Resin composition, resin composite material, liquid sealant, sealant, method for producing sealant, and electronic device

Abstract

To provide a resin composition having a low thermal expansion coefficient after curing, having a small filler particle size, and allowing adequate filling even in narrow gaps.SOLUTION: A resin composition comprises zeolite, an epoxy resin, and a curing agent, the zeolite having a particle diameter of 5.0 μm or less and a sphericity of 0.7 or more, and the curing agent having at least one amino group in one molecule.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Liquid sealants used as underfill materials are required to have excellent injectability, adhesion, curing properties, storage stability, etc., and to be free of voids. In addition, the parts sealed with the liquid sealant are required to have excellent moisture resistance, thermal cycle resistance, reflow resistance, crack resistance, warping resistance, etc. In order to satisfy the above requirements, liquid sealants mainly composed of epoxy resins are widely used as underfill materials.

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

[0004] [Patent Document 1] JP 2007-56070 A Summary of the Invention [Problem to be solved by the invention]

[0005] Liquid sealants using inorganic fillers such as silica filler do not have a sufficiently low thermal expansion coefficient, and from the standpoint of thermal cycle resistance, etc., there is a demand for a further reduction in the thermal expansion coefficient.

[0006] Furthermore, in liquid sealant applications that fill gaps of about 10 μm, such as underfill materials for narrow gaps, if the particle size of the inorganic filler is too large, the inorganic filler will not allow the liquid composition to spread into the gap, making it impossible to completely fill the desired gap, which may result in voids. It is generally said that if voids occur during filling of the liquid sealant, the solder will be partially exposed and break, adversely affecting reliability. In the future, it is expected that devices and the components that make them up will continue to become smaller, and semiconductor chips will also become smaller, thinner, and 3D stacked. For such applications, it is thought that mounting with an even narrower gap of around 25 μm will be required, rather than the current narrow gap of around 50 μm.

[0007] Therefore, an object of the present invention is to provide a resin composition that has a low coefficient of thermal expansion after curing, contains a small filler particle size, and allows sufficient filling even in narrow gaps. [Means for solving the problem]

[0008] The gist of the present invention is as follows. [1] A resin composition comprising a zeolite, an epoxy resin, and a curing agent, wherein the zeolite has a particle size of 5.0 μm or less and a sphericity of 0.7 or more, and the curing agent has at least one amino group in one molecule. [2] The resin composition according to [1] above, wherein the zeolite has d6r as a CBU. [3] The resin composition according to the above [1] or [2], wherein the zeolite contains a zeolite having an oxygen ring structure of 8 or less members. [4] The resin composition according to any one of the above [1] to [3], wherein the zeolite comprises a zeolite having a CHA structure. [5] The resin composition according to any one of the above [1] to [4], wherein the zeolite has a circularity of 0.800 or more. [6] The resin composition according to any one of the above [1] to [5], wherein the zeolite is an aluminosilicate. [7] The resin composition according to any one of the above [1] to [6], in which when cured to a gel fraction of 80% or more, the ratio (CTE2 / CTE1) of the average coefficient of thermal expansion (CTE2) at 150 to 200°C to the average coefficient of thermal expansion (CTE1) at 25 to 100°C of the cured product is less than 3.00. [8] The resin composition according to any one of the above [1] to [7], wherein when cured to a gel fraction of 80% or more, the cured product has a glass transition temperature (Tg) of 125 to 150°C. [9] The resin composition according to any one of the above [1] to [8], wherein the equivalent number of the curing agent is 0.6 to 1.4 relative to the equivalent number of the epoxy resin.

[10] The resin composition according to any one of the above [1] to [9], wherein the content of the zeolite is 40 to 70 mass %.

[11] A resin composite material formed by curing the resin composition according to any one of the above [1] to

[10] .

[12] A liquid sealant comprising the resin composition according to any one of [1] to

[10] above.

[13] An encapsulant comprising the resin composite material described in

[11] above.

[14] An electronic device comprising the resin composite material described in

[11] above.

[15] A method for producing an encapsulant, comprising the steps of filling a gap with the resin composition according to any one of the above [1] to

[10] and then curing the composition. Effect of the Invention

[0009] According to the present invention, it is possible to provide a resin composition which has a low coefficient of thermal expansion after curing, contains a small filler particle size, and allows sufficient filling even in a narrow gap. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] [Resin composition] The resin composition of the present invention (hereinafter sometimes referred to as "the resin composition") contains zeolite, an epoxy resin, and a curing agent. The zeolite used here is a spherical zeolite having a particle size of 5.0 μm or less and a sphericity of 0.7 or more, and the curing agent is characterized by having at least one amino group in one molecule. Each component will be described in detail below.

[0011] <Zeolite> The zeolite used in the resin composition of the present invention (hereinafter sometimes referred to as "the present zeolite") is characterized by a particle size of 5.0 μm or less and a sphericity of 0.7 or more. The zeolite having a particle size of 5.0 μm or less can be sufficiently filled even in a narrow gap, and is particularly preferable when used as an underfill material, for example. The present zeolite will be described in detail below.

[0012] (Zeolite particle size) The particle size of the present zeolite means the diameter of the largest circle (equivalent circle diameter) having an area equal to the projected area of ​​the particle when the particle is observed with a scanning electron microscope (SEM). The present zeolite may be formed into secondary particles by agglomeration of multiple zeolite particles. In this case, the particle size of the zeolite is the particle size of the primary particles. The particle size of the present zeolite is 5.0 μm or less, as described above. When the particle size of the zeolite is 5.0 μm or less, as described above, the resin composition can be sufficiently filled even in a narrow gap. From the above viewpoint, the smaller the particle size of the present zeolite, the more preferable, and the lower limit is not particularly limited. In addition, when the particle size of the zeolite is small, it is easily mixed uniformly with other components such as resin, and when a molded body is formed, the surface smoothness is easily increased. Specifically, the particle size of the present zeolite is preferably less than 5.0 μm, more preferably 4.5 μm or less, and even more preferably 4.0 μm or less. On the other hand, there is no particular restriction on the lower limit, but from the viewpoints of ease of handling and of preventing the viscosity of the present resin composition from increasing, the lower limit may be 0.05 μm or more, 0.1 μm or more, 0.3 μm or more, 0.5 μm or more, or 1.0 μm or more. When using zeolite, a plurality of zeolite particles are usually used instead of one zeolite particle. That is, in one aspect of the present invention, it is preferable to use a zeolite group containing at least the present zeolite particle. In one aspect of the present invention, the zeolite consisting of such a plurality of zeolite particles has an average primary particle size in the range of 0.05 to 5.0 μm, more preferably 0.1 to 4.0 μm, and even more preferably 0.5 to 3.5 μm. The average primary particle size of the zeolite is determined by measuring the particle size of 50 randomly selected zeolites (powder, particles in a liquid composition or resin composite material described later) and averaging the measured particle sizes. In addition, the volumetric particle size distribution of the zeolite is preferably in the range of 0.05 to 5.0 μm in terms of median diameter (d50), more preferably in the range of 0.1 to 4.0 μm, and even more preferably in the range of 0.5 to 3.5 μm. By having the median diameter within this range, the proportion of zeolite that exhibits the effects of the present invention increases, and the effects of the present invention can be easily obtained with a smaller amount.

[0013] (Zeolite structure) Zeolite is a compound that contains silicon or aluminum and oxygen and has a TO4 unit (T element is an element other than oxygen that constitutes the framework) as a basic unit. Specific examples of zeolite include crystalline porous aluminosilicates, crystalline porous aluminophosphates (ALPOs), and crystalline porous silicoaluminophosphates (SAPOs). The zeolite of the present invention may have any of the above structures, but is preferably an aluminosilicate. Zeolite is made up of structural units called Composite Building Units (hereinafter sometimes referred to as "CBUs"), which are made up of several (several to several tens) TO4 units connected together. This gives it regular channels (tubular pores) and cavities. The CBU and the crystal structure of zeolite, which will be described later, can be shown by the code that specifies the structure of zeolite, as defined by the International Zeolite Association (IZA). The structure of zeolite can be identified using the Zeolite Structure Database 2018 Edition (http: / / www.iza-structure.org / databases / ) based on the X-ray diffraction pattern obtained by an X-ray structure analyzer (e.g., BRUKER's tabletop X-ray diffractometer D2PHASER).

[0014] (Zeolite framework) The framework of the present zeolite preferably has d6r as the CBU, which makes it easier to obtain a resin composite material with a low thermal expansion coefficient, as described in detail below. As the CBU, examples of zeolites having d6r 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 having a -WEN type structure. Among these, from the viewpoint of easy particle size control, zeolites having an 8-membered oxygen ring or less structure are particularly preferred. Zeolites having an 8-membered oxygen ring or less structure include zeolites having AEI, AFT, AFX, CHA, ERI, KFI, SAT, SAV, SFW, and TSC type structures. Among these, zeolites having AEI, AFX, CHA, and ERI type structures are particularly preferred, and zeolites having CHA type structures are most preferred, since the structure is stable even when the shape is controlled. In this specification, the structure having an 8-membered oxygen ring means a structure in which the number of oxygen elements is 8 when the number of oxygen elements is the largest among the pores composed of oxygen and T elements (elements other than oxygen that constitute the framework) that form the zeolite framework. The above zeolites may be used alone or in combination of two or more kinds.

[0015] (Average thermal expansion coefficient of zeolite) The average thermal expansion coefficient of the present zeolite is preferably low because it is easy to reduce the average thermal expansion coefficient of the liquid composition and the resin composite material described later with a small amount of zeolite. In addition, it is also preferable that the amount of zeolite is small, so that various physical properties of the resin are unlikely to change due to the addition of zeolite. In particular, it is preferable that the average thermal expansion coefficient is low because it can suppress the increase in viscosity of the liquid composition described later. Specifically, the average thermal expansion coefficient of zeolite is usually less than 0 ppm / K, preferably -2 ppm / K or less, more preferably -3 ppm / K or less, even more preferably -5 ppm / K or less, particularly preferably -6 ppm / K or less, and most preferably -8 ppm / K or less.

[0016] On the other hand, considering that the zeolite is used as a liquid composition and a resin composite material containing zeolite and an epoxy resin, which will be described later, the average thermal expansion coefficient of the zeolite is preferably high in that the difference with the average thermal expansion coefficient of the resin is small and the zeolite and the resin are not easily peeled off. Therefore, the average thermal expansion coefficient of the zeolite is usually -1000 ppm / K or more, preferably -900 ppm / K or more, more preferably -800 ppm / K or more, even more preferably -700 ppm / K or more, particularly preferably -500 ppm / K or more, and especially preferably -300 ppm / K or more. And, in particular, when used for applications in contact with other materials such as sealing materials and substrates, it is preferable that the average thermal expansion coefficient is high, specifically, -100 ppm / K or more, more preferably -50 ppm / K or more, even more preferably -40 ppm / K or more, particularly preferably -30 ppm / K or more, especially preferably -25 ppm / K or more, and most preferably -20 ppm / K or more. The average thermal expansion coefficient of zeolite can be measured by calculating the lattice constant using the X-ray diffractometer "D8ADVANCE" manufactured by BRUKER and the X-ray diffraction analysis software "JADE". In order to eliminate the influence of moisture desorption, the zeolite is usually measured in a dry state. The average thermal expansion coefficient of zeolite is usually measured in the range of 50 to 100°C. That is, it is a numerical value that represents the displacement of the lattice constant per 1°C from the average lattice constant at 50°C and the average lattice constant at 100°C when the temperature of the zeolite is raised. Here, the average lattice constant at each temperature is the average value of the lattice constants of the a-axis, b-axis, and c-axis. The average thermal expansion coefficient is measured by gradually raising the temperature after waiting until the lattice constant stabilizes.

[0017] Generally, the thermal expansion coefficient of resins is large in high temperature ranges. Therefore, it is preferable that the average thermal expansion coefficient of zeolite is low, especially when the temperature is raised to a high temperature range. Specifically, the average thermal expansion coefficient (high temperature range) in the range of 50 to 350°C is preferably -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 thermal expansion coefficient (high temperature range) of zeolite is a numerical value representing the displacement of the lattice constant per 1°C from the average lattice constant at 50°C and the average lattice constant at 350°C when the zeolite is heated.

[0018] (Zeolite shape) The present zeolite is preferably spherical. By having a spherical shape of the zeolite, it is easy to include the zeolite in the epoxy resin while suppressing an increase in the viscosity of the resin composition containing the zeolite. Specifically, it is preferable that the zeolite has the following sphericity and roundness.

[0019] <<Sphericity>> The sphericity of the present zeolite is 0.7 or more, and preferably 0.8 or more. The upper limit of the sphericity is not particularly limited, and may be 1 or less. The sphericity of a cube, which is common in normal zeolites, is 0.58. In the present application, the "sphericity" is the average value of 10 particles obtained by a scanning electron microscope (SEM). In this specification, "sphericity" is defined as "the ratio of the minimum diameter to the maximum diameter of a particle." The maximum diameter and the minimum diameter can be determined by observation with a scanning electron microscope (SEM).

[0020] <<Circularity>> The circularity of the present zeolite is preferably 0.800 or more, more preferably 0.810 or more, even more preferably 0.820 or more, particularly preferably 0.830 or more, and most preferably 0.840 or more. The upper limit of the circularity is not particularly limited, and may be 1 or less. The circularity of the zeolite in the case of a cube, which is common in ordinary zeolites, is 0.785. In this specification, "roundness" is defined as "4 x π x area / (circumference) 2The area and circumference can be determined by observation with a scanning electron microscope (SEM). In this application, the "roundness" is the average value of 10 particles obtained with a scanning electron microscope (SEM).

[0021] (Zeolite framework density) The framework density of the present zeolite is not particularly limited as long as the effect of the present invention is not impaired. The framework density of the zeolite is preferably low in that the structural vibration of the zeolite is likely to occur and the average thermal expansion coefficient is likely to be low. Therefore, the framework density of the zeolite is preferably 17.0T / 1000Å or less. 3 Less than or equal to 16.0T / 1000Å, more preferably 3 The following is the result. On the other hand, it is preferable that the framework density of the zeolite is high in order to increase the structural stability of the zeolite. The framework density of the zeolite is preferably 12.0T / 1000Å. 3 More preferably, 13.0T / 1000Å or more 3 More preferably, 14.0T / 1000Å or more 3 When the framework density is within the above range, the zeolite can be used as a stable filler. The framework density refers to the number of T atoms present per unit volume of zeolite, and is a value determined by the structure of the zeolite. In this specification, the numerical values ​​described in the IZA Zeolite Structure Database 2017 Edition (http: / / www.iza-structure.org / databases / ) may be used.

[0022] Framework density: 16.0T / 1000Å 3 Larger, 17.0T / 1000Å 3 Examples of the following zeolites include zeolites of the ERI, LTL, LTN, MOZ, OFF, SAT, SSF and -WEN structure types. Framework density: 15.0T / 1000Å 3Larger, 16.0T / 1000Å 3 Examples of the following zeolites include zeolites of the AEI, AFT, AFV, AFX, AVL, EAB, GME, LEV, MWW and SFW type structures. Framework density: 14.0T / 1000Å 3 Larger, 15.0T / 1000Å 3 Examples of zeolites that may be mentioned include zeolites of the CHA, KFI, SAS and SAV structure types. Framework density: 14.0T / 1000Å 3 Examples of zeolites falling within the following ranges include zeolites of EMT, FAU, JSR, SBS, SBT, and TSC type structures.

[0023] (Zeolite Composition) The composition of the present zeolite is not particularly limited as long as the effects of the present invention are not impaired, but an aluminosilicate containing at least aluminum atoms and silicon atoms in the framework structure is preferred because it is advantageous for application to filler applications. Zeolites may be used alone or in any combination and ratio of two or more types.

[0024] In addition, when elements such as gallium, iron, boron, titanium, zirconium, tin, zinc, phosphorus, etc. are used instead of silicon or aluminum, the molar ratio of the oxide of the substituted element may be converted into the molar ratio of alumina or silica. Specifically, when gallium is used instead of aluminum, the molar ratio of gallium oxide may be converted into the molar ratio of alumina.

[0025] (Silica / Alumina Molar Ratio (SAR) of Zeolite) The silica / alumina molar ratio of the present zeolite (hereinafter, sometimes referred to as "SAR", "Si / Al2 molar ratio", or "Si / Al2 ratio") is not particularly limited as long as the effects of the present invention are not impaired. The SAR (Si / Al2 ratio) of the zeolite is preferably high in order to increase the moisture resistance of the resin composite material described below and to make it easier to control the amount of counter cations. Thus, the SAR (Si / Al2 ratio) of the zeolite is usually 2 or more, preferably 3 or more, more preferably 3.5 or more, even more preferably 4 or more, particularly preferably 4.5 or more, and most preferably 5 or more. On the other hand, the SAR (Si / Al2 ratio) of zeolite is preferably low in terms of easy and 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 further preferably 100 or less. When the Si / Al2 ratio is within the above range, the amount of counter cations is easily controlled, and the production cost of zeolite is also low. The Si / Al2 ratio of the zeolite can be adjusted by the type and ratio of the silicon-containing compound and aluminum-containing compound in the raw materials, the type and amount of the structure-directing agent, the use of seed crystals, and synthesis conditions such as temperature and time.

[0026] (Zeolite counter cation) The counter cation of the present zeolite is not particularly limited as long as the effect of the present invention is not impaired. The counter cation 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, more preferably, it is a proton, a Li ion, a Na ion, or a K ion. In the case of an alkali metal ion or an alkaline earth metal ion, the smaller the size, the more likely the zeolite is to exhibit an average thermal expansion coefficient of less than 0 ppm / K, which is preferable. Among them, the counter cation of the zeolite is preferably a proton, since it is easy to reduce the average thermal expansion coefficient of the resin composite. 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.

[0027] (Zeolite crystallinity) The crystallinity of the present zeolite is not particularly limited as long as the effect of the present invention is not impaired. The reason is that it is assumed that the Composite Building Unit (CBU) is a factor that has a greater influence on the average thermal expansion coefficient of the resin composite than the structure specified by the IZA code. The crystallinity of the zeolite can be calculated by comparing a certain X-ray diffraction peak determined by an X-ray diffractometer (e.g., BRUKER's tabletop X-ray diffractometer D2PHASER) with the X-ray diffraction peak of the reference zeolite. A specific calculation example is the crystallinity of LTA-type zeolite in Scientific Reports 2016, 6, Article number: 29210.

[0028] (Surface treatment for zeolite) The present zeolite may be subjected to a surface treatment such as a silylation treatment or a fluorination treatment, as long as the effect of the present invention is not impaired. The surface treatment may be a physical treatment or a chemical treatment.

[0029] (Zeolite content) From the viewpoint of suppressing an increase in viscosity of the resin composition while lowering the thermal expansion coefficient, the content of the zeolite in the resin composition is preferably 40 to 70 mass %, more preferably 45 to 65 mass %, and even more preferably 50 to 60 mass %, relative to the total amount of the resin composition.

[0030] (Inorganic filler) The resin composition may contain other inorganic fillers in addition to the zeolite. The other inorganic fillers are not particularly limited as long as they do not impair the effects of the present invention, and examples thereof include at least one type selected from the group consisting of metals, carbon, metal carbides, metal oxides, and metal nitrides. Examples of metals include silver, copper, aluminum, gold, nickel, iron, and titanium. Examples of carbon include carbon black, carbon fiber, graphite, fullerene, and diamond. Examples of metal carbides include silicon carbide, titanium carbide, and tungsten carbide. Examples of metal oxides include magnesium oxide, aluminum oxide (alumina), silicon 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.

[0031] In addition, when the present resin composition contains an inorganic filler other than the present zeolite, the content of the present zeolite in the total filler is preferably 90% by mass or more, and more preferably 95% by mass or more, in order to fully exert the effects of the present zeolite. An embodiment in which the present zeolite is 100% by mass and no filler other than the present zeolite is included is also possible.

[0032] (Total amount of inorganic filler) The total content of all inorganic fillers (total inorganic fillers) contained in the present resin composition is preferably high in terms of the ease of manifesting the effect as a filler. On the other hand, when the present resin composition is liquid (hereinafter sometimes referred to as "liquid composition"), it is preferable that the total content is low in terms of high fluidity and ease of filling narrow spaces. Specifically, the total content of all inorganic fillers is preferably 30% by mass or more, more preferably 35% by mass or more, and particularly preferably 40% by mass or more, based on the total amount of the liquid 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.

[0033] (Dispersant) The resin composition may contain a dispersant to improve the dispersibility of inorganic fillers such as the zeolite. The dispersant contained in the liquid composition containing a resin and a filler is mainly added to a liquid composition containing a resin and a filler having a large polarity difference, thereby improving the interface state between the two and improving compatibility. This can produce effects such as lowering the viscosity, improving the dispersibility of the filler, preventing filler aggregation and sedimentation, etc.

[0034] Examples of the dispersant include acrylic dispersants and polymer dispersants. Here, the term "polymer dispersant" refers to a dispersant with a weight average molecular weight of 1,000 or more. The dispersant is preferably a polymer dispersant. The main chain skeleton of the polymer dispersant is not particularly limited, but examples thereof include polyurethane skeleton, polyacrylic skeleton, polyester skeleton, polyamide skeleton, polyimide skeleton, polyurea skeleton, etc., and from the viewpoint of storage stability, polyurethane skeleton, polyacrylic skeleton, and polyester skeleton are preferred. The structure of the polymer dispersant is also not particularly limited, but examples thereof include random structure, block structure, comb structure, star structure, etc., and similarly, from the viewpoint of storage stability, block structure or comb structure is preferred. In addition, the dispersant is preferably a solvent-free dispersant, particularly a solvent-free polymer dispersant, which does not contain a solvent. By using a dispersant that does not contain a solvent, it is possible to prevent the dispersant from volatilizing and causing voids when the composition is cured by heating. As the dispersant, a commercially available product can be used. Examples of the commercially available product include the following dispersants, and among these, a dispersant having at least one functional group of an amino group or an amine salt may be used.

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

[0036] The content of the dispersant is preferably high, for example, in terms of making it easy to uniformly disperse the inorganic filler in the liquid composition. On the other hand, the content of the dispersant is preferably low, in terms of making it difficult for the thermal expansion coefficient to increase due to phase separation between the inorganic filler and the resin such as an epoxy resin to occur. Therefore, the content of the dispersant is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 0.1% by mass or more and 25% by mass or less, based on the total amount of the composition, in order to make it easy to fill the liquid composition into a narrow space and to make it easy to have a low thermal expansion coefficient after curing.

[0037] <Zeolite manufacturing method> The zeolite can be produced by a known method. For example, when producing a CHA type zeolite, the method described in JP-A-2009-097856 can be referred to. More specifically, an aluminum atom raw material, a silica atom raw material, an organic structure directing agent, and the like are mixed to prepare an aqueous gel. The order of mixing is usually such that the aluminum atom raw material is mixed into water, and then the silica atom raw material and the organic structure directing agent are mixed therein. The prepared aqueous gel is then hydrothermally synthesized, and the product is separated, washed with water, dried, and calcined to remove the contained organic matter, thereby obtaining a zeolite.

[0038] The particularly preferred zeolite described above can be produced by the following method (hereinafter sometimes referred to as "this production method"). The method for producing the present zeolite includes a step of hydrothermally synthesizing a raw material composition containing a silicon atom raw material, an aluminum atom raw material, an organic structure directing agent, and water. The method for producing the present zeolite preferably further includes a calcination step. The calcination conditions can be appropriately determined according to the type of zeolite to be produced or the conditions of hydrothermal synthesis, etc. For example, in the case of CHA-type zeolite suitable for the present invention, the temperature is preferably in the range of 500°C to 700°C, more preferably in the range of 550°C to 650°C. The calcination time is preferably 3 to 10 hours, more preferably 4 to 8 hours, and even more preferably 5 to 7 hours. The calcination atmosphere is not particularly limited, and may be in air or a nitrogen atmosphere. If necessary, a desired zeolite (hereinafter, sometimes referred to as "seed zeolite") may be used.

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

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

[0041] <<Organic structure directing agent>> As the organic structure directing agent, various known substances such as tetraethylammonium hydroxide (TEAOH) and tetrapropylammonium hydroxide (TPAOH) can be used. Among these, N,N,N-trimethyl-1-adamantaammonium hydroxide (TMAdaOH) is preferred. The amount of the organic structure directing agent used is, in terms of molar ratio to silicon (Si) contained in the raw material composition, usually 0.01 or more, preferably 0.02 or more, more preferably 0.03 or more, particularly preferably 0.04 or more, and most preferably 0.05 or more. On the other hand, it is usually 1 or less, preferably 0.6 or less, more preferably 0.55 or less, and even more preferably 0.5 or less. By using it within this range, it is thought that it is easy to grow high-purity spherical zeolite with few by-products.

[0042] <<Wed>> When using a seed crystal zeolite described later, the amount of water used is preferably 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 easy crystal formation. By setting the amount of water within this range, crystal formation is easy and preferable. In addition, when zeolite is hydrothermally synthesized under conditions in which the amount of water is increased to dilute the raw material concentration, zeolite with a large particle size is likely to be obtained. In addition, in terms of easy cost reduction effect for waste liquid 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 25 or less.

[0043] <<Alkali metal atom source>> Zeolite may be produced using an alkali metal atom raw material. When using an alkali metal atom raw material, the alkali metal atom is not particularly limited, and any known alkali metal atom used in the synthesis of zeolite may be used, but at least one alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium is preferred. Note that multiple types of alkali metal atoms may be used.

[0044] <<Seed Zeolite>> In the present zeolite production method, a seed zeolite may be used. When a seed zeolite is used, one type may be used alone, or two or more types may be used in any combination and ratio.

[0045] <<Mixing of raw materials (preparation of pre-reaction raw material composition)>> The raw material composition can usually be obtained by mixing the silicon atom raw material, the aluminum atom raw material, the organic structure directing agent, and water, and then adding a seed crystal zeolite, if used. In the production of zeolite, in addition to the above-mentioned components, components such as an acid component for accelerating the reaction and a metal stabilizer such as polyamine may be added at any step as necessary.

[0046] <<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 the raw material for a certain period of time under a predetermined temperature condition. In particular, when the reaction is scaled up, it is preferable to age the raw material while stirring it for a certain period of time, since this improves the stirrability and makes the raw material more uniform. The temperature for aging is usually 100°C or less, preferably 95°C or less, more preferably 90°C or less, and although there is no particular limit, the temperature for aging is usually 0°C or more, preferably 10°C or more. The aging temperature may be constant during aging, or may be changed stepwise or continuously. The aging time is not particularly limited, but is usually 2 hours or more, preferably 3 hours or more, more preferably 5 hours or more, and on the other hand, it is usually 30 days or less, preferably 10 days or less, and more preferably 4 days or less.

[0047] <<Hydrothermal synthesis>> Next, the obtained raw material composition is subjected to hydrothermal synthesis. Hydrothermal synthesis is usually carried out by placing the raw material composition prepared as described above or an aqueous gel obtained by maturing the raw material composition in a pressure-resistant container, and maintaining the mixture at a predetermined temperature under self-generated pressure or under gas pressure to an extent that does not inhibit crystallization, while stirring, rotating or rocking the container, or leaving it stationary. The reaction temperature during hydrothermal synthesis is usually 120°C or higher, preferably 130°C or higher, more preferably 140°C or higher, and particularly preferably 150°C or higher, in order to increase the reaction rate. On the other hand, it is usually 230°C or lower, preferably 220°C or lower, more preferably 200°C or lower, and even more preferably 190°C or lower. The reaction time is not particularly limited, but is usually 2 hours or more, preferably 3 hours or more, 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 may be changed stepwise or continuously.

[0048] <Epoxy resin> The resin composition of the present invention contains an epoxy resin. As the epoxy resin used in the present invention, it is preferable to use an epoxy compound having an aromatic ring such as a bisphenol A type skeleton, a bisphenol F type skeleton, or a biphenyl skeleton, since the thermal expansion coefficient of the resin composite material formed by curing the resin composition of the present invention is likely to be low. Specifically, 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 resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, aminophenol type epoxy resin, aliphatic epoxy resin, copolymer epoxy resin of aliphatic epoxy resin and aromatic epoxy resin, etc. are exemplified, among which bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, and naphthalene ring-containing 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.

[0049] In addition, it is preferable to use a polyfunctional epoxy resin, since the glass transition temperature of the resin composite material obtained by thermally curing the resin composition is likely to be high. As the polyfunctional epoxy resin, various phenols such as phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, dicyclopentadiene phenol resin, phenol aralkyl resin, naphthol novolac resin, biphenyl novolac resin, terpene phenol resin, heavy oil modified phenol resin, and various phenols such as polyhydric phenol resins obtained by condensation reaction of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, and glycidyl ether type polyfunctional epoxy resins such as epoxy resins produced from epihalohydrin and various phenolic compounds are preferable.

[0050] From the viewpoint of fluidity, the epoxy resin used in the present 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 resins is specified in JIS K7233 (1986), and a single cylinder rotational viscometer method is suitable. The viscosity of the epoxy resin used in the present invention at 23°C may be measured using a B-type rotational viscometer ("LVDV-1 Pri", Brookfield, spindle: S62), which is one of the single cylinder rotational viscometer methods.

[0051] From the viewpoint of viscosity control, the epoxy resin preferably has an epoxy equivalent of 50 g / eq or more and 500 g / eq or less, more preferably 90 g / eq or more and 150 g / eq or less. The epoxy equivalent is preferably high in terms of excellent heat resistance. On the other hand, it is preferably low in terms of the fact that the melting point of the epoxy resin is lowered and the viscosity is lowered, thereby improving the filling property of the resin composition and easily increasing the bonding property by filling. The epoxy resin may be used alone or in any combination and ratio of two or more kinds. When the resin is mixed, the epoxy equivalent is the equivalent weight of the mixture.

[0052] The content of the epoxy resin in the resin composition is preferably low in that the content of inorganic fillers such as zeolite is relatively high and the thermal expansion coefficient is easily reduced. On the other hand, it is preferable that the content is high in that the excellent physical properties of the epoxy resin are easily maintained. As described above, from the viewpoint of maintaining both the excellent physical properties of the resin and the heat resistance (resistance to thermal expansion) of the cured resin composition, specifically, the content is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total amount of the 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.

[0053] <Hardening agent> The present resin composition contains a curing agent. The curing agent is a substance that contributes to the crosslinking reaction between crosslinking groups of the epoxy resin. The curing agent used in the present invention is a curing agent having at least one amino group in one molecule (hereinafter, may be referred to as the present curing agent). The present curing agent may be any curing agent that cures by polymerization together with the epoxy resin, and may be either liquid or solid as long as the resin composition has fluidity at room temperature (25°C). Examples of the curing agent include amine-based curing agents and carboxylic acid dihydrazide curing agents, and from the viewpoints of flowability, pot life, etc., the amine-based curing agents are preferred.

[0054] Examples of the amine-based curing agent include linear aliphatic amines, cyclic aliphatic amines, aliphatic aromatic amines, aromatic amines, etc., and aromatic amines are preferred from the viewpoints of heat resistance and electrical properties. As the aromatic amine, an amino group is directly bonded to an aromatic ring, and an aromatic amine containing one or two aromatic rings per molecule is more preferred. The proportion of aromatic amine in the present curing agent is preferably from 50% by mass to 100% by mass, more preferably from 70% by mass to 100% by mass, and further preferably from 90% by mass to 100% by mass. Examples of amine-based curing agents include aromatic amine curing agents with one aromatic ring, such as m-phenylenediamine, 1,3-diaminotoluene, 1,4-diaminotoluene, 2,4-diaminotoluene, 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, and 2,4-diaminoanisole; 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-methylenebis(2-ethylaniline), 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 3,3' Examples of aromatic amine curing agents include aromatic amine curing agents with two aromatic rings, such as 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane and 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane; hydrolysis condensation products of aromatic amine curing agents; aromatic amine curing agents having a polyether structure, such as polytetramethylene oxide di-p-aminobenzoate and polytetramethylene oxide di-para-aminobenzoate; condensation products of aromatic diamines and epichlorohydrin; reaction products of aromatic diamines and styrene.

[0055] As the present curing agent, a commercially available product may be used. Specific examples of commercially available products include an amine curing agent manufactured by Nippon Kayaku Co., Ltd. (product name: Kayahard-AA), an amine curing agent manufactured by Mitsubishi Chemical Corporation (product name: jER Cure (registered trademark) 113, product name: jER Cure (registered trademark) W), etc., but are not limited thereto. In addition, the present curing agent may be used alone or in combination of two or more kinds.

[0056] The ratio of the equivalent number of the epoxy resin contained in the resin composition to the equivalent number of the curing agent is not particularly limited, but from the viewpoint of keeping the unreacted amounts of each small, the ratio of the equivalent number of the epoxy resin to the equivalent number of the curing agent (equivalent number of the curing agent / equivalent number of the epoxy resin, hereinafter sometimes referred to as "equivalent ratio") is preferably set in the range of 0.6 to 1.4, more preferably in the range of 0.7 to 1.3, even more preferably in the range of 0.8 to 1.2, and particularly preferably in the range of 0.8 to 1.0. The resin composition may contain other curing agents in addition to the curing agent of the present invention, such as phenol-based curing agents, acid anhydride-based curing agents, and imidazole-based curing agents.

[0057] (Reactive diluent) When the resin composition is liquid, the resin composition may contain a reactive diluent. The reactive diluent is not particularly limited as long as it contains at least one type of monofunctional epoxy compound. The monofunctional epoxy compound is an epoxy compound having one epoxy group, and has been used as a reactive diluent to adjust the viscosity of an epoxy resin composition. The monofunctional epoxy compound is roughly classified into an aliphatic monofunctional epoxy compound and an aromatic monofunctional epoxy compound, and from the viewpoint of viscosity, it is preferable to use an aromatic monofunctional epoxy compound.

[0058] (Other additives) In addition to the above, the present resin composition may appropriately contain other additives selected from a coupling agent, an ultraviolet protection agent, an antioxidant, a plasticizer, a flame retardant, a colorant, a flow improver, an antifoaming agent, an ion trapping agent, and the like.

[0059] In addition, when the resin composition is liquid, the resin composition is preferably solvent-free. By making the resin composition solvent-free, it is possible to prevent the occurrence of voids and the like due to the evaporation of the solvent when the liquid composition is heat-cured. In addition, the term "solvent" refers to a volatile component, and in this specification, the term includes water and organic solvents. A solvent-free liquid composition is one that does not substantially contain a solvent, and for example, the content of the solvent is preferably less than 3% by mass, more preferably less than 1% by mass, and most preferably 0% by mass, based on the total amount of the liquid composition.

[0060] (Method of producing the resin composition) The resin composition can be obtained by mixing and kneading the epoxy resin, zeolite, curing agent, other inorganic fillers, dispersants, reactive diluents, and other additive components that are used as necessary, using a vacuum mixer, mixing rolls, planetary mixer, etc., and degassing as necessary. The order of mixing these components is arbitrary as long as there are no particular problems such as the generation of reactions or precipitates. Any two or three or more of the constituent components may be mixed in advance, and the remaining components may then be mixed, or all of the components may be mixed at once.

[0061] (Average Coefficient of Thermal Expansion (CTE)) When the present resin composition is cured to a gel fraction of 80% or more, the average coefficient of thermal expansion (CTE1) of the cured product at 25 to 100°C is preferably 0 ppm / K or more, more preferably 2 ppm / K or more, even more preferably 4 ppm / K or more, and particularly preferably 10 ppm / K or more, while it is preferably 100 ppm / K or less, more preferably 50 ppm / K or less, and even more preferably 30 ppm / K or less. Such an epoxy resin composition has a low average coefficient of thermal expansion at temperatures equal to or lower than the glass transition temperature, and is therefore useful as a material requiring various heat resistance properties, and is particularly effective in application to electronic devices.

[0062] When the present resin composition is cured to a gel fraction of 80% or more, the average coefficient of thermal expansion (CTE2) of the cured product at 150 to 200°C is preferably close to the average coefficient of thermal expansion of the surrounding materials, in order to prevent the resin composite material described below from being deformed by the surrounding temperature environment, heat generation, etc., and to prevent damage due to the difference in average thermal expansion with the surrounding materials. Therefore, when the liquid composition is used as an underfill material or the like in the manufacture of semiconductor devices, it is preferable to make the average coefficient of thermal expansion of the cured product as close as possible to the average coefficient of thermal expansion of the semiconductor substrate (e.g., 3 to 4 ppm / K). From the above viewpoints, the average coefficient of thermal expansion (CTE2) is preferably 0 ppm / K or more, more preferably 2 ppm / K or more, even more preferably 4 ppm / K or more, and particularly preferably 10 ppm / K or more. On the other hand, it is preferably 200 ppm / K or less, more preferably 150 ppm / K or less, even more preferably 100 ppm / K or less, and particularly preferably 80 ppm / K or less.

[0063] The average thermal expansion coefficient and the glass transition temperature (Tg) described later may be measured by thermomechanical analysis of a resin composite (cured product) obtained by curing a resin composition to a gel fraction of 80% or more. Specific measurement conditions are as described in the Examples.

[0064] (Temperature dependence of average thermal expansion coefficient) When the resin composition is cured to a gel fraction of 80% or more, the ratio (CTE2 / CTE1) of the average thermal expansion coefficient (CTE2) at 150-200°C to the average thermal expansion coefficient (CTE1) at 25-100°C of the cured product is preferably less than 3.00. If the ratio is less than 3.00, the change in the average thermal expansion coefficient due to temperature is small, which is preferable from the viewpoint of warping resistance. From the above viewpoints, the ratio is more preferably 2.98 or less, and even more preferably 2.96 or less. There is no particular restriction on the lower limit of the ratio, but it is usually 2 or more.

[0065] (glass transition temperature) The glass transition temperature (Tg) of the cured product when the resin composition is cured to a gel fraction of 80% or more is not particularly limited. For example, when the Tg is high as an underfill material, it is considered preferable because the part sealed with the underfill material has high bump protection at high temperatures and excellent thermal cycle resistance (see, for example, JP 2017-110146 A). From such a viewpoint, the glass transition temperature (Tg) is preferably 50°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, particularly preferably 125°C or higher, and most preferably 135°C or higher. When Tg is the lower limit or higher, the heat resistance is sufficient. In addition, there is no particular upper limit for the glass transition temperature (Tg), and a temperature of 150° C. or lower can be used without any problems. The glass transition temperature (Tg) can be measured by a thermomechanical analyzer (TMA) as described above. Specifically, it can be measured by the method described in the Examples.

[0066] <Resin composite material> The resin composite of the present invention (hereinafter, sometimes referred to as "the resin composite") can be obtained by curing the above-mentioned resin composition. More specifically, the resin composite is a resin composite containing an epoxy resin, a zeolite, and a curing agent.

[0067] In the present resin composite, the epoxy resin and zeolite are as described above. In addition to the epoxy resin and zeolite, the present resin composite may also contain other components contained in the present resin composition as appropriate. The content of each component in the present resin composite is as described above, except that the total amount of the resin composite is used as the standard instead of the total amount of the resin composition. Furthermore, the present resin composite is preferably cured to a gel fraction of 80% or more, and is cured by the curing agent contained in the present resin composition described above.

[0068] (Method of manufacturing resin composite material) The present resin composite can be obtained by curing the liquid composition. The curing is preferably performed by heating. The method for producing the present resin composite is not particularly limited as long as the resin composite exhibits preferable performance, and can be appropriately performed using a known method according to the blending component composition of the liquid composition.

[0069] The resin composite material is preferably formed, for example, by filling the liquid composition into gaps between components of various products such as electronic devices and then curing the liquid composition. The resin composite material may also be formed by applying the liquid composition to components of various products and curing the liquid composition. The liquid composition can also be molded into a desired shape, for example, by curing the liquid composition in a mold. In the manufacture of such a molded product, injection molding, injection compression molding, extrusion molding, or compression molding can be used. The molding of the resin composite, i.e., curing, can be performed under the respective curing temperature conditions. The resin composite can also be obtained by cutting out the cured liquid composition into a desired shape. The heating temperature during thermal curing is not particularly limited, depending on 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, a high-quality resin composite material can be easily obtained in a short time.

[0070] <Application> The resin composition and the resin composite can be used, for example, in catalyst modules, molecular sieve membrane modules, optical components, moisture absorbing components, foods, building components, and components and packaging components for electronic devices, and are preferably used in electronic devices. Thus, the present invention provides, as a preferred embodiment, an electronic device containing the resin composite. The electronic device is a device that has two or more electrodes and controls the current flowing between the electrodes or the voltage generated by electricity, light, magnetism, or chemical substances, or generates light, an electric field, or a magnetic field by the applied voltage or current. Specific examples include resistors, rectifiers (diodes), switching elements (transistors, thyristors), amplifier elements (transistors), memory elements, chemical sensors, or devices in which these elements are combined or integrated. Other examples include photodiodes or phototransistors that generate photocurrent, electroluminescent elements that emit light by applying an electric field, and optical elements such as photoelectric conversion elements or solar cells that generate electromotive force by light. The electronic device is preferably a semiconductor device. The semiconductor device may have at least a semiconductor substrate, and examples thereof include devices in which a semiconductor chip is mounted on a substrate, and devices in which semiconductor chips and semiconductor substrates are stacked in multiple layers.

[0071] When the present resin composition is in a liquid state, it is preferably used as a liquid sealant, and in this case, the resin composite material formed by curing the liquid composition serves as the sealant. The liquid sealant may be used as a sealant that fills gaps formed in components by filling the gaps and then curing the gaps. A method for producing a sealant that includes a step of filling the gaps with a resin composition and then curing the resin composition is also within the scope of the present invention. In addition, the liquid sealant may be used as a sealant for filling gaps between components by, for example, applying the liquid sealant onto various components, overlaying another component on the liquid sealant, and then appropriately curing the liquid sealant. In this case, the liquid sealant may be appropriately cured to a B-stage before overlaying the other component. Among these, the resin composition of the present invention, particularly a liquid composition in which the present resin composition is in a liquid state, is preferably used for filling a gap and curing it, i.e., it is preferable to produce a sealant by filling a gap with the resin composition of the present invention and then curing it.

[0072] The resin composition of the present invention is preferably used as a liquid sealant, and particularly preferably used as an underfill material. The underfill material is preferably used in the manufacture of electric devices, particularly semiconductor devices, and is preferably used for filling gaps formed between a substrate and a semiconductor chip, between substrates, between semiconductor chips, etc. The substrate may be a known substrate, and may be a substrate made of an organic material such as an epoxy resin substrate or a phenol resin substrate. The semiconductor chip may be formed from a semiconductor substrate such as a silicon substrate. The resin composition of the present invention has a low coefficient of thermal expansion when cured, and when used as an underfill material, the difference in thermal expansion coefficient between the composition and semiconductor substrates and the like is reduced, thereby improving thermal cycle resistance and the like.

[0073] The underfill material is preferably used as a sealant that fills the gap between the substrate and the semiconductor chip in a laminate in which the semiconductor chip is mounted on the substrate, and then hardens by heating to seal the gap between the substrate and the chip. In this case, the semiconductor chip may be bonded to the surface of the substrate on which the wiring pattern is formed via bumps by, for example, reflow before the underfill material is filled.

[0074] The underfill material may be used in the manufacture of semiconductor devices by the pre-apply method. Specifically, on the surface of a semiconductor chip on which a plurality of bumps are formed, the underfill material is filled between the plurality of bumps to form an underfill layer. Here, the filled underfill material may be B-staged as necessary. Thereafter, the semiconductor chip on which the underfill layer is formed may be placed on the surface of the substrate with the surface on which the underfill layer is formed facing the substrate. Next, the underfill layer is hardened by heating and pressing, etc. to become an encapsulant, and the semiconductor chip may be bonded to the surface of the substrate on which the wiring pattern is formed via the bumps.

[0075] In the pre-apply method, an underfill material may be applied to the surface of a substrate on which a wiring pattern is formed to form an underfill layer. Here, the applied underfill layer may be B-staged as necessary. Then, the semiconductor chip on which the bumps are formed may be placed on the substrate on which the underfill layer is formed, with the surface on which the bumps are formed facing the surface of the substrate on which the underfill layer is formed. Then, the underfill layer is hardened by heating and pressing to become an encapsulant, and the semiconductor chip may be bonded to the surface of the substrate on which the wiring pattern is formed via the bumps.

[0076] In the above description, the underfill material is used as a sealant to fill the gap between the substrate and the semiconductor chip, but the use of the underfill material is not particularly limited, and the underfill material may be used to fill the gap between semiconductor chips, or as a sealant to fill the gap between substrates, etc. Furthermore, the substrate is not limited to a substrate made of an organic material, and may be a semiconductor substrate, etc. EXAMPLES

[0077] The present invention will be described in more detail below using examples and comparative examples. However, the present invention is not limited to the following examples and comparative examples as long as it does not deviate from the gist of the present invention.

[0078] (Physical property evaluation) The physical properties were evaluated as follows.

[0079] (Average coefficient of thermal expansion, CTE1 and CTE2) The average thermal expansion coefficient of the cured product when the resin composition was cured to a gel fraction of 80% or more was measured by thermomechanical analysis using a method conforming to JIS K7197 (2012). The measurement was performed by the compression method using a thermomechanical analyzer (TMA SS7100, manufactured by SII NanoTechnology). Specifically, when the resin composition was cured to a gel fraction of 80% or more, the cured product (resin composite) was cut into a size of φ6 mm x 10 mm, and measured using a thermomechanical analyzer by decreasing the temperature from 200°C to 20°C at a rate of 5°C / min using a compression method. The temperature change in the amount of change in sample length from 25 to 100°C was measured, and the slope of the tangent was recorded as the average coefficient of thermal expansion (CTE1). In addition, the temperature change in the amount of change in the length of the sample was measured at 150 to 200° C., and the slope of the tangent was taken as the average coefficient of thermal expansion (CTE2).

[0080] (glass transition temperature) When the resin composition was cured to a gel fraction of 80% or more, the glass transition temperature (Tg) of the cured product was measured by a thermomechanical analyzer (TMA). Specifically, the measurement was performed using the same device and conditions as in the evaluation of the thermal expansion coefficient, and a graph was created with temperature on the X-axis and linear expansion coefficient on the Y-axis. CTE'1 was determined from the slope of the tangent line at 15 to 75°C of this graph, and CTE'2 was determined from the slope of the tangent line at 150 to 200°C, and the glass transition temperature Tg (°C) was determined from the intersection of CTE'1 and CTE'2.

[0081] Production Example 1 (Production of Zeolite) Into the vessel were sequentially added N,N,N-trimethyl-1-adamantylammonium hydroxide (TMAdaOH) manufactured by Seichem Co., Ltd. as a structure directing agent (SDA), "Kyoward 200S" manufactured by Kyowa Chemical Industry Co., Ltd. as aluminum hydroxide, and "AEROSIL200" manufactured by Nippon Aerosil Co., Ltd. as silica. The composition and molar ratio of the obtained mixture was SiO2:Al2O3:TMAdaOH:H2O=1.0:0.025:0.4:20. After thorough mixing, the obtained mixture was placed in a pressure-resistant container and subjected to hydrothermal synthesis in an oven at 150°C for 48 hours. After suction filtration and washing, it was dried. The obtained powder was fired at 600°C for 6 hours under air flow to remove the TMAdaOH, which is a structure-directing agent (SDA), to obtain CHA-type zeolite. The obtained zeolite was a zeolite in which the particle diameter of each particle was in the range of 1.0 μm to 10 μm, and the average primary particle diameter was 3.1 μm. The average primary particle diameter was the average value of the particle diameters of 50 randomly selected primary particles. In addition, the average thermal expansion coefficient at 50 to 100°C was -9.0 ppm / K, the average thermal expansion coefficient at 50 to 350°C was -17.0 ppm / K, the Si / Al2 ratio was 27.8, the sphericity was 0.85, the circularity was 0.845, the c-axis length was 14.67 Å, ​​and the counter cation was a proton type.

[0082] Next, examples of the resin composition and the resin composite material of the present invention will be described. <Composition ingredients> The components used in preparing the resin compositions and resin composites are as follows:

[0083] <Epoxy resin> (A) Bisphenol F type epoxy resin: Nippon Steel Chemical & Material Co., Ltd., product name "YDF-8170C", epoxy equivalent weight 155 to 165 g / equivalent (B) p-Aminophenol type epoxy resin: manufactured by Mitsubishi Chemical Corporation, product name "jER630", epoxy equivalent: 97g / equivalent <Amine-based hardener> (C) Aromatic polyamine: manufactured by Mitsubishi Chemical Corporation, product name "jER Cure W" (D) Mixture of 3,3'-diethyl-4,4'-diaminodiphenylmethane (melting point 46°C) and polycondensate of formaldehyde-2-ethylaniline: manufactured by Nippon Kayaku Co., Ltd., product name "Kayahard AA", amine value: 126g / Eq, liquid at room temperature <Acid anhydride hardener> (E) Acid anhydride (main component: hydrogenated methyl nadic acid anhydride): manufactured by New Japan Chemical Co., Ltd., product name "Rikacid HNA-100" (acid anhydride equivalent: 174-184) <Filler> As the (F) zeolite filler, the zeolite produced in the above Production Example 1 was used. (G) Silica filler: Admatechs Co., Ltd., product name "SE 2 2 0 0 - SEJ" (average particle size 0.5 μm) (H) Silica filler: Admatechs Co., Ltd., product name "YA 0 5 0 C - SZ 2" (average particle size 50 nm) (I) Silica filler: Admatechs Co., Ltd., product name "YA 0 10 C - SZ 2" (average particle size 10 nm)

[0084] Example 1 The amine-based curing agent and zeolite filler (referred to as "CHA" in Table 1) shown in Table 1 were mixed in the amounts shown in Table 1 with respect to 100 parts by mass of epoxy resin. The mixture was then mixed for 5 minutes at 1500 rpm using a vacuum mixer (EME Corporation, "V-mini 300") to prepare a resin composition (liquid composition). This liquid composition was poured into a mold and heated at 80°C for 2 hours, then heated at 120°C for 2 hours to cure to a gel fraction of 80% or more, and then demolded to obtain a resin composite material. The results of the evaluation using the above evaluation method are shown in Table 1.

[0085] Examples 2 and 3 A resin composition (liquid composition) was obtained in the same manner as in Example 1, except that the content of CHA in Example 1 was set to the amount shown in Table 1. A resin composite material was also obtained in the same manner as in Example 1. The results of evaluation by the above evaluation methods are shown in Table 1.

[0086] Comparative Example 1 A resin composition (liquid composition) was obtained in the same manner as in Example 1, except that an acid anhydride curing agent was used in place of the amine curing agent in the amount shown in Table 1. A resin composite material was also obtained in the same manner as in Example 1. The results of evaluation using the above evaluation methods are shown in Table 1.

[0087] Comparative Example 2 A resin composition (liquid composition) was obtained in the same manner as in Example 1, except that a silica filler (component (G): 189.0 parts by mass, component (H): 18.2 parts by mass, component (I): 10.9 parts by mass) was used instead of the zeolite filler in Example 1. A resin composite material was also obtained in the same manner as in Example 1. The results evaluated by the above evaluation methods are shown in Table 1.

[0088] Comparative Example 3 A resin composition (liquid composition) was obtained in the same manner as in Example 1, except that a silica filler (component (G): 199.8 parts by mass, component (H): 18.2 parts by mass) was used instead of the zeolite filler in Example 1. A resin composite material was also obtained in the same manner as in Example 1. The results of evaluation using the above evaluation methods are shown in Table 1.

[0089] [Table 1]

[0090] From the results of Examples 1 to 3, the resin composition of the present invention is expected to have excellent thermal cycle resistance because the average coefficient of thermal expansion (CTE) is small when cured, and in particular, the average coefficient of thermal expansion (CTE2) at high temperatures above Tg is small. In addition, it is understood that the resin composition has high heat resistance because CTE2 / CTE1 is small and the glass transition temperature (Tg) is high compared to the comparative examples. Furthermore, since the particle size of the filler is small, high filling properties can be achieved even in narrow gaps. [Industrial Applicability]

[0091] According to the present invention, it is possible to provide a resin composition that has a low thermal expansion coefficient after curing, has a small filler particle size, and can sufficiently fill even narrow gaps. In other words, the present invention is suitable for an encapsulant, and is particularly useful as an underfill material.

Claims

1. A resin composition comprising a zeolite, an epoxy resin, and a curing agent, wherein the zeolite has a particle size of 5.0 μm or less and a sphericity of 0.7 or more, and the curing agent has at least one amino group in one molecule.

2. The resin composition of claim 1 , wherein the zeolite has a CBU of d6r.

3. The resin composition according to claim 1 , wherein the zeolite comprises a zeolite having an oxygen ring structure of 8 or less members.

4. The resin composition according to claim 1 , wherein the zeolite comprises a zeolite having a CHA structure.

5. The resin composition according to claim 1, wherein the zeolite has a circularity of 0.800 or more.

6. The resin composition according to claim 1 , wherein the zeolite is an aluminosilicate.

7. The resin composition according to claim 1, wherein the ratio (CTE2 / CTE1) of the average thermal expansion coefficient (CTE2) at 150 to 200 ° C to the average thermal expansion coefficient (CTE1) at 25 to 100 ° C of the cured product when cured to a gel fraction of 80% or more is less than 3.

00.

8. 2. The resin composition according to claim 1, wherein the cured product has a glass transition temperature (Tg) of 125 to 150° C. when cured to a gel fraction of 80% or more.

9. 2. The resin composition according to claim 1, wherein the equivalent number of the curing agent is 0.6 to 1.4 relative to the equivalent number of the epoxy resin.

10. The resin composition according to claim 1, wherein the content of the zeolite is 40 to 70 mass%.

11. A resin composite material formed by curing the resin composition according to any one of claims 1 to 10.

12. A liquid sealant comprising the resin composition according to any one of claims 1 to 10.

13. An encapsulant comprising the resin composite material according to claim 11.

14. An electronic device comprising the resin composite material according to claim 11.

15. A method for producing a sealing material, comprising a step of filling a gap with the resin composition according to any one of claims 1 to 10, and then curing the composition.

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