coefficients, but liquid compositions containing zeolites tend to have high viscosity, which reduces the injectability when used as an underfill material. Therefore, it is difficult to obtain a liquid sealant with good injectability while keeping the thermal expansion coefficient of the cured product low. Furthermore, even if a large amount of inorganic filler is used to lower the thermal expansion coefficient, viscosity increases and mechanical properties change, among other problems.

[0006] In contrast, if a zeolite with a lower coefficient of thermal expansion is available, the coefficient of thermal expansion of the resin composite can be reduced with a smaller amount, and the increase in viscosity and changes in resin properties caused by the use of zeolite can be suppressed. Therefore, the present invention aims to provide a zeolite with a lower coefficient of thermal expansion. It also aims to apply the zeolite with a lower coefficient of thermal expansion to various applications where suppression of thermal expansion is required, such as resin substrates. Furthermore, the present invention aims to provide a liquid composition that can lower the thermal expansion coefficient of the cured product while also lowering its viscosity, and an epoxy resin composite material obtained by curing the liquid composition. Furthermore, the present invention also aims to provide a liquid composition containing zeolite that can prevent viscosity from increasing, and an epoxy resin composite material obtained from the liquid composition. [Means for solving the problem]

[0007] The gist of this invention is as follows: [1] A zeolite having a particle size of 1.0 μm or more and 10 μm or less, containing d6r as CBU, and being an aluminosilicate. [2] The zeolite described in [1] above, wherein the c-axis length of the lattice constant is 14.80 Å or less. [3] A spherical zeolite as described in [1] or [2] above. [4] A zeolite as described in any of [1] to [3] above, wherein the sphericity is 0.6 or greater and 1 or less. [5] A zeolite as described in any of [1] to [4] above, having a roundness of 0.786 or more and 1 or less. [6] A zeolite according to any of the above [1] to [5], wherein the average thermal expansion coefficient determined by the following method is -1000 ppm / K or more and less than 0 ppm / K. (Note that the average thermal expansion coefficient is determined in accordance with JIS K7197 (2012) by measuring the temperature dependence of the change in sample length at 50-100°C using the compression method of thermomechanical analysis, and then calculating it from the slope of the tangent line.) [7] A zeolite according to any of the above [1] to [6], wherein the average thermal expansion coefficient at 50 to 350°C, determined by the following method, is between -1000 ppm / K and -9.5 ppm / K. (Note that the average thermal expansion coefficient is determined in accordance with JIS K7197 (2012) by measuring the temperature dependence of the change in sample length between 50 and 350°C using the compression method of thermomechanical analysis, and then determining it from the slope of the tangent line.) [8] A method for producing zeolite, comprising the steps of hydrothermally synthesizing a raw material composition containing silicon atom raw material, water-soluble aluminum atom raw material, organic structure-regulating agent and water, and then calcining, wherein the composition is characterized in that the content of alkali metal atoms other than the organic structure-regulating agent is 0.05 moles or less per mole of Si atoms. [9] The method for producing zeolite according to [8], further comprising the step of maturing the raw material composition before the hydrothermal synthesis.

[10] A composition containing the zeolite and resin described in any of [1] to [7] above.

[11] The composition according to

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

[0008] According to the present invention, zeolite with a lower coefficient of thermal expansion can be provided. Further, by using this zeolite, thermal expansion can be suppressed in a composite material with a resin. Moreover, since the thermal expansion of the resin can be suppressed with a small amount, an increase in the viscosity of the resin composition due to the use of zeolite and a change in the physical properties of the resin due to the inclusion of zeolite can be suppressed.

Brief Description of the Drawings

[0009] [Figure 1] It is a chart showing the particle size distribution of the zeolite of Example 1. [Figure 2] It is a chart showing the particle size distribution of the zeolite of Example 2. [Figure 3] It is a chart showing the particle size distribution of the zeolite of Comparative Example 2.

Modes for Carrying Out the Invention

[0010] Hereinafter, the present invention will be described with reference to embodiments. [First Embodiment] <Zeolite> The zeolite according to the first embodiment of the present invention is an aluminosilicate having a particle size of 1.0 μm or more and 10 μm or less and containing d6r as CBU. One of the features of the zeolite of the present invention is that the particle size is larger compared to ordinary zeolite, and the particle size is 1.0 μm or more and 10 μm or less. Hereinafter, the zeolite according to the first embodiment of the present invention will be described in detail. Zeolite having a particle size of 1.0 μm or more and 10 μm or less may be hereinafter referred to as "large particle size zeolite".

[0011] (Particle Size of Zeolite) The particle size of the zeolite according to the first embodiment of the present invention means the diameter of the circle (equivalent circle diameter) having the maximum diameter with an area equal to the projected area of the particle in the observation of the particle by a scanning electron microscope (SEM). The zeolite according to the first embodiment of the present invention may have a plurality of zeolite particles aggregated to form secondary particles. In this case, the particle size of the zeolite is the particle size of the primary particles. When adding the zeolite to a resin, the particle size of the zeolite of the present invention is preferably large in terms of its viscosity being difficult to increase. On the other hand, it is preferably small in terms of being easily and uniformly mixed with other components such as resins and having high surface smoothness. Specifically, 1.5 μm or more is preferable, and 2.0 μm or more is more preferable. On the other hand, 8 μm or less is preferable, and 5 μm or less is more preferable. When using zeolite, usually, it is not used as one zeolite particle but as a plurality of zeolite particle groups. That is, as one aspect of the present invention, it is preferable to use it as a zeolite group containing at least the zeolite particles according to the first embodiment of the present invention. In one aspect composed of such a plurality of zeolite particles, the average particle size of the zeolite 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 particle size of the zeolite is obtained by randomly selecting 50 zeolites (particles in the powder, liquid composition or resin composite material described later) and measuring their particle sizes, and taking the average value. Also, as the particle size distribution of the zeolite on a volume basis, the median diameter (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. When the median diameter is within this range, the proportion of the zeolite that exhibits the effects of the present invention increases, and the effects of the present invention can be obtained more easily with a smaller amount.

[0012] (Structure of Zeolite) Zeolites are compounds composed of silicon or aluminum and oxygen, with TO4 units (T elements being elements other than oxygen that constitute the framework) as their basic units. Specifically, zeolites include crystalline porous aluminosilicates, crystalline porous aluminophosphates (ALPO), and crystalline porous silicoaluminophosphates (SAPO), but the zeolite according to the first embodiment of the present invention is an aluminosilicate. Zeolite is composed of structural units called Composite Building Units (hereinafter sometimes referred to as "CBUs"), which are made up of several (several to dozens) TO4 units connected together. As a result, it has regular channels (tubular pores) and cavities. The crystal structures of CBU and the zeolites described later can be represented by the zeolite structure code defined by the International Zeolite Association (IZA). The structure of a zeolite can be determined using the 2018 Zeolite Structure Database (http: / / www.iza-structure.org / databases / ) based on the X-ray diffraction pattern obtained by an X-ray structural analyzer (for example, the BRUKER D2PHASER desktop X-ray diffractometer).

[0013] (Zeolite skeleton) The zeolite skeleton according to the first embodiment of the present invention contains d6r as CBU. Including d6r makes it easier to obtain a resin composite material with a low coefficient of thermal expansion, which will be described in detail later. Examples of zeolites containing d6r as CBU include AEI, AFT, AFV, AFX, AVL, CHA, EAB, EMT, ERI, FAU, GME, JSR, KFI, LEV, LTL, LTN, MOZ, MSO, MWW, OFF, SAS, SAT, SAV, SBS, SBT, SFW, SSF, SZR, TSC, and zeolites with a -WEN type structure. Of these, zeolites with an oxygen ring of 8 members or less are particularly preferred from the viewpoint of ease of particle size control. Examples of zeolites with an oxygen ring of 8 members or less include AEI, AFT, AFX, CHA, ERI, KFI, SAT, SAV, SFW, and TSC type zeolites. Among these, AEI, AFX, CHA, and ERI type zeolites are more preferred because their structure remains stable even when their shape is controlled, and CHA type zeolites are the most preferred. In this specification, an oxygen ring of 8 members refers to a structure in which the number of oxygen elements is 8 in the pores composed of oxygen and T elements (elements other than oxygen that constitute the skeleton) that form the zeolite skeleton.

[0014] (Average thermal expansion coefficient of zeolite) The average thermal expansion coefficient of the zeolite according to the first embodiment of the present invention is preferably low because it is easy to reduce the average thermal expansion coefficient of the liquid composition and resin composite material described later with a small amount. It is also preferable that the various physical properties of the resin do not change easily due to the addition of zeolite because it is used in small amounts. In particular, it is preferable that it is low because it can suppress the increase in viscosity of the liquid composition described later. Specifically, the average thermal expansion coefficient of the zeolite is usually less than 0 ppm / K, preferably -2 ppm / K or less, more preferably -3 ppm / K or less, even more preferably -5 ppm / K or less, particularly preferably -6 ppm / K or less, and most preferably -8 ppm / K or less.

[0015] On the other hand, considering the liquid composition containing zeolite and resin and the resin composite material described later, it is preferable that the average thermal expansion coefficient of the zeolite be high, as the difference from the average thermal expansion coefficient of the resin is small, making it difficult for the zeolite and resin to separate. Therefore, the average thermal expansion coefficient of the zeolite is usually -1000 ppm / K or higher, preferably -900 ppm / K or higher, more preferably -800 ppm / K or higher, even more preferably -700 ppm / K or higher, particularly preferably -500 ppm / K or higher, and especially preferably -300 ppm / K or higher. Furthermore, when used in applications where it comes into contact with other materials such as sealing materials or substrates, a higher coefficient is preferable, 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. The average thermal expansion coefficient of zeolite can be measured by calculating the lattice constant using a BRUKER D8ADVANCE X-ray diffractometer and JADE X-ray diffraction analysis software. To eliminate the effects of water desorption, the zeolite is measured in a dry state. The average thermal expansion coefficient of zeolite is typically measured in the range of 50 to 100°C. Specifically, it represents the displacement of the lattice constant per degree Celsius, calculated by comparing the average lattice constant at 50°C with the average lattice constant at 100°C. Here, the average lattice constant at each temperature is the average of the lattice constants along the a, b, and c axes. The measurement of the average thermal expansion coefficient is performed by gradually increasing the temperature after waiting for the lattice constant to stabilize.

[0016] Resins generally tend to have a high coefficient of thermal expansion at high temperatures. Therefore, it is preferable that the average coefficient of thermal expansion of zeolite be low, especially when heated to high temperatures. Specifically, the average coefficient of thermal expansion (high temperature range) in the range of 50 to 350°C is preferably -9.5 ppm / K or less, more preferably -10.0 ppm / K or less, and even more preferably -12.5 ppm / K or less. Here, the average coefficient of thermal expansion (high temperature range) of zeolite is a value that represents the displacement of the lattice constant per degree Celsius, obtained by comparing the average lattice constant at 50°C and the average lattice constant at 350°C when the zeolite is heated.

[0017] (Shape of zeolite) The zeolite according to the first embodiment of the present invention is preferably spherical in shape because it is easy to incorporate into resins while suppressing an increase in viscosity. Specifically, it is preferably spherical and round as follows.

[0018] <<Sphericity>> The sphericity of the zeolite is preferably 0.6 or higher, more preferably 0.65 or higher, and particularly preferably 0.70 or higher. Furthermore, there is no upper limit to the sphericity; it may be 1 or less. For example, the sphericity of a cubic zeolite, which is common, is 0.58. In this specification, "sphericity" is defined as "the ratio of the minimum diameter to the maximum diameter of a particle." The maximum and minimum diameters can be determined by observation using a scanning electron microscope (SEM).

[0019] <<Roundness>> The roundness 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 upper limit to the roundness, and it may be 1 or less. Note that the roundness of the cubic zeolite, which is common, is usually 0.785. In this specification, "roundness" is defined as "4 × π × area / (circumference)".2 It is defined as "[...]." The area and circumference can be determined by observation using a scanning electron microscope (SEM).

[0020] (c-axis length of zeolite) In the zeolite according to the first embodiment of the present invention, it is preferable that the c-axis length of the lattice constant is short. It is thought that a short c-axis length leads to larger transverse lattice vibrations, causing negative expansion and a lower average thermal expansion coefficient. Specifically, the c-axis length is preferably 14.80 Å or less, more preferably 14.78 Å or less, even more 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. In this specification, the c-axis length refers to the length of the c-axis at room temperature (23°C). The lattice constant of the zeolite can be measured using a BRUKER D8ADVANCE X-ray diffractometer and calculated using the least squares method with the JADE X-ray diffraction analysis software.

[0021] (Zeolite framework density) The framework density of the zeolite in the present invention is not particularly limited, as long as the effects of the present invention are not impaired. A low framework density of the zeolite is preferable because it makes the zeolite more susceptible to structural vibration and tends to result in a lower average coefficient of thermal expansion. Therefore, the framework density of the zeolite is preferably 17.0 T / 1000 Å. 3 More preferably, 16.0T / 1000Å 3 The following applies: On the other hand, a high zeolite framework density is preferable because it tends to increase the structural stability of the zeolite. The zeolite framework density is preferably 12.0T / 1000Å. 3 More preferably, 13.0T / 1000Å 3 More preferably, 14.0T / 1000Å 3 That concludes the explanation. When the framework density is within the above range, zeolite can be used as a stable filler. Note that the framework density indicates the number of T atoms present per unit volume of zeolite and is a value determined by the structure of the zeolite. In this specification, the numerical values described in the 2017 version of the IZA Zeolite Structure Database (http: / / www.iza-structure.org / databases / ) may be used.

[0022] When the framework density is greater than 16.0 T / 1000 Å 3 and less than 17.0 T / 1000 Å 3 Examples of the following zeolites include zeolites of the ERI, LTL, LTN, MOZ, OFF, SAT, SSF, and -WEN type structures. When the framework density is greater than 15.0 T / 1000 Å 3 and less than 16.0 T / 1000 Å 3 Examples of the following zeolites include zeolites of the AEI, AFT, AFV, AFX, AVL, EAB, GME, LEV, MWW, and SFW type structures. When the framework density is greater than 14.0 T / 1000 Å 3 and less than 15.0 T / 1000 Å 3 Examples of the following zeolites include zeolites of the CHA, KFI, SAS, and SAV type structures. When the framework density is less than or equal to 14.0 T / 1000 Å 3 Examples of zeolites existing in the following ranges include zeolites of the EMT, FAU, JSR, SBS, SBT, and TSC type structures.

[0023] (Silica / alumina molar ratio (SAR) of zeolite) The silica / alumina molar ratio (sometimes referred to as "SAR," "Si / Al2 molar ratio," or "Si / Al2 ratio") of the zeolite according to the first embodiment of the present invention is not particularly limited as long as the effects of the present invention are not impaired. A high SAR (Si / Al2 ratio) of the zeolite is preferable in that it improves the moisture resistance of the resin composite material described later and makes it easier to control the amount of countercations. Therefore, the SAR (Si / Al2 ratio) of the zeolite is usually 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, a low SAR (Si / Al2 ratio) of zeolite is preferable for ease of inexpensive production. Therefore, the SAR (Si / Al2 ratio) of zeolite is usually 2000 or less, preferably 1000 or less, more preferably 500 or less, and even more preferably 100 or less. When the Si / Al2 ratio is within the above range, it is easier to control the amount of countercations, and the manufacturing cost of the zeolite is also kept low.

[0024] (Zeolite countercations) The countercation of the zeolite according to the first embodiment of the present invention is not particularly limited as long as the effects of the present invention are not impaired. The countercation of the zeolite is usually 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. When it is an alkali metal ion or an alkaline earth metal ion, the smaller its size, the more likely the zeolite is to exhibit an average thermal expansion coefficient of less than 0 ppm / K, which is preferable. In particular, when the countercation of the zeolite is a proton, it is preferable because it tends to lower the average thermal expansion coefficient of the resin composite material. That is, the zeolite 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 particularly preferably a proton type.

[0025] (Zeolite crystallinity) The crystallinity of the zeolite according to the first embodiment of the present invention is not particularly limited, as long as the effects of the present invention are not impaired. This is because the Composite Building Unit (CBU) is presumed to be a more influential factor than the structure defined by the code of IZA, due to its average thermal expansion coefficient of the epoxy resin composite. The crystallinity of the zeolite can be determined by comparing it with the X-ray diffraction peak of the zeolite, which is based on a reference X-ray diffraction peak obtained using an X-ray diffractometer (for example, a BRUKER D2PHASER desktop X-ray diffractometer). A specific example of calculation is the crystallinity of LTA-type zeolite in Scientific Reports 2016, 6, Article number: 29210.

[0026] (Surface treatment of zeolite) The zeolite may be surface-treated, such as silylation, to the extent that the effects of the present invention are not impaired. The surface treatment is not limited to physical or chemical treatment.

[0027] (Method of manufacturing zeolite) The method for producing the zeolite of the present invention (hereinafter sometimes referred to as "the method for producing the zeolite of the present invention") will be described in detail below. The present invention provides a method for producing zeolite, comprising the steps of hydrothermally synthesizing a raw material composition containing silicon atom raw material, water-soluble aluminum atom raw material, organic structure-regulating agent, and water, and then calcining the composition. Here, the raw material composition contains 0.05 moles or less of alkali metal atoms other than organic structure-determining agents per mole of Si atoms. Furthermore, a desired zeolite (hereinafter sometimes referred to as "seed crystal zeolite") may be used as needed.

[0028] <<Silicon Atom Raw Materials>> The silicon atom raw material used in the zeolite production method of the present invention is not particularly limited, and various known substances can be used. For example, colloidal silica, amorphous silica, sodium silicate, trimethylethoxysilane, tetraethyl orthosilicate, aluminosilicate gel, and zeolite can be used. Among these, amorphous silica is preferred because it contains less alkali metal. These may be used individually, or two or more may be used in any combination and ratio.

[0029] <<Aluminum atomic raw material>> The aluminum atom raw material should be a water-soluble material. Furthermore, aluminum hydroxide is preferred because it has a low alkali metal content, and water-soluble amorphous aluminum hydroxide is particularly preferred in order to grow the zeolite into a spherical shape without aging.

[0030] <<Alkali Metal Atom Raw Materials>> Alkali metal atom raw materials are not required, but if they are used, the content of alkali metal atoms other than organic structure-determining agents per mole of Si atoms should be 0.05 moles or less. When alkali metal atom raw materials are used, the alkali metal atoms are not particularly limited, and known alkali metals used in zeolite synthesis can be used, but at least one alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium is preferred. The amount of alkali metal used is preferably 0.045 or less, more preferably 0.04 or less, even more preferably 0.035 or less, and particularly preferably 0.03 or less, in terms of molar ratio to silicon (Si) contained in the raw material composition. It is thought that a small amount of alkali metal atom raw material makes it easier for the zeolite to grow spherical, resulting in a shorter c-axis length of the crystal lattice and a tendency for the average coefficient of thermal expansion to become negatively large.

[0031] <<Organic structure directing agent>> Various known substances such as tetraethylammonium hydroxide (TEAOH) and tetrapropylammonium hydroxide (TPAOH) can be used as organic structure-determining agents. Of these, N,N,N-trimethyl-1-adamantaammonium hydroxide (TMAdaOH) is preferred. The amount of organic structure-determining agent used is typically 0.01 or more, preferably 0.02 or more, more preferably 0.03 or more, particularly preferably 0.04 or more, and most preferably 0.05 or more, in molar ratio to silicon (Si) contained in the raw material composition. On the other hand, it is typically 1 or less, preferably 0.6 or less, more preferably 0.55 or less, and even more preferably 0.5 or less. It is believed that this range facilitates the growth of high-purity spherical zeolites with fewer by-products.

[0032] <<Seed crystal zeolite>> In the manufacturing method of the present invention, a zeolite can be used as a seed crystal. When using a seed crystal zeolite, one type may be used alone, or two or more types may be used in any combination and ratio.

[0033] <<Water>> When using seed crystal zeolite, the amount of water used is usually 5 or more, preferably 7 or more, more preferably 9 or more, and even more preferably 10 or more, in terms of the molar ratio to silicon (Si) contained in the raw material composition other than the seed crystal zeolite, from the viewpoint of facilitating crystal formation. This range is preferable as it facilitates crystal formation. Furthermore, it is thought that zeolites with larger particle sizes can be easily produced by synthesizing under conditions where the raw material concentration is diluted by increasing the amount of water. On the other hand, in order to sufficiently obtain the effect of reducing the cost of wastewater treatment, the molar ratio to silicon (Si) is usually 50 or less, preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0034] <<Mixing of raw materials (preparation of raw material composition before reaction)>> The raw material composition can usually be obtained by mixing silicon atom raw materials, aluminum atom raw materials, an organic structure-regulating agent, and water, and then adding seed crystal zeolite if used. In addition to the components mentioned above, other components such as acidic components that promote the reaction and metal stabilizers such as polyamines may be added as needed at any step in the present invention.

[0035] <<Aging>> The raw material composition prepared as described above may be hydrothermally synthesized immediately after preparation, but in order to obtain a zeolite with higher crystallinity, it is preferable to age it for a certain period of time under predetermined temperature conditions. In particular, when scaling up the reaction, it is preferable to age the raw materials while stirring them for a certain period of time, as this improves agitation and makes it easier to make the raw materials more uniform. The temperature during aging is usually 100°C or lower, preferably 95°C or lower, more preferably 90°C or lower, and there is no particular lower limit, but it is usually 0°C or higher, preferably 10°C or higher. The aging temperature may be constant during aging, or it may be changed in stages or continuously. The aging time is not particularly limited, but is usually 2 hours or more, preferably 3 hours or more, more preferably 5 hours or more, and on the other hand, is usually 30 days or less, preferably 10 days or less, and even more preferably 4 days or less.

[0036] <<Hydrothermal synthesis>> Next, the obtained raw material composition is subjected to hydrothermal synthesis. Hydrothermal synthesis is typically carried out by placing the raw material composition prepared as described above, or the aqueous gel obtained by maturing it, into a pressure-resistant container and maintaining a predetermined temperature under self-generated pressure or under gas pressure that does not inhibit crystallization, while stirring, rotating or oscillating the container, or while remaining still. The reaction temperature during hydrothermal synthesis is usually 120°C or higher to accelerate the reaction rate, preferably 130°C or higher, more preferably 140°C or higher, and particularly preferably 150°C or higher. On the other hand, it is usually 230°C or lower, preferably 220°C or lower, more preferably 200°C or lower, and even more preferably 190°C or lower. The reaction time is not particularly limited, but is usually 2 hours or more, preferably 3 hours or more, and more preferably 5 hours or more, and on the other hand, it is usually 30 days or less, preferably 10 days or less, more preferably 7 days or less, and even more preferably 5 days or less. The reaction temperature may be constant during the reaction, or it may be changed stepwise or continuously. The reason why the zeolite according to the first embodiment of the present invention can be produced by the zeolite production method of the present invention is presumed to be as follows. When producing zeolite, alkali metals are generally used to dissolve the raw material components. In contrast, the zeolite production method of the present invention does not use alkali metals, or if it does, it is used in an amount less than a certain amount. As a result, crystals are more likely to grow in the raw material composition starting from the organic structure-determining agent, and from this starting point, the crystals are more likely to grow in a spherical shape. It is then presumed that distortion occurs in the crystal lattice during the process of crystal growth into a spherical shape, and that this distortion is fixed by firing. This presumption is supported by the fact that the c-axis length of the crystal lattice in Examples 1 to 3 (produced by the zeolite production method of the present invention), described later, is shorter than that of Comparative Examples 1 (no firing) and 2 (using sodium hydroxide). Furthermore, it is presumed that the zeolite according to the first embodiment of the present invention tends to have a low average thermal expansion coefficient due to the presence of strain in the crystal lattice. In other words, it is thought that the zeolite shrinks when heated as the strain is relieved due to the presence of strain in the crystal lattice. Also, for similar reasons, it is presumed that the zeolite according to the first embodiment of the present invention tends to have an even lower average thermal expansion coefficient in the high-temperature range (50 to 350°C). This presumption is also supported by the fact that the average thermal expansion coefficients of Examples 1 to 3, which have a shorter c-axis length in the crystal lattice, are lower than those of Comparative Examples 1 and 2, as will be discussed later in the comparison between Examples 1 to 3 and Comparative Examples 1 to 2.

[0037] [Second Embodiment] <Composition> A composition according to a second embodiment of the present invention (hereinafter sometimes referred to as "the composition of the present invention") is a composition containing the zeolite according to the first embodiment and a resin. As will be described later, the zeolite according to the first embodiment tends to have an extremely low average coefficient of thermal expansion. Therefore, by including the zeolite, the thermal expansion of the composite material made of the composition according to the second embodiment can be suppressed. When the composition of the present invention is in liquid form (hereinafter sometimes referred to as "the liquid composition of the present invention"), the amount of zeolite contained in the resin composition is preferably 25% by mass or more, more preferably 30% by mass or more, even more preferably 35% by mass or more, even more preferably 40% by mass or more, particularly preferably 45% by mass or more, and especially preferably 50% by mass or more, based on the total amount of the composition, from the viewpoint of suppressing viscosity increase and lowering the coefficient of thermal expansion. 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, when the resin composition contains fillers other than the zeolite according to the first embodiment, the zeolite content in the total fillers is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, most preferably 70% by mass or more, and most preferably 90% by mass or more, as this reduces the increase in viscosity during resin mixing and makes it easier to reduce the thermal expansion coefficient of the cured product. The composition of the present invention may be liquid, gel-like, or solid, but hereinafter, when referred to as "liquid," it means that it is liquid at room temperature (23°C). In a preferred embodiment, the composition of the present invention can be liquid when the resin is an epoxy resin.

[0038] (resin) The resin used in the composition according to the second embodiment of the present invention is not particularly limited as long as it exhibits the effects of the present invention, but from the viewpoint of further exhibiting the effects as a composite material, it is preferable that it be at least one selected from the group consisting of epoxy resins and polyimide resins. In particular, epoxy resins are preferred when used as a liquid composition useful as a sealant, etc. Furthermore, polyimide resins are preferred when used as a composition useful as a substrate, etc. 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, based on the total amount of the composition, from the viewpoint of maintaining the excellent physical properties of the resin and achieving both heat resistance (resistance to thermal expansion) as a 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.

[0039] <<Epoxy resin>> In the present invention, it is preferable to use epoxy compounds having aromatic rings, such as bisphenol A type skeletons, bisphenol F type skeletons, and biphenyl skeletons, as the coefficient of thermal expansion of the epoxy resin composite material obtained by curing the liquid composition tends to be low. Specifically, examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalene ring-containing epoxy resin, epoxy resin having a dicyclopentadiene skeleton, phenol novolac type epoxy resin, cresol novolac 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, naphthalene ring-containing epoxy resin, and aminophenol type epoxy resin are preferred, and more preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene ring-containing epoxy resin, aminophenol type epoxy resin, and biphenyl type epoxy resin are used.

[0040] In terms of the tendency for the glass transition temperature of epoxy resin composites obtained by thermosetting liquid compositions to be high, it is preferable to use polyfunctional epoxy resins. Preferred polyfunctional epoxy resins include various phenols such as phenol novolac resins, cresol novolac resins, bisphenol A novolac resins, dicyclopentadienephenol resins, phenol aralkyl resins, naphthol novolac resins, biphenyl novolac resins, terpene phenol resins, and heavy oil-modified phenol resins, as well as glycidyl ether type polyfunctional epoxy resins such as epoxy resins produced from various phenol compounds such as polyhydric phenol resins obtained by condensation reactions of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, and glyoxal, and epihalohydrins.

[0041] From the viewpoint of fluidity, the epoxy resin used in this invention preferably has a viscosity of 5 Pa·s or less at 23°C, and more preferably 0.1 to 3 Pa·s. The method for measuring the viscosity of epoxy resin is specified in JIS K7233 (1986), and the single-cylinder rotational viscometer method is suitable. The viscosity of the epoxy resin used in this invention at 23°C is preferably measured using a B-type rotational viscometer ("LVDV-1Pri", manufactured by Brookfield, spindle: S62), which is one of the single-cylinder rotational viscometer methods.

[0042] From the viewpoint of viscosity control, the epoxy resin preferably has an epoxy equivalent of 50 g / equivalent to 500 g / equivalent, and more preferably 90 g / equivalent to 150 g / equivalent. A high epoxy equivalent is preferable in terms of excellent heat resistance. On the other hand, a low epoxy equivalent is preferable in terms of the fact that a lower melting point or lower viscosity of the epoxy resin leads to good fillability of the liquid composition and easier bonding by filling. Epoxy resins may be used individually or mixed in any combination and ratio of two or more types, but in the case of a mixture, the epoxy equivalent shall be the equivalent of the mixture.

[0043] The epoxy resin content in the liquid composition of the present invention is preferably low in terms of the relative amount of inorganic fillers and the like, which makes it easier to lower the coefficient of thermal expansion. On the other hand, it is preferable that the epoxy resin content is high in terms of the ease with which the excellent physical properties of the epoxy resin are maintained. Specifically, it is preferably 5% by mass or more, and more preferably 10% by mass or more, based on the total amount of the 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.

[0044] (Hardening agent) The liquid composition of the present invention preferably further contains a curing agent. A curing agent is a substance that contributes to the crosslinking reaction between crosslinking groups of an epoxy resin. There are no particular restrictions on the curing agent, and those generally known as epoxy resin curing agents can be used. Examples include phenolic curing agents, aliphatic amines, polyetheramines, alicyclic amines, aromatic amines and other amine-based curing agents, acid anhydride-based curing agents, amide-based curing agents, tertiary amines, imidazoles and their derivatives, organophosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halogenated amine complexes, polymercaptan-based curing agents, isocyanate-based curing agents, blocked isocyanate-based curing agents, and dicyandiamine compounds. From the viewpoint of imparting fluidity and rapid curing, acid anhydride-based curing agents are preferred as curing agents.

[0045] Specific examples of phenolic curing agents include bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 1,4-bis(4-hydroxyphenoxy)benzene, 1,3-bis(4-hydroxyphenoxy)benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolac, bisphenol A novolac, o-cresol novolac, m-cresol novolac, p-cresol novolac, xylenol novolac, poly-p-hydroxystyrene, hydroquinone, resorcinol, catechol, t-butylcatechol, t-butylhydroquinone, fluoroglycinol, pyrogallol, t-butylpyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, Examples include 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allyl or polyallylized dihydroxynaphthalenes, allylated bisphenol A, allylated bisphenol F, allylated phenol novolac, allylated pyrogallol, and the like.

[0046] Specific examples of amine-based curing agents include aliphatic amines such as ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, and tetra(hydroxyethyl)ethylenediamine. Examples of polyetheramines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propylamine), polyoxypropylenediamine, and polyoxypropylene triamines. Examples of alicyclic amines include isophoronediamine, metacenediamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, and norbornenediamine. Examples of aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethylphenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl)ethylamine, diaminodiethyldimethyldiphenylmethane, and α,α'-bis(4-aminophenyl)-p-diisopropylbenzene.

[0047] Specific examples of acid anhydride-based curing agents include dodecenyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyl octadecanediic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenedicarboxylic acid anhydride, methylcyclohexenetetracarboxylic acid anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzoyl anhydride. Examples include phenonetetracarboxylic anhydride, ethylene glycol bistrimellitate dianhydride, hetic anhydride, nadic anhydride, methylnadic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dimethyl-6-(2-methyl-1-propenyl)-4-cyclohexene-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, and 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride.

[0048] Examples of amide-based curing agents include dicyandiamide and polyamide resins. Examples of tertiary amines include 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol. Imidazoles and their derivatives include 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole, 2-ethyl-4(5)-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, and 2,4-diamino-6-[2'-methylimidazole]. Examples include dazolyl-(1')-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resins with the above imidazoles or polymer-encapsulated imidazoles.

[0049] Examples of organophosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine. Examples of phosphonium salts include tetraphenylphosphonium-tetraphenylborate, tetraphenylphosphonium-ethyltriphenylborate, and tetrabutylphosphonium-tetrabutylborate. Examples of tetraphenylboron salts include 2-ethyl-4-methylimidazole-tetraphenylborate and N-methylmorpholine-tetraphenylborate. These curing agents may be used individually or mixed in any combination and ratio of two or more types.

[0050] When the liquid composition of the present invention contains a curing agent, the curing agent content is preferably such that the effect of residual unreacted epoxy groups or functional groups of the curing agent is less likely to occur. In the case of a phenolic curing agent, amine curing agent, or acid anhydride curing agent, the equivalent ratio of epoxy groups in the epoxy resin to functional groups in the curing agent (functional groups in the curing agent / epoxy groups in the epoxy resin) is in the range of 0.8 to 2.0, and more preferably in the range of 0.8 to 1.5.

[0051] When the curing agent is an amide-based curing agent, tertiary amine, imidazole and its derivatives, organophosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron-halogenated amine complexes, polymercaptan-based curing agents, isocyanate-based curing agents, blocked isocyanate-based curing agents, etc., it is preferable to use 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more, per 100 parts by mass of epoxy resin. On the other hand, it is preferable to use 20 parts by mass or less, and more preferably 10 parts by mass or less. In the case of dicyandiamine compounds, it is preferable to use 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more, per 100 parts by mass of epoxy resin. On the other hand, it is preferable to use 10 parts by mass or less, and more preferably 6 parts by mass or less.

[0052] <<Polyimide resin>> In the present invention, polyimide resins obtained from tetracarboxylic dianhydrides and diamines are preferred because they tend to have a low coefficient of thermal expansion of the resin composite material, and they have excellent properties such as heat resistance, mechanical strength, electrical properties, and solvent resistance. In particular, aromatic polyimides obtained from aromatic tetracarboxylic dianhydrides and aromatic diamines are preferred. More specifically, it is preferable to use a polyimide powder obtained by polymerizing and imidizing an aromatic tetracarboxylic acid component and p-phenylenediamine, then scattering a polyimide precursor solution onto the resulting polyimide resin powder and granulating it, and then compounding it with a filler to form a resin composite material. Furthermore, the polyimide powder is granulated by binding polyimide precursors together, and in this aggregate, the polyimide precursor acts as a binder. As the polyimide precursor, for example, polyamic acid is used, and the polyimide precursor solution used as a raw material is polyamic acid produced by reacting a tetracarboxylic dianhydride with a diamine in the presence of a basic compound with a pKa of 7.5 or higher, using water and / or an alcohol-based solvent as the reaction solvent.

[0053] A preferred embodiment in the second embodiment is a liquid resin composition in which an epoxy resin is used as the resin and the zeolite according to the first embodiment is contained, wherein the viscosity is 1 Pa·s or more and 30 Pa·s or less, and the zeolite content is 40 to 70% by mass. The liquid resin composition is useful as an underfill material (hereinafter sometimes referred to as "liquid sealant"), and after curing, it can reduce the average coefficient of thermal expansion, making it suitable as a sealant.

[0054] Furthermore, another preferred embodiment in the second embodiment is a composite material that uses epoxy resin as the resin and contains zeolite according to the first embodiment, wherein the zeolite content is 40 to 70% by mass and the average thermal expansion coefficient at 25 to 100°C is 10 to 30 ppm / K. Because this composite material has a low average coefficient of thermal expansion between 25 and 100°C, it is useful as a material for various applications, and is particularly effective for electronic devices.

[0055] [Third Embodiment] <Composition> The compositions of the present invention may also contain, as inorganic fillers, zeolites other than the zeolite of the first embodiment, or inorganic fillers other than zeolites (hereinafter, both may be collectively referred to as "other inorganic fillers" or simply "inorganic fillers"). Therefore, the composition according to the third embodiment of the present invention is a composition containing the zeolite, resin and other inorganic fillers according to the first embodiment described above. Here, the resin is as described in detail in the composition according to the second embodiment.

[0056] (Inorganic filler) Inorganic fillers other than zeolites include at least one selected from the group consisting of metals, carbon, metal carbides, metal oxides, and metal nitrides. Examples of metals include silver, copper, aluminum, gold, nickel, iron, and titanium. Examples of carbon include carbon black, carbon fiber, graphite, fullerene, and diamond. Examples of metal carbides include silicon carbide, titanium carbide, and tungsten carbide. Examples of metal oxides include magnesium oxide, aluminum oxide (alumina), silicon oxide such as silica, calcium oxide, zinc oxide, yttrium oxide, zirconium oxide, cerium oxide, ytterbium oxide, and SiAlON (ceramics composed of silicon, aluminum, oxygen, and nitrogen). Examples of metal nitrides include boron nitride, aluminum nitride, and silicon nitride.

[0057] Other inorganic fillers that have a low coefficient of thermal expansion include zeolites, metal nitrides, and metal oxides.

[0058] (Shape of inorganic filler) The shape of the inorganic filler is not particularly limited, as long as the composition and resin composite exhibit desirable performance. It may be spherical, whisker-shaped, fibrous, plate-shaped, or aggregates thereof, but a spherical shape is preferred because it suppresses viscosity increase. The sphericity of the inorganic filler is preferably 0.6 or higher, more preferably 0.65 or higher, and particularly preferably 0.70 or higher. Furthermore, there is no particular upper limit to the sphericity; it may be 1 or less. Therefore, in the third embodiment of the present invention, the large-particle zeolite and the other inorganic filler preferably have a sphericity of 0.6 or higher, more preferably 0.65 or higher, and particularly preferably 0.70 or higher. Furthermore, it is preferable that the sphericity of the other inorganic filler is higher than that of the large-particle zeolite. Furthermore, the roundness of the other 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, and it is acceptable as long as it is 1 or less. The methods for measuring sphericity and roundness are as described above.

[0059] (Particle size of inorganic fillers) In the case of a liquid composition, the particle size of the inorganic filler is preferably small in order to easily fill the liquid composition even in narrow spaces. On the other hand, it is preferable that the particle size is large in order to prevent the viscosity of the liquid composition from becoming too high. When using a combination of fillers with small and large specific surface areas, a larger specific surface area increases the interaction between the filler and the resin, which tends to increase the viscosity of the liquid composition. Therefore, to reduce the viscosity of the liquid composition, it is preferable that the specific surface area of ​​the filler is small. The specific surface area tends to increase as the particle size decreases. Also, the specific surface area differs depending on the shape of the filler, with a spherical shape having the smallest specific surface area. Therefore, from the viewpoint of viscosity reduction, it is preferable that the inorganic filler is close to spherical and has a large particle size. In particular, for large particle size zeolites, it is preferable that their specific surface area is 1 × 10⁻⁶. -6 ( / m) or less is preferred, and 0.8 × 10 -6 ( / m) or less is even more preferable. In this invention, it is preferable that the particle size of the inorganic filler is smaller than that of the large-particle filler. When small-particle and large-particle fillers are used in combination, the small particles can fill the gaps between the large particles, resulting in a larger filling volume, a lower coefficient of thermal expansion, and reduced viscosity increase. Therefore, it is preferable that the particle size of the inorganic filler is smaller than that of the large-particle filler. Thus, it is preferable that the particle size of the inorganic filler is 0.1 μm or more and 1.0 μm (hereinafter also referred to as "small-particle inorganic filler"). Therefore, in terms of easily lowering the coefficient of thermal expansion, it is preferable that the composition of this invention contains both large-particle zeolite and small-particle inorganic filler. The particle size of the inorganic filler is measured in the same manner as the zeolite according to the first embodiment described above. That is, the particle size of the inorganic filler refers to the diameter of the circle with the largest diameter (equivalent circle diameter) that has 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 particle.

[0060] Zeolites are inorganic fillers with a low coefficient of thermal expansion, and can lower the coefficient of thermal expansion of epoxy resin composites, which are cured products of liquid compositions in one preferred embodiment of the present invention. However, because of their porous structure, they have a large specific surface area, and when added in large quantities, the viscosity of the liquid composition tends to increase. In the present invention, as a result of various studies, it has been found that by including small-particle inorganic fillers in addition to large-particle zeolites such as the zeolite of the first embodiment described above in the liquid composition, it is possible to lower the coefficient of thermal expansion of the liquid epoxy resin composite while preventing an increase in viscosity, thereby achieving a low viscosity liquid composition.

[0061] (Total amount of inorganic filler) The total content of all inorganic fillers (total inorganic fillers) in the composition is preferably high in terms of how easily the filler effect is exhibited. On the other hand, in the case of a liquid composition, it is preferable to have a low content in terms of high fluidity and ease of filling into narrow spaces. Specifically, in the composition according to the third embodiment of the present invention, the total content of all inorganic fillers is preferably 30% by mass or more, more preferably 35% by mass or more, and particularly preferably 40% by mass or more, based on the total amount of the composition. On the other hand, it is preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0062] (Content of large-grain zeolite) In the composition according to the third embodiment of the present invention, when the resin composition is a liquid composition, the content of the zeolite of the first embodiment in the composition is preferably 20% by mass or more, more preferably 25% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and most preferably 45% by mass or more, based on the total amount of the liquid composition, from the viewpoint of suppressing viscosity increase while keeping the coefficient of thermal expansion low. 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 zeolite (large particle size zeolite) content in the total filler is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, most preferably 70% by mass or more, and most preferably 90% by mass or more, because it results in a small increase in viscosity during resin mixing and easily reduces the thermal expansion coefficient of the cured product.

[0063] (Content of other inorganic fillers) The content of other inorganic fillers is preferably high in order to allow the filler's effect to be fully realized. On the other hand, in the case of a liquid composition, it is preferable to have a low content in order to increase the fluidity of the liquid composition and make it easier to fill into narrow spaces. In particular, when the other inorganic fillers are small-particle inorganic fillers, the specific surface area is large and the viscosity tends to increase, so fluidity can be increased by reducing the amount used. In the composition according to the third embodiment of the present invention, the content of other inorganic fillers is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more, based on 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.

[0064] [Fourth Embodiment] <Composition> In the case of a liquid composition, the composition of the present invention may contain a dispersant to improve the dispersibility of inorganic fillers such as large-particle zeolite. Therefore, the composition according to the fourth embodiment of the present invention is a composition containing the zeolite, resin, and dispersant according to the first embodiment described above. Here, the resin is as described in detail in the composition according to the second embodiment. The inventors have found that when a composition containing epoxy resin and zeolite filler is in liquid form, a dispersant having at least an amino group or an amine salt is superior from the viewpoint of viscosity reduction. Therefore, in terms of easily achieving low viscosity, it is preferable that the composition of the present invention contains a dispersant having at least an amino 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 of the functional groups of an amino group and an amine salt. Furthermore, from the viewpoint of reducing viscosity when the composition is in liquid form, it is preferable that the dispersant has an amino group at its terminus. The amine salt may be modified with an acid group such as phosphoric acid. In the fourth embodiment of the present invention, by using a specific dispersant, it is possible to prevent the viscosity of the liquid composition from becoming high, even while using zeolite as an inorganic filler.

[0065] (Dispersant) The composition according to the fourth embodiment of the present invention contains a dispersant to improve the dispersibility of inorganic fillers such as zeolites. Dispersants used in compositions containing resins and fillers are mainly added to liquid compositions containing resins and fillers with a large difference in polarity to improve the interfacial state between the two and improve compatibility. This can produce effects such as reducing viscosity, improving the dispersibility of fillers, and preventing filler aggregation and sedimentation.

[0066] Examples of dispersants in the fourth embodiment include acrylic dispersants and polymeric dispersants. Here, "polymeric dispersant" means a dispersant with a weight-average molecular weight of 1,000 or more. The main chain skeleton of the polymeric dispersant is not particularly limited, but examples include polyurethane skeleton, polyacrylic skeleton, polyester skeleton, polyamide skeleton, polyimide skeleton, and polyurea skeleton, with polyurethane skeleton, polyacrylic skeleton, and polyester skeleton being preferred in terms of storage stability. The structure of the polymeric dispersant is also not particularly limited, but examples include random structure, block structure, comb structure, and star structure, with block structure or comb structure being preferred in terms of storage stability.

[0067] Polymeric dispersants have structures with polar groups at their terminals or intramolecular structures, and it is known that their effects differ depending on the surface polarity of the inorganic filler. Examples of terminal polar groups include carboxyl groups, amino groups, phosphate groups, and hydroxyl groups, while examples of intramolecular structures include esters and fatty acid amides.

[0068] Furthermore, the dispersant is preferably a solvent-free type dispersant, particularly a solvent-free polymer dispersant. The absence of a solvent in the dispersant prevents void formation due to the dispersant volatilizing during heat curing of the composition. In this embodiment, from the viewpoint of reducing viscosity, a dispersant having at least an amino group or an amine salt is preferred. Details of the dispersant having at least an amino group or an amine salt will be described in the sixth embodiment below.

[0069] Commercially available dispersants can also be used. Examples of commercially available polymeric dispersants include the DISPERBYK series (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, 2155) from BIC-Chemie, and the EFKA series (4) from BASF Japan. 008, 4009, 4010, 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4340, 4400, 4401, 4402, 4403, 4406, 4800, 5010, 5044, 5054, 5055, 5063, 5064, 5065, 5066, 5070, 5244, and the Solsperse series commercially available from Lubrizol: 3000, 5000, 11200, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 2 4000SC, 24000GR, 26000, 28000, 31845, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 36000, 36600, 37500, 38500, 39000, 53095, 54000, 55000, 56000, 71000, and the DISPARLON series commercially available from Kusumoto Kasei Co., Ltd.: 1210, 1220, 1831, 1850, 1860, 2100, 2150, 2200, 7004, KS-260, KS-273N, KS-860, KS-873N , PW-36, DN-900, DA-234, DA-325, DA-375, DA-550, DA-1200, DA-1401, DA-7301, PB-711, PB-821, PB-822, PN-411, PA-111 from the Ajisper series sold by Ajinomoto Co., Inc., 104A, 104C, 104E, 104H, 104S, 104BC, 104DPM, 104PA, 104PG-50, 420, 440, DF110D, DF110L, DF37, DF58, DF75,Examples include DF210, CT111, CT121, CT131, CT136, GA, TG, TGE, STG and E1004 from the Orphine series (commercially available from Nisshin Chemical Industry Co., Ltd.), 70, 2120, and 2190 from the SN Sparse series (manufactured by Sannopco Co., Ltd.), the Adekacol and Adekatol series (commercially available from ADEKA Corporation), and the Sannonic series, Naroacty CL series, Emulmin series, Newpol PE series, Ionet M series, Ionet D series, Ionet S series, Ionet T series, and Sansepara 100 (commercially available from Sanyo Chemical Industries, Ltd.).

[0070] In the fourth embodiment, a high dispersant content is preferable in that it facilitates the uniform dispersion of inorganic fillers, for example, when the composition is liquid. On the other hand, a low dispersant content is preferable in that it reduces the likelihood of an increase in the coefficient of thermal expansion due to phase separation between the inorganic filler and resins such as epoxy resins. To facilitate the filling of liquid compositions into narrow spaces and to achieve a low coefficient of thermal expansion after curing, the dispersant content is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 0.1% by mass or more and 25% by mass or less, based on the total amount of the composition.

[0071] In each of the above embodiments, when the composition is a liquid composition, a low viscosity of the liquid composition is preferable in terms of ease of filling the composition into a narrow space. On the other hand, a high viscosity is preferable in terms of preventing dripping during composition filling. The viscosity of the liquid composition at 23°C is preferably 0.1 Pa·s or higher, more preferably 1 Pa·s or higher, even more preferably 5 Pa·s or higher, and particularly preferably 10 Pa·s or higher. On the other hand, it is preferably 250 Pa·s or lower, more preferably 200 Pa·s or lower, even more preferably 150 Pa·s or lower, and particularly preferably 30 Pa·s or lower.

[0072] A preferred embodiment of the above composition is a liquid composition in which an epoxy resin is used as the resin and the zeolite of the first embodiment is used as the zeolite. Here, the viscosity is preferably 1 Pa·s or more and 30 Pa·s or less. Furthermore, the zeolite content is preferably 40 to 70% by mass. The liquid composition is useful as an underfill material and is suitable as a sealant because it can reduce the average coefficient of thermal expansion after curing.

[0073] When the compositions in the second to fourth embodiments described above are in liquid form, they can be cured to form a resin composite material. For example, if the resin is an epoxy resin, the resin composite material will be an epoxy resin composite material. Details of the epoxy resin composite material will be described later. Also, if the resin is a polyimide resin, the resin composite material will be a polyimide resin composite material.

[0074] The average thermal expansion coefficient of the resin composite material at 25 to 100°C is preferably 0 ppm / K or higher, more preferably 2 ppm / K or higher, even more preferably 4 ppm / K or higher, and particularly preferably 10 ppm / K or higher. On the other hand, it is preferably 200 ppm / K or lower, even more preferably 100 ppm / K or lower, and particularly preferably 30 ppm / K or lower.

[0075] In particular, in the composition of the second embodiment, when epoxy resin is used as the resin and the zeolite of the first embodiment is used as the zeolite, the zeolite content is preferably 40 to 70% by mass, and the average thermal expansion coefficient at 25 to 100°C is preferably 10 to 30 ppm / K. Such resin composites have a low average thermal expansion coefficient at temperatures below the glass transition temperature, making them useful as materials requiring various heat resistances, and they are particularly effective for application in electronic devices.

[0076] <Resin composite material> In one embodiment of the present invention, a resin composite can be obtained by curing the above-described composition (the composition of the second to fourth embodiments). For example, if the resin is an epoxy resin, an epoxy resin composite can be obtained. When the resin is an epoxy resin, the composition is preferably a liquid composition. Methods for producing the epoxy resin composition and the epoxy resin composite will be described later. Furthermore, if the resin is a polyimide resin, a polyimide resin composite material can be obtained. A method for manufacturing the polyimide resin composite material can be, for example, the method described below.

[0077] (Method for manufacturing polyimide resin composite materials) Various known presses for molding thermoplastic resins can be used to mold polyimide resin composites. The heating temperature during molding is not particularly limited and is influenced by the properties of the resin used, but is usually 250°C or higher, preferably 300°C or higher, more preferably 350°C or higher, and even more preferably 390°C or higher. Furthermore, from the viewpoint of preventing resin degradation during heating and pressing, it is preferable to use a vacuum press that can reduce the amount of oxygen in the press during heating, or a press equipped with a nitrogen purging device.

[0078] (Reactive diluent) The liquid composition of the present invention may contain a reactive diluent. The reactive diluent is not particularly limited as long as it contains at least one monofunctional epoxy compound. A monofunctional epoxy compound is an epoxy compound having one epoxy group and has been conventionally used as a reactive diluent to adjust the viscosity of epoxy resin compositions. Monofunctional epoxy compounds are broadly classified into aliphatic monofunctional epoxy compounds and aromatic monofunctional epoxy compounds, and from the viewpoint of viscosity, aromatic monofunctional epoxy compounds are preferred.

[0079] (Other additives) In addition to the above, the liquid composition may appropriately contain other additives selected from coupling agents, UV inhibitors, antioxidants, plasticizers, flame retardants, colorants, flow improvers, defoamers, ion trappers, etc.

[0080] Furthermore, in this embodiment, the liquid composition is preferably solvent-free. By being solvent-free, it is possible to prevent the generation of voids and other defects due to the volatilization of the solvent when the liquid composition is heat-cured. Note that the term "solvent" refers to volatile components and in this specification includes water and organic solvents. A solvent-free liquid composition is one that substantially does not contain solvent, and 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.

[0081] (Viscosity of liquid composition) The liquid composition is a composition that is fluid at room temperature (23°C). The viscosity of the liquid composition of the present invention is preferably low in terms of ease of filling even narrow spaces. On the other hand, a high viscosity is preferable in terms of preventing dripping during filling. The viscosity of the liquid composition at 23°C is preferably 0.1 Pa·s or higher, more preferably 1 Pa·s or higher, even more preferably 5 Pa·s or higher, and particularly preferably 10 Pa·s or higher. On the other hand, it is preferably 250 Pa·s or lower, more preferably 200 Pa·s or lower, even more preferably 150 Pa·s or lower, and particularly preferably 30 Pa·s or lower. The viscosity of the liquid composition can be measured in the same manner as the viscosity measurement method for epoxy resins described above. The viscosity of the liquid composition used in this invention at 23°C is preferably measured using a Type B rotational viscometer, which is one of the single-cylinder rotational viscometers. For example, the Type B rotational viscometer described in the examples may be used.

[0082] (Average thermal expansion coefficient) When the liquid composition of the present invention is cured, it is preferable that the average thermal expansion coefficient (CTE1) is low in terms of preventing deformation of the epoxy resin composite material due to ambient temperature and heat generation. On the other hand, it is preferable that it be close to the average thermal expansion coefficient of the surrounding material in terms of preventing damage due to differences in average thermal expansion properties with the surrounding material. Therefore, when the liquid composition is used as an underfill material or the like in the manufacture of semiconductor devices, it is preferable that it be close to the average thermal expansion coefficient of the semiconductor substrate (for example, 3 to 4 ppm / K). From the above viewpoints, the liquid composition of the present invention preferably has an average coefficient of thermal expansion (CTE1) of 0 ppm / K or more when cured, more preferably 2 ppm / K or more, even more preferably 4 ppm / K or more, and particularly preferably 10 ppm / K or more. On the other hand, it is preferably 200 ppm / K or less, even more preferably 100 ppm / K or less, and particularly preferably 30 ppm / K or less.

[0083] The average thermal expansion coefficient and the glass transition temperature (Tg) of the cured product obtained by curing the liquid composition can be determined by measuring the average thermal expansion coefficient of the epoxy resin composite material (cured product) obtained by curing the liquid composition to a gel fraction of 80% or more. The average thermal expansion coefficient (CTE1) is determined in accordance with JIS K7197 (2012) by measuring the temperature dependence of the change in sample length at 25 to 100°C using the compression method by thermomechanical analysis, and is obtained from the slope of the tangent line. The specific measurement conditions for the average thermal expansion coefficient are as described in the examples.

[0084] (Glass transition temperature) The glass transition temperature (Tg) of the epoxy resin composite material obtained by curing the liquid composition of the present invention is not particularly limited. For example, when the Tg is high for the underfill material, the portion sealed with the underfill material has high protection against bumps at high temperatures and is preferable because it has excellent thermal cycling resistance (see, for example, Japanese Patent Application Publication No. 2017-110146). From such an viewpoint, the glass transition temperature (Tg) of the cured product of the liquid composition according to the fourth embodiment is preferably 50°C or higher, more preferably 80°C or higher. Furthermore, since warping at room temperature (23°C) tends to be less pronounced when the glass transition temperature is 150°C or lower, the glass transition temperature (Tg) is preferably 50 to 150°C, and more preferably 80 to 150°C. The glass transition temperature (Tg) can be measured using a thermomechanical analyzer (TMA). Specifically, it can be measured by the method described in the examples.

[0085] (Method for producing a liquid composition) The liquid composition of the present invention can typically be obtained by mixing and kneading epoxy resin, inorganic filler, a curing agent, a dispersant, a reactive diluent, and other additive components as needed using a vacuum mixer, mixing roll, planetary mixer, etc., and degassing as needed. The order in which these components are added is arbitrary, as long as there are no particular problems such as the occurrence of reactions or precipitates. Two or three or more of the constituent components may be mixed in advance and then the remaining components may be mixed, or all of them may be mixed at once. Furthermore, for example, zeolite with a particle size of 1.0 μm or more and 10 μm or less, and inorganic filler with a particle size of 0.1 μm or more and less than 1.0 μm may be used as raw materials when manufacturing the liquid composition to include the large-particle zeolite and small-particle inorganic filler produced by the above method in the liquid composition, or large-particle zeolite and small-particle inorganic filler produced by other methods may be included in the liquid composition.

[0086] <Epoxy resin composite material> The epoxy resin composite material according to the present invention can be obtained by curing the above-described liquid composition. The epoxy resin composite material is an epoxy resin composite material containing an epoxy resin and an inorganic filler, and it is preferable that the inorganic filler contains zeolite with a particle size of 1.0 μm or more and 10 μm or less (large particle size zeolite) and inorganic filler with a particle size of 0.1 μm or more and less than 1.0 μm (small particle size inorganic filler). By containing large particle size zeolite and small particle size inorganic filler, the epoxy resin composite material can be manufactured from a liquid composition with a relatively low viscosity while keeping the coefficient of thermal expansion low.

[0087] The glass transition temperature (Tg) of the epoxy resin composite material obtained by curing the liquid composition according to the present invention is not particularly limited. For example, when the Tg is high for the underfill material, the portion sealed with the underfill material has high protection against bumps at high temperatures and is preferable because it has excellent thermal cycling resistance (see, for example, Japanese Patent Application Publication No. 2017-110146). From this viewpoint, the glass transition temperature (Tg) of the cured product of the liquid composition according to the present invention is preferably 50°C or higher, more preferably 80°C or higher. Furthermore, since warping at room temperature (23°C) tends to be less pronounced when the glass transition temperature is 150°C or lower, the glass transition temperature (Tg) is preferably 50 to 150°C, and more preferably 80 to 150°C. The glass transition temperature (Tg) can be measured using a thermomechanical analyzer (TMA). Specifically, it can be measured by the method described in the examples.

[0088] The average thermal expansion coefficient (CTE1) and glass transition temperature of the epoxy resin composite material according to the present invention are, from the same viewpoint as above, the preferred ranges for these are the same as the preferred ranges for when the liquid composition is cured. Furthermore, the average thermal expansion coefficient and glass transition temperature can be measured for the epoxy resin composite material using the measurement method described above.

[0089] (Method of manufacturing epoxy resin composite material) Epoxy resin composites can be obtained by curing a liquid composition. Curing is preferably done by heating. There are no particular limitations on the method for producing epoxy resin composites, as long as the epoxy resin composite exhibits desirable performance, and it can be carried out appropriately using known methods, depending on the composition of the liquid composition and other factors.

[0090] Epoxy resin composites are preferably manufactured by filling gaps in the components of various products, such as electronic devices, with a liquid composition, and then curing and molding it. Alternatively, epoxy resin composites may be manufactured by applying a liquid composition to the components of various products, curing and molding them. Furthermore, the liquid composition can be molded into a desired shape by curing it, for example, while it is contained in a mold. Such molded articles can be manufactured using injection molding, injection compression molding, extrusion molding, or compression molding. The molding, or curing, of the epoxy resin composite can be carried out under the respective curing temperature conditions. The epoxy resin composite can also be obtained by carving the cured liquid composition into a desired shape. The heating temperature during heat curing is not particularly limited and is influenced by the curing agent used, but is usually 30°C or higher, preferably 50°C or higher, more preferably 60°C or higher, and even more preferably 80°C or higher. On the other hand, the heating temperature is usually 400°C or lower, preferably 350°C or lower, more preferably 300°C or lower, and even more preferably 250°C or lower. When the curing temperature is within the above range, it is easy to obtain high-quality resin composites in a short time.

[0091] (Application) 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 products, building components, and components and packaging materials for electronic devices, and are most preferably used in electronic devices. Accordingly, the present invention provides, in a preferred embodiment, an electronic device containing a resin composite, and more preferably, an electronic device containing an epoxy resin composite. An electronic device is a device having two or more electrodes that controls the current flowing between the electrodes or the voltage generated by electricity, light, magnetism, or chemical substances, or a device that generates light, an electric field, or a magnetic field by an applied voltage or current. Specifically, examples include resistors, rectifiers (diodes), switching elements (transistors, thyristors), amplifying elements (transistors), memory elements, or chemical sensors, or devices that combine or integrate these elements. Also, optical elements such as photodiodes or phototransistors that generate photocurrent, electroluminescent elements that emit light when an electric field is applied, and photoelectric conversion elements or solar cells that generate electromotive force from light can also be mentioned. Semiconductor devices are preferred among electronic devices. Semiconductor devices preferably have at least a semiconductor substrate, for example, a device on which a semiconductor chip is mounted on a substrate, or a device in which semiconductor chips or semiconductor substrates are stacked in multiple layers.

[0092] The liquid composition of the present invention is preferably used as a liquid encapsulant, and in this case, the epoxy resin composite material formed by curing the liquid composition is preferably used as an encapsulant. Liquid sealants are best used as sealing materials to fill gaps formed in constituent materials, and then harden to fill those gaps. Furthermore, the liquid sealant may be used as a sealant to fill gaps between components by, for example, applying it to various components, then placing another component on top of the liquid sealant, and then curing it as appropriate. In this case, the liquid sealant may be cured to a B-stage before the other component is placed on top. Among these, the liquid composition of the present invention is preferably used for applications where it is filled into gaps and then cured. That is, it is preferable to manufacture a sealing material by filling a gap with the liquid composition of the present invention and then curing it. The liquid composition of the present invention has low viscosity and can be filled into narrow gaps without creating voids or the like.

[0093] The liquid composition of the present invention is preferably used as a liquid encapsulant, and particularly preferably as an underfill material. The underfill material is preferably used in the manufacture of electrical devices, especially semiconductor devices, and is preferably used to fill gaps formed between a substrate and a semiconductor chip, between substrates, between semiconductor chips, etc. The substrate can be a known substrate, and it is preferable to use an organic material substrate such as an epoxy resin substrate or a phenolic resin substrate. The semiconductor chip is preferably formed from a semiconductor substrate such as a silicon substrate. The liquid composition of the present invention has a low coefficient of thermal expansion of its cured product. When used as an underfill material, the difference in coefficient of thermal expansion with that of semiconductor substrates and the like becomes smaller, thereby improving thermal cycling resistance and other properties.

[0094] The underfill material is preferably used as a sealing material to seal the gap between the substrate and the semiconductor chip in a laminate in which a semiconductor chip is mounted on a substrate, and is then cured by heating. In this case, it is preferable that the semiconductor chip is bonded to the surface of the substrate, which has a wiring pattern formed via bumps, for example by reflow soldering, before the underfill material is filled.

[0095] Underfill material may be used in the manufacture of semiconductor devices by the pre-apply method. Specifically, underfill material is filled between multiple bumps on the surface of a semiconductor chip on which multiple bumps have been formed, thereby forming an underfill layer. The filled underfill material may be B-staged as needed. Subsequently, the semiconductor chip with the underfill layer formed on it should be placed on the surface of a substrate with the side on which the underfill layer is formed facing the substrate. Then, the underfill layer is hardened by heating and pressing to become a encapsulant, and the semiconductor chip is bonded to the surface of the substrate on which the wiring pattern has been formed via the bumps.

[0096] Alternatively, in the pre-apply method, an underfill layer may be formed by applying an underfill agent to the surface of a substrate on which a wiring pattern has been formed. The applied underfill layer may be B-staged as needed. After that, the semiconductor chip with bumps formed on it should be placed on the substrate with the underfill layer so that the side with the bumps faces the surface of the substrate on which the underfill layer has been formed. Then, the underfill layer is hardened by heating and pressing to become a encapsulant, and the semiconductor chip is bonded to the surface of the substrate on which the wiring pattern has been formed via the bumps.

[0097] In the above explanation, we described an example where the underfill material is used as a sealing material to fill the gap between the substrate and the semiconductor chip. However, the use of the underfill material is not particularly limited; it may also be used to fill the gaps between semiconductor chips, or as a sealing material to fill the gaps between substrates. Furthermore, the substrate is not limited to an organic material substrate, but may also be a semiconductor substrate or the like. [Examples]

[0098] The present invention will be described in more detail below with reference to examples, comparative examples, and reference examples, but the present invention is not limited to the following examples, comparative examples, and reference examples, unless it deviates from the spirit of the invention.

[0099] <Zeolite Synthesis> [Example 1] (Manufacturing of Zeolite Filler A1) In a container, N,N,N-trimethyl-1-adamantaammonium hydroxide (TMAdaOH) manufactured by Seichem Corporation was added sequentially as a structure directing agent (SDA), Kyowa Chemical Industry Co., Ltd.'s "Kyoward 200S" as aluminum hydroxide, and Nippon Aerosil Co., Ltd.'s "AEROSIL200" as silica. The composition and molar ratio of the resulting mixture were SiO2:Al2O3:TMAdaOH:H2O = 1.0:0.025:0.4:20. After thorough mixing, the mixture was placed in a pressure vessel and hydrothermally synthesized in an oven at 150°C for 48 hours. After suction filtration and washing, it was dried. The resulting powder was calcined at 600°C for 6 hours under air circulation to remove the structure directing agent (SDA), TMAdaOH, and obtain a CHA-type zeolite. The obtained zeolite consisted of particles with a particle size distribution as shown in Figure 1, with each particle having a particle size between 1.0 μm and 10 μm, and an average primary particle size of 3.1 μm. The average primary particle size was the average of the particle sizes of 50 randomly selected primary particles. Furthermore, the average thermal expansion coefficient at 50-100°C was -9.0 ppm / K, the average thermal expansion coefficient at 50-350°C was -17.0 ppm / K, the Si / Al2 ratio was 27.8, the sphericity was 0.85, the roundness was 0.845, the c-axis length was 14.67 Å, ​​and the countercation was of the proton type.

[0100] [Example 2] (Manufacturing of Zeolite Filler A2) In Example 1, a CHA-type zeolite was obtained in the same manner as in Example 1, except that the hydrothermal synthesis process involved rotating the heat-resistant container. The obtained zeolite consisted of particles with a particle size distribution as shown in Figure 2, with 99% of the particles having a particle size between 1.0 μm and 10 μm by volume. The average primary particle size was 2.4 μm. The average primary particle size was measured in the same manner as in Example 1. The average thermal expansion coefficient at 50-100°C was -9.0 ppm / K, the average thermal expansion coefficient 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 countercation was of the proton type.

[0101] [Example 3] (Manufacturing of Zeolite Filler A3) In Example 2, hydrothermal synthesis, drying, and calcination were carried out in the same manner as in Example 2, except that the composition and molar ratio of the raw material mixture were SiO2:Al2O3:TMAdaOH:H2O = 1.0:0.020:0.4:20, to obtain a CHA-type zeolite. Of the obtained zeolite, 81% of the particles had a particle size in the range of 1.0 μm to 10 μm by volume. The average primary particle size was 1.2 μm. The average primary particle size was measured in the same manner as in Example 1. Furthermore, the average thermal expansion coefficient at 50-100°C was -13.7 ppm / K, the average thermal expansion coefficient at 50-350°C was -12.9 ppm / K, the Si / Al2 ratio was 28.2, the sphericity was 0.84, the roundness was 0.835, the c-axis length was 14.59 Å, and the countercation was of the proton type.

[0102] [Comparative Example 1] (Manufacturing of Zeolite Filler A4) In a container, N,N,N-trimethyl-1-adamantaammonium hydroxide (TMAdaOH) manufactured by Seichem Corporation and aluminum hydroxide manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. were sequentially added as structure directing agents (SDA). After aging at 80°C for 12 hours, "CAB-O-SIL M-5" manufactured by Cabot Corporation was added as silica. The composition and molar ratio of the resulting mixture were SiO2:Al2O3:TMAdaOH:H2O = 1.0:0.025:0.4:20. After thorough mixing, the resulting mixture was placed in a pressure vessel and hydrothermally synthesized in an oven at 150°C for 48 hours. CHA-type zeolite was obtained by suction filtration and washing. The obtained zeolite had particle sizes ranging from 1.0 μm to 10 μm, and its average primary particle size was 3.1 μm. The average primary particle size was measured in the same manner as in Example 1. Furthermore, the average thermal expansion coefficient at 50-100°C was -5.0 ppm / K, and since TMAdaOH decomposed when heated above 300°C, the average thermal expansion coefficient at 50-350°C could not be measured. 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.

[0103] [Comparative Example 2] (Manufacturing of Zeolite Filler A5) In a container, the following were sequentially added as structure directing agents (SDAs): N,N,N-trimethyl-1-adamantaammonium hydroxide (TMAdaOH) manufactured by Seichem Corporation, sodium hydroxide manufactured by Kishida Chemical Co., Ltd., potassium hydroxide manufactured by Kishida Chemical Co., Ltd., aluminum hydroxide manufactured by Aldrich Corporation, and "Snowtex 40" manufactured by Nissan Chemical Corporation as silica. 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 a seed crystal and mixing thoroughly, the resulting mixture was placed in a pressure vessel and hydrothermal synthesis was carried out in a 160°C oven for 48 hours while rotating the heat-resistant vessel. The powder obtained by suction filtration and washing was calcined at 600°C for 6 hours under air circulation to remove the structural regulator and obtain a CHA-type zeolite. The obtained zeolite consisted of particles with a particle size distribution as shown in Figure 3, with 17% of the particles having a particle size between 1.0 μm and 10 μm by volume. The average primary particle size was 0.5 μm. The average primary particle size was measured in the same manner as in Example 1. The average thermal expansion coefficient at 50-100°C was -4.9 ppm / K, the average thermal expansion coefficient at 50-350°C was -5.87 ppm / K, the Si / Al2 ratio was 20.0, and the shape was cubic. The sphericity was 0.59, the roundness was 0.785, the c-axis length was 14.83 Å, and the countercations were sodium and potassium type.

[0104] The results of Examples 1-3 and Comparative Examples 1 and 2 are summarized in Table 1.

[0105] [Table 1]

[0106] From the results in Table 1, it can be seen that the zeolite according to the first embodiment of the present invention has a large average primary particle size and is spherical based on the results of sphericity and roundness. Furthermore, since the coefficient of thermal expansion is large in the negative direction, it can be seen that the thermal shrinkage rate is large. Therefore, it is considered that a resin composite material with suppressed thermal expansion can be obtained by using this zeolite in combination with a resin. Furthermore, the zeolite of Comparative Example 1, which was not calcined after hydrothermal synthesis, had a c-axis length similar to that of the zeolite of Comparative Example 2, which was produced by a conventional manufacturing method. In contrast, the zeolite of Example 1, which was produced by calcining after hydrothermal synthesis, had a shorter c-axis length. Therefore, it is presumed that the zeolite of the present invention has a lower coefficient of thermal expansion due to its shorter c-axis length.

[0107] Next, examples of the composition and resin composite material of the present invention are shown below. <Composition ingredients> The compounding components used in the preparation of the liquid composition and resin composite material are as follows: <Inorganic filler> Zeolite fillers A1, A3, and A4 were those produced in the above-described examples.

[0108] The inorganic fillers other than zeolite fillers A1 to A5 are as follows: Silica Filler A: Manufactured by Ryumori Co., Ltd., product name "HL-3100" (average particle size 45 μm, perfectly spherical silica filler) Silica Filler B: Admatex Co., Ltd. Product name "SC2053-SQ" (Silica with an average particle size of 0.5 μm, where the particle size of each particle is between 0.1 μm and less than 1.0 μm, sphericity 0.95) Zeolite filler B: (CHA zeolite with individual particle sizes within the range of less than 1.0 μm, average primary particle size 0.1-0.2 μm, sphericity 0.58)

[0109] <Epoxy resin> Manufactured by Mitsubishi Chemical Corporation, product name "jER630" (p-aminophenol type epoxy resin, epoxy equivalent: 97g / equivalent) <Polyimide Powder> Manufactured by Ube Industries, Ltd., product name "UIP-R" (polyimide, average particle size: 7 μm, specific gravity 1.39) <Hardening agent> Acid anhydride-based curing agent: Manufactured by Hitachi Chemical Co., Ltd., product name "HN-2200" (methyltetrahydrophthalic anhydride, amine equivalent 83g / equivalent) <Dispersant> Dispersant A: Manufactured by BIC Chemie Japan, wetting dispersant, product name "DISPERBYK-2152" (amino group-containing ultramolecular weight polyester, comb-type, solvent-free) Dispersant B: Manufactured by BIC Chemie Japan, wetting dispersant, product name "DISPERBYK-145" (comb-type polymer polyester-terminated phosphate-modified amine salt, solvent-free) Dispersant C: Manufactured by BIC Chemie Japan, wetting dispersant, product name "BYK-W9010" (polyester phosphate, solvent-free)

[0110] (Evaluation of physical properties) The physical properties were evaluated as follows: (Gel fraction) The gel fraction of the resin composite material was measured using the following procedure. A resin composite material sample, prepared under curing conditions of 80°C for 2 hours followed by 120°C for 2 hours, was cut out in the range of 0.5 to 0.6 g and placed on a wire mesh. The wire mesh was then immersed in acetone and left to stand for 24 hours. After that, the wire mesh was removed from the acetone and vacuum-dried. The gel fraction was defined as the ratio of the weight of the sample after immersion to the weight before immersion. (Viscosity of liquid composition) The viscosity of the liquid composition at 23°C was measured using a B-type rotational viscometer. For viscosity between 0.1 and 100 Pa·s, the Brookfield LVDV-1 Pri with spindles S64 and S63 was used, while for viscosity exceeding 100 Pa·s, the Brookfield HBDV-E with spindle S-07 was used. The values ​​measured at 20 rpm were used as representative values ​​for the viscosity of each sample.

[0111] (Average thermal expansion coefficient (CTE1) of epoxy resins and epoxy resin composites) The average thermal expansion coefficient of epoxy resin composites obtained by curing a liquid composition to a gel fraction of 80% or more was measured by thermomechanical analysis in accordance with JIS K7197 (2012). A thermomechanical analyzer (instrument name: TMA SS7100, manufactured by SII Nanotechnology Co., Ltd.) was used for measurement by compression. Specifically, the epoxy resin composite was cut to a size of φ6 mm × 10 mm, and the temperature was measured by compression from 200°C to 20°C at a rate of 5°C / min using a thermomechanical analyzer. The temperature change of the change in sample length between 25 and 100°C was measured, and the slope of the tangent line was defined as the average thermal expansion coefficient (CTE1).

[0112] (Average thermal expansion coefficient (CTE1) of polyimide resin and polyimide resin composites) The average thermal expansion coefficient of the polyimide resin composite obtained by curing to a gel fraction of 80% or more was measured by thermomechanical analysis in accordance with JIS K7197 (2012). A thermomechanical analyzer (instrument name: TMA SS7100, manufactured by SII Nanotechnology Co., Ltd.) was used for measurement by compression. Specifically, the polyimide resin composite was cut to a size of 10 mm in width, 6 mm in thickness, and 10 mm in height, and the temperature was measured by cooling from 200°C to 20°C at a rate of 5°C / min using the thermomechanical analyzer by compression. The temperature change of the change in sample length between 25 and 100°C was measured, and the slope of the tangent line was defined as the average thermal expansion coefficient (CTE1).

[0113] (Glass transition temperature of epoxy resin composites) The glass transition temperature (Tg) of epoxy resin composites obtained by curing a liquid composition to a gel fraction of 80% or more was measured using a thermomechanical analyzer (TMA). Specifically, measurements were performed using the same apparatus and conditions as for the evaluation of the thermal expansion coefficient described above, and a graph was created with temperature on the X axis and the linear expansion coefficient on the Y axis. CTE'1 was determined from the slope of the tangent line in the 15-75°C range of this graph, and CTE'2 was determined from the slope of the tangent line in the 150-200°C range. The glass transition temperature Tg (°C) was determined from the intersection of CTE'1 and CTE'2.

[0114] [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 (EME Co., Ltd., "V-mini 300"). The viscosity of this liquid composition at 23°C was measured with a rotational viscometer. Subsequently, the mixture was poured into a mold and heated at 80°C for 2 hours, then heated at 120°C for 2 hours to cure to a gel fraction of 80% or more, and then demolded to obtain an epoxy resin composite material.

[0115] [Comparative Example 3] As shown in Table 2, 21 g of epoxy resin, 29 g of hardener, and 50 g of silica filler A were weighed into a cup and mixed by hand. A liquid composition and a resin composite were obtained in the same manner as in Example 4, except for the mixing ratio.

[0116] [Comparative Example 4] As shown in Table 2, 17 g of epoxy resin, 23 g of hardener, and 60 g of zeolite filler B were weighed into a cup and mixed by hand. A liquid composition and a resin composite were obtained in the same manner as in Example 4, except for the mixing ratio.

[0117] [Example 5] To obtain the formulations shown in Table 2, 21 g of epoxy resin, 29 g of hardener, and 50 g of zeolite filler A1 were weighed into a cup and mixed by hand. A liquid composition and a resin composite were obtained in the same manner as in Example 4, except for the mixing ratio.

[0118] [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. A liquid composition and a resin composite were obtained in the same manner as in Example 4, except for the mixing ratio.

[0119] [Example 7] As shown in Table 2, 17 g of resin, 23 g of curing agent, 59 g of zeolite filler A1, and 1 g of dispersant C were weighed into a cup and mixed. A liquid composition and a resin composite were obtained in the same manner as in Example 4, except for the mixing ratio.

[0120] [Example 8] As shown in Table 2, 17 g of epoxy resin, 23 g of curing agent, 59 g of zeolite filler A1, and 1 g of dispersant A were weighed into a cup and mixed. A liquid composition and a resin composite were obtained in the same manner as in Example 4, except for the mixing ratio.

[0121] [Example 9] As shown in Table 2, 17 g of epoxy resin, 23 g of curing agent, 59 g of zeolite filler A1, and 1 g of dispersant B were weighed into a cup and mixed. A liquid composition and a resin composite were obtained in the same manner as in Example 4, except for the mixing ratio.

[0122] [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. A liquid composition and a resin composite were obtained in the same manner as in Example 4, except for the mixing ratio.

[0123] The viscosity of the liquid compositions in Examples 4-10 and Comparative Examples 3-4 was measured, and the average thermal expansion coefficient (CTE1) and glass transition temperature (Tg) of the epoxy resin composite were also measured. The results are shown in Table 2.

[0124] [Table 2]

[0125] [Comparative Example 5] In Example 6, a liquid composition and a resin composite were obtained in the same manner as in Example 6, except that a zeolite filler was not used. The viscosity of the liquid composition was 0.4 Pa·s, and the average coefficient of thermal expansion (CTE1) of the epoxy resin composite was 64 ppm / K. [Example 11] In Example 6, a liquid composition and a resin composite were obtained in the same manner as in Example 6, except that zeolite filler A3 was used instead of zeolite filler A1. The average coefficient of thermal expansion (CTE1) of the epoxy resin composite was 20 ppm / K. [Reference example 1] In Example 6, a liquid composition and a resin composite were obtained in the same manner as in Example 6, except that zeolite filler A4 was used instead of zeolite filler A1. The average coefficient of thermal expansion (CTE1) of the epoxy resin composite was 30 ppm / K.

[0126] Examples 5 to 11 confirmed that by including the zeolite according to the present invention, a low-viscosity liquid composition can be obtained, and that the thermal expansion coefficient of the resin composite material cured from this liquid composition can be reduced. In particular, a comparison of Examples 5 and 11, which contain the zeolite of Example 1 or 3, with Reference Example 1, which contains the zeolite of Comparative Example 1, confirmed that by including the zeolite according to the present invention, a resin composite material with a low thermal expansion coefficient can be obtained. Furthermore, as is clear from the results in Table 2, the resin composites of Examples 5 and 6 containing the zeolite according to the present invention had a lower coefficient of thermal expansion compared to the resin composite of Comparative Example 3 containing large-particle silica filler. Also, the liquid compositions of Examples 5 and 6 containing the zeolite according to the present invention had lower viscosity compared to the liquid composition of Comparative Example 4 containing small-particle zeolite. In other words, it was confirmed that by including the zeolite according to the present invention, a low-viscosity liquid composition can be obtained, and the coefficient of thermal expansion of the resin composite material cured from this liquid composition can be lowered. In Examples 4 and 10, by using a combination of large-particle zeolite and small-particle inorganic filler, the viscosity of the liquid composition was reduced while lowering the coefficient of thermal expansion of the epoxy resin composite obtained by curing the liquid composition. In contrast, in Comparative Example 3, when large-particle silica filler was included, and its content was similar to that of the large-particle zeolite in Example 10, the viscosity of the liquid composition decreased, but the average coefficient of thermal expansion (CTE1) increased. Furthermore, although Examples 5 and 10 contained similar amounts of large-particle zeolite, both were able to reduce viscosity while also lowering the average coefficient of thermal expansion (CTE1) to some extent. In particular, Example 10 showed an even lower average coefficient of thermal expansion (CTE1) compared to Example 5. In Comparative Example 4 and Example 6, the average coefficient of thermal expansion (CTE1) decreased when zeolite filler was included, and when the zeolite filler content was increased even further than in Comparative Example 3 and Example 5. Here, since the viscosity of the liquid composition in Example 6 did not increase compared to Comparative Example 4, it was considered suitable as an underfill material to be used to fill gaps. In other words, it was confirmed that a low viscosity liquid composition can be obtained by using the large-particle zeolite of the present invention, and by curing this, a resin composite material with a low coefficient of thermal expansion can be obtained.

[0127] As shown in Table 2, a comparison of Examples 8 and 9 with Examples 6 and 7 revealed that the addition of dispersant A or B resulted in viscosity reduction, confirming that dispersants A and B containing amino groups or amine salts are effective in reducing viscosity. Furthermore, the addition of dispersants resulted in sufficiently high glass transition temperatures (Tg) for the resin composites in Examples 8 and 9, demonstrating excellent thermal cycling resistance, and confirming that their average thermal expansion coefficient is also suitable for underfill materials.

[0128] [Example 12] 21 g of polyimide powder and 9 g of zeolite filler A1 prepared in Example 1 were weighed into a cup, mixed, and then spread into a press mold. The mold was set in a high-temperature vacuum press (manufactured by Kitagawa Seiki Co., Ltd.), and pressed at a press temperature of 390°C and a press pressure of 8 MPa for 30 minutes. Upon demolding, a molded body measuring 11 cm in length, 2.5 cm in width, and 6 mm in thickness was obtained. 10 mm sections were cut from each end, and the average coefficient of thermal expansion was measured. The results are shown in Table 3.

[0129] [Comparative Example 6] In Example 12, a molded article was manufactured in the same manner as in Example 12, except that zeolite filler A4, which was produced in Comparative Example 1, was used as the zeolite. The average coefficient of thermal expansion was then measured. The results are shown in Table 3.

[0130] [Comparative Example 7] In Example 12, a molded article was manufactured in the same manner as in Example 12, except that a zeolite filler was not used, and its average thermal expansion coefficient was measured. The results are shown in Table 3.

[0131] [Table 3]

[0132] Table 3 confirms that, even with polyimide resins, a resin composite material with a low coefficient of thermal expansion can be obtained by using the large-particle zeolite of the present invention. [Industrial applicability]

[0133] According to the present invention, a low-viscosity liquid composition can be provided. Furthermore, by curing this liquid composition, a resin composite material with a low coefficient of thermal expansion can be provided. In other words, according to the composition of the present invention, a sealing material with excellent injectability and heat resistance can be obtained, and is particularly useful as an underfill material. Furthermore, the resin composite material with a low coefficient of thermal expansion of the present invention is also useful as a sealing material manufactured by press molding or the like.

Claims

1. A zeolite having a particle size of 1.0 μm or more and 10 μm or less, containing d6r as CBU, and being an aluminosilicate.

2. The zeolite according to claim 1, wherein the c-axis length of the lattice constant is 14.80 Å or less.

3. The zeolite according to claim 1 or 2, which is spherical in shape.

4. A zeolite according to any one of claims 1 to 3, wherein the sphericity is 0.6 or more and 1 or less.

5. A zeolite according to any one of claims 1 to 4, wherein the roundness is 0.786 or more and 1 or less.

6. The zeolite according to any one of claims 1 to 5, wherein the average thermal expansion coefficient determined by the following method is -1000 ppm / K or more and less than 0 ppm / K. (Note that the average thermal expansion coefficient is determined in accordance with JIS K7197 (2012) by measuring the temperature dependence of the change in sample length at 50-100°C using the compression method of thermomechanical analysis, and then determining it from the slope of the tangent line.)

7. The zeolite according to any one of claims 1 to 6, wherein the average thermal expansion coefficient at 50 to 350°C, determined by the following method, is -1000 ppm / K or more and -9.5 ppm / K or less. (Note that the average thermal expansion coefficient is determined in accordance with JIS K7197 (2012) by measuring the temperature dependence of the change in sample length between 50 and 350°C using the compression method of thermomechanical analysis, and then determining it from the slope of the tangent line.)

8. A method for producing zeolite, comprising the steps of hydrothermally synthesizing a raw material composition containing silicon atom raw material, water-soluble aluminum atom raw material, organic structure-regulating agent, and water, and then calcining, wherein the composition is characterized in that the content of alkali metal atoms other than the organic structure-regulating agent is 0.05 moles or less per mole of Si atoms.

9. The method for producing zeolite according to claim 8, further comprising the step of maturing the raw material composition before the hydrothermal synthesis.

10. A composition containing the zeolite and resin according to any one of claims 1 to 7.

11. The composition according to claim 10, wherein the resin is at least one selected from the group consisting of epoxy resins and polyimide resins.

Images