Resin composition, liquid sealing agent, sealing material, and method for producing sealing material

Abstract

To provide a resin composition that has low coefficient of thermal expansion after curing and is low in viscosity.SOLUTION: A resin composition comprises a zeolite and an epoxy resin, wherein the epoxy resin comprises a polyglycidyl ether of an aliphatic polyhydric alcohol having 3 to 30 carbon atoms.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition, a liquid encapsulant, an encapsulating material, and a method for producing the encapsulating material.

Background Art

[0002] A liquid encapsulant used as an underfill material is required to be excellent in injectability, adhesiveness, curability, storage stability, etc. Further, it is required that the portion encapsulated by the liquid encapsulant be excellent in moisture resistance, thermal cycle resistance, reflow resistance, crack resistance, warpage resistance, etc. In order to satisfy the above requirements, as a liquid encapsulant used as an underfill material, those having an epoxy resin as a main component are widely used.

[0003] Further, in order to improve the moisture resistance and thermal cycle resistance, particularly the thermal cycle resistance, of the portion encapsulated by the liquid encapsulant, a filler made of an inorganic substance such as a silica filler (hereinafter sometimes referred to as an "inorganic filler") is used in the liquid encapsulant, whereby it is known to control the difference in thermal expansion coefficient between a substrate made of an organic material such as an epoxy resin and a semiconductor element, and to reinforce bump electrodes (see Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Liquid encapsulants using inorganic fillers such as silica fillers do not have a sufficiently low coefficient of thermal expansion, and from the viewpoint of thermal cycle resistance and the like, it is required to further lower the coefficient of thermal expansion. Further, zeolite is known as an inorganic filler having a low coefficient of thermal expansion, but a liquid composition containing zeolite tends to have a high viscosity, and when used as an underfill material, the injectability deteriorates. Therefore, it is difficult to obtain a liquid encapsulant with good injectability while lowering the coefficient of thermal expansion of the cured product.

[0006] Therefore, an object of the present invention is to provide a resin composition having a low coefficient of thermal expansion after curing and a low viscosity.

Means for Solving the Problems

[0007] As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by using a resin composition having a specific configuration, and have completed the present invention. The gist of the present invention is as follows. [1] A resin composition containing zeolite and an epoxy resin, wherein the epoxy resin contains a polyvalent glycidyl ether of an aliphatic polyhydric alcohol having 3 to 30 carbon atoms. [2] The resin composition according to [1] above, wherein the zeolite has d6r as CBU. [3] The resin composition according to [1] or [2] above, wherein the zeolite contains a zeolite having a structure of an oxygen 8-membered ring or less. [4] The resin composition according to any one of [1] to [3] above, wherein the zeolite contains a zeolite having a CHA type structure. [5] The resin composition according to any one of [1] to [4] above, wherein the sphericity of the zeolite is 0.7 or more. [6] The resin composition according to any one of [1] to [5] above, wherein the roundness of the zeolite is 0.800 or more. [7] The resin composition according to any one of [1] to [6] above, wherein the zeolite is an aluminosilicate. [8] Further containing a curing agent, the curing agent including an acid anhydride-based curing agent, the resin composition according to any one of [1] to [7] above. [9] The resin composition according to any one of [1] to [8] above, wherein the epoxy resin is liquid at 25°C.

[10] The resin composition according to any one of [1] to [9] above, wherein the epoxy resin substantially does not contain a carbon-chlorine bond.

[11] The resin composition according to any one of [1] to

[10] above, wherein the total amount of the all-inorganic filler containing the zeolite is 30 to 95% by mass.

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

[11] above.

[13] A sealing material obtained by filling the gap with the resin composition according to any one of [1] to

[11] above and then curing it.

[14] A method for manufacturing a sealing material, comprising a step of filling a gap with the resin composition according to any one of [1] to

[11] above and then curing it. [Advantages of the Invention]

[0008] According to the present invention, it is possible to provide a resin composition having a low coefficient of thermal expansion after curing and a low viscosity. [Embodiments for Carrying Out the Invention]

[0009] [Resin Composition] The resin composition of the present invention (hereinafter, may be referred to as "the present resin composition") contains zeolite and an epoxy resin. The resin composition of the present invention is preferably liquid, and when the present resin composition is liquid (hereinafter, may be referred to as "liquid composition"), it is preferably used as a liquid encapsulant, and is particularly suitable as an underfill material. Hereinafter, each constituent element will be described in detail. However, when it is assumed that the composition is liquid, the resin composition shall be read as a liquid composition.

[0010] [Zeolite] (Particle Size of Zeolite) The particle size of the zeolite is preferably 5.0 μm or less. When the particle size of the zeolite is 5.0 μm or less, the resin composition can be sufficiently filled even in a narrow gap. From the above viewpoints, the smaller the particle size of the zeolite, the more preferable, and the lower limit is not particularly limited. In addition, when the particle size of the zeolite is small, there is also an advantage that it is easily mixed uniformly with other components such as resin. Specifically, the particle size of the zeolite is preferably less than 5.0 μm, more preferably 4.5 μm or less, and even more preferably 4.0 μm or less.

[0011] On the other hand, there is no particular limitation on the lower limit value. However, from the viewpoints of easy handling and difficulty in increasing the viscosity of the resin composition, it may be 0.05 μm or more, may be 0.1 μm or more, may be 0.3 μm or more, may be 0.5 μm or more, or may be 1.0 μm or more. The particle size of the zeolite means the diameter (equivalent circle diameter) of the largest circle having an area equal to the projected area of the particle in the observation of the particles by a scanning electron microscope (SEM). In addition, the zeolite may be formed by aggregation of a plurality of zeolite particles to form secondary particles. In this case, the particle size of the zeolite is the particle size of the primary particles.

[0012] When using zeolite, usually, zeolite particles are not used alone but as a plurality of zeolite particle groups. That is, in one aspect of the present invention, it is preferable to use it as a zeolite group containing at least the zeolite particles. In one aspect composed of such a plurality of zeolite particles, the average primary particle size of the zeolite is preferably 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 obtained by randomly selecting 50 zeolites (powder, particles in the liquid composition described later), measuring their particle sizes, and taking the average value. Further, as for the particle size distribution of the zeolite on a volume basis, the median diameter (d50) is preferably in the range of 0.05 to 5.0 μm, 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. When the median diameter is within this range, the effects of the present invention can be obtained more easily with a smaller amount.

[0013] (Structure of Zeolite) Zeolite is a compound composed of silicon or aluminum and oxygen, with a TO 4 unit (where the T element is an element other than oxygen that constitutes the framework) as the basic unit. Specifically, zeolites include crystalline porous aluminosilicates (aluminosilicates), crystalline porous aluminophosphates (ALPOs), or crystalline porous silicoaluminophosphates (SAPOs), etc. The zeolite of the present invention may have any of the above structures, but aluminosilicates are preferred. Zeolite is a TO 4 unit formed by connecting several (several to dozens) of them, called a Composite Building Unit (hereinafter sometimes referred to as "CBU"). Therefore, it has regular channels (tubular pores) and cavities (voids). Regarding this CBU and the crystal structure of the zeolite described later, it can be shown by the code that defines the zeolite structure determined by the International Zeolite Association (IZA). The structure of the zeolite can be specified based on the X-ray diffraction pattern obtained by an X-ray structure analyzer (for example, the desktop X-ray diffractometer D2PHASER manufactured by BRUKER) using the zeolite structure database 2018 version (http: / / www.iza-structure.org / databases / ).

[0014] (Framework of Zeolite) The framework of this zeolite preferably has d6r as the CBU. By having d6r, a resin composition with a low coefficient of thermal expansion after curing can be easily obtained. As a CBU, examples of zeolites having d6r include zeolites of 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 -WEN type structures, etc. Among these, from the viewpoint of easy particle size control, zeolites having a structure with an oxygen 8-membered ring or less are particularly preferred. Examples of zeolites having a structure with an oxygen 8-membered ring or less include zeolites of AEI, AFT, AFX, CHA, ERI, KFI, SAT, SAV, SFW, and TSC type structures, etc. Among these, zeolites of AEI, AFX, CHA, and ERI type structures are particularly preferred because the structure is stable even with shape control, and zeolites having a CHA type structure are most preferred. In this specification, the structure having an oxygen 8-membered 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. Also, the above zeolite may be used alone or in combination of two or more kinds.

[0015] (Average coefficient of thermal expansion of zeolite) The average coefficient of thermal expansion of this zeolite is preferably low because it is easy to reduce the average coefficient of thermal expansion of the liquid composition described later by a small amount. Also, it is preferable in that various physical properties of the resin are less likely to change due to the addition of the zeolite because the amount of the zeolite is small. In particular, it is also preferably low because it can suppress the increase in viscosity of the liquid composition described later. Specifically, the average coefficient of thermal expansion of the zeolite is usually less than 0 ppm / K, preferably -2 ppm / K or less, more preferably -3 ppm / K or less, still 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 one hand, considering the use of the zeolite as a liquid composition containing the zeolite and the resin described later, it is preferable that the difference in the average coefficient of thermal expansion from that of the resin is small and it is difficult for the zeolite and the resin to separate. Therefore, the average coefficient of thermal expansion of the zeolite is usually -1000 ppm / K or more, preferably -900 ppm / K or more, more preferably -800 ppm / K or more, still more preferably -700 ppm / K or more, particularly preferably -500 ppm / K or more, and most preferably -300 ppm / K or more. In particular, when used for sealing material applications, it is preferably high, specifically, -100 ppm / K or more, more preferably -50 ppm / K or more, still more preferably -40 ppm / K or more, particularly preferably -30 ppm / K or more, most preferably -25 ppm / K or more, and most preferably -20 ppm / K or more. Incidentally, the average coefficient of thermal expansion of the zeolite can be measured by calculating the lattice constant using an X-ray diffractometer "D8 ADVANCE" manufactured by BRUKER and X-ray diffraction analysis software "JADE". Here, in order to exclude the influence of moisture desorption, the zeolite is usually measured in a dried state. The measurement of the average coefficient of thermal expansion of the zeolite is usually carried out in the range of 50 to 100 °C. That is, it is a numerical value representing the displacement of the lattice constant per degree Celsius from the average lattice constant at 50 °C when the zeolite is heated and the average lattice constant at 100 °C. 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. Incidentally, the measurement of the average coefficient of thermal expansion is carried out by gradually heating after waiting until the lattice constant becomes stable.

[0017] Resins generally tend to have a large coefficient of thermal expansion in the high-temperature range. Therefore, the average coefficient of thermal expansion of zeolite is preferably low, especially when heating up to the high-temperature range. 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 numerical value representing the displacement of the lattice constant per degree Celsius from the average lattice constant at 50 °C and the average lattice constant at 350 °C when the zeolite is heated.

[0018] (Shape of zeolite) This zeolite is preferably spherical. By having a spherical shape, it is possible to suppress an increase in the viscosity of the resin composition containing the zeolite. Specifically, it preferably has the following sphericity and roundness.

[0019] <<Sphericity>> The sphericity of this zeolite is preferably 0.7 or more, more preferably 0.8 or more. Also, 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 zeolites, is 0.58. In this application, "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 the particle". The maximum diameter and the minimum diameter can be determined by observation with a scanning electron microscope (SEM).

[0020] <<Roundness>> The roundness of this 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. Also, the upper limit of the roundness is not particularly limited and may be 1 or less. The roundness of a cube, which is common in zeolites, is 0.785. In this specification, "roundness" is defined as "4×π×area / (circumference) 2It is defined as "". The area and circumference can be determined by observation with a scanning electron microscope (SEM). In the present application, the "circularity" is the average value of 10 particles obtained by a scanning electron microscope (SEM).

[0021] (Framework density of zeolite) The framework density of the present zeolite is not particularly limited as long as the effects of the present invention are not impaired. The framework density of zeolite is preferably low in that the structural vibration of zeolite is likely to occur and the average coefficient of thermal expansion is likely to be low. Therefore, the framework density of zeolite is preferably 17.0 T / 1000 Å 3 More preferably, it is 16.0 T / 1000 Å or less. 3 It is as follows. On the other hand, the framework density of zeolite is preferably high in that the structural stability of zeolite is likely to be high. The framework density of zeolite is preferably 12.0 T / 1000 Å 3 More preferably, it is 13.0 T / 1000 Å or more. 3 More preferably, it is 14.0 T / 1000 Å or more. 3 It is as follows. When the framework density is within the above range, zeolite can be used as a stable filler. The framework density indicates the number of T atoms present per unit volume of zeolite and is a value determined by the structure of zeolite. In this specification, the numerical values described in the 2017 edition 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 or equal to 17.0 T / 1000 Å 3 Examples of zeolites include ERI, LTL, LTN, MOZ, OFF, SAT, SSF, and zeolites of the -WEN type structure. When the framework density is 15.0 T / 1000 Å 3Greater than 16.0 T / 1000 Å 3 Examples of the following zeolites include zeolites of AEI, AFT, AFV, AFX, AVL, EAB, GME, LEV, MWW, and SFW framework structures. The framework density is 14.0 T / 1000 Å 3 Greater than 15.0 T / 1000 Å 3 Examples of the following zeolites include zeolites of CHA, KFI, SAS, and SAV framework structures. The framework density is 14.0 T / 1000 Å 3 Examples of zeolites existing in the following ranges include zeolites of EMT, FAU, JSR, SBS, SBT, and TSC framework structures.

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

[0024] In addition, when elements such as gallium, iron, boron, titanium, zirconium, tin, zinc, and phosphorus are used instead of silicon and aluminum, the molar ratio of the oxide of the substituted element may be converted as the molar ratio of alumina or silica. Specifically, when gallium is used instead of aluminum, the molar ratio of gallium oxide may be converted to 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", "molar ratio of Si / Al 2 ", or "Si / Al 2 ratio".) is not particularly limited as long as the effects of the present invention are not impaired. The SAR (Si / Al 2The (ratio) is preferably high in that the moisture resistance of the cured product is increased and it is easy to control the amount of the counter cation. Therefore, the SAR (Si / Al 2 ratio) of the zeolite is usually 2 or more, preferably 3 or more, more preferably 3.5 or more, still more preferably 4 or more, particularly preferably 4.5 or more, and most preferably 5 or more. On the other hand, the SAR (Si / Al 2 ratio) of the zeolite is preferably low in that it is easy to be manufactured at low cost. Therefore, the SAR (Si / Al 2 ratio) of the zeolite is usually 2000 or less, preferably 1000 or less, more preferably 500 or less, and still more preferably 100 or less. When the Si / Al 2 ratio is within the above range, it is easy to control the amount of the counter cation, and the manufacturing cost of the zeolite can also be reduced. The Si / Al 2 ratio of the zeolite can be adjusted by the types and ratios of the silicon-containing compound and the aluminum-containing compound as raw materials, the types and amounts of the structure-directing agent, the use of seed crystals, the synthesis conditions such as temperature and time, and the like.

[0026] (Counter cation of zeolite) The counter cation of the present zeolite is not particularly limited as long as the effects of the present invention are not impaired. The counter cation of the zeolite is usually a proton, an alkali metal ion, or an alkaline earth metal ion. Preferably, it is a proton or an alkali metal ion, and more preferably, it is 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 the size, the more preferable because the zeolite is more likely to exhibit an average thermal expansion coefficient of less than 0 ppm / K. Among them, the counter cation of the zeolite is preferably a proton because the average thermal expansion coefficient of the cured product is likely to decrease. That is, as the zeolite, preferably, it is a proton type or an alkali metal type, and more preferably, it is a proton type, a Li type, a Na type, or a K type.

[0027] (Crystallinity of zeolite) The crystallinity of the zeolite is not particularly limited as long as the effects of the present invention are not impaired. The reason is that the Composite Building Unit (CBU) is presumed to be a factor that has a greater influence on the average coefficient of thermal expansion of the cured product than the structure defined by the code of IZA. The crystallinity of the zeolite can be determined by comparing the X-ray diffraction peak of the zeolite with a certain X-ray diffraction peak determined by an X-ray diffractometer (for example, the desktop X-ray diffractometer D2PHASER manufactured by BRUKER). As a specific calculation example, the crystallinity of the LTA-type zeolite in Scientific Reports 2016, 6, Article number: 29210 can be mentioned.

[0028] (Surface treatment of zeolite) The zeolite may be subjected to surface treatments such as silylation treatment and fluorination treatment as long as the effects of the present invention are not impaired. The surface treatment may be a physical treatment or a chemical treatment.

[0029] (Content of zeolite) The content of the zeolite in the resin composition is preferably 40 to 80% by mass, more preferably 45 to 75% by mass, and even more preferably 50 to 65% by mass, based on the total amount of the resin composition, from the viewpoint of suppressing the increase in the viscosity of the resin composition and lowering the coefficient of thermal expansion.

[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 the effects of the present invention are not impaired, and examples include at least one selected from the group consisting of metals, carbon, metal carbides, metal oxides, and metal nitrides. Examples of metals include silver, copper, aluminum, gold, nickel, iron, and titanium. Examples of carbon include carbon black, carbon fiber, graphite, fullerene, diamond, etc. Examples of metal carbides include silicon carbide, titanium carbide, tungsten carbide, etc. Examples of metal oxides include magnesium oxide, aluminum oxide (alumina), silicon oxides such as silica, calcium oxide, zinc oxide, yttrium oxide, zirconium oxide, cerium oxide, ytterbium oxide, sialon (a ceramic composed of silicon, aluminum, oxygen, and nitrogen), etc. Examples of metal nitrides include boron nitride, aluminum nitride, silicon nitride, etc.

[0031] When the resin composition contains other inorganic fillers other than this zeolite, the content of this zeolite in all the fillers is preferably 90% by mass or more, more preferably 95% by mass or more, from the viewpoint that the effects of this zeolite can be sufficiently exhibited. An embodiment where this zeolite is 100% by mass and does not contain fillers other than this zeolite may also be possible.

[0032] (Total amount of inorganic fillers) The total content of all inorganic fillers (total inorganic fillers) contained in the resin composition is preferably large in terms of easily exhibiting the effect as a filler. On the other hand, when the resin composition is liquid, it is preferably small in terms of high fluidity and easy filling into a narrow space. Specifically, the total content of the total inorganic fillers is preferably 30% by mass or more, more preferably 35% by mass or more, particularly preferably 40% by mass or more with respect to 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, particularly preferably 80% by mass or less.

[0033] (Dispersant) This resin composition may contain a dispersant in order to enhance the dispersibility of inorganic fillers such as this zeolite. The dispersant contained in the liquid composition containing a resin and a filler is mainly added to the liquid composition containing a resin and a filler with a large polarity difference, thereby improving the interfacial state between the two and enhancing the compatibility. As a result, it is possible to exhibit effects such as viscosity reduction, improvement in filler dispersibility, prevention of filler aggregation and sedimentation.

[0034] Examples of the dispersant include acrylic dispersants and polymer dispersants. Here, the "polymer dispersant" means a dispersant having a weight average molecular weight of 1,000 or more. The dispersant is preferably a polymer dispersant. In addition, the main chain skeleton of the polymer dispersant is not particularly limited, and examples include polyurethane skeletons, polyacrylic skeletons, polyester skeletons, polyamide skeletons, polyimide skeletons, and polyurea skeletons. From the viewpoint of storage stability, polyurethane skeletons, polyacrylic skeletons, and polyester skeletons are preferred. Also, the structure of the polymer dispersant is not particularly limited, and examples include random structures, block structures, comb-shaped structures, and star-shaped structures. Similarly, from the viewpoint of storage stability, block structures or comb-shaped structures are preferred. In addition, the dispersant is preferably a solvent-free type dispersant, particularly a solvent-free type polymer dispersant. By the dispersant not containing a solvent, it is possible to prevent the dispersant from volatilizing and voids from occurring when the composition is heat-cured. Commercially available products can be used as the dispersant. Examples of commercially available products include the following dispersants, and a dispersant having at least one of the functional groups of amino groups and amine salts may be used.

[0035] As commercially available products of polymer dispersants, there are 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, which are commercially available from BYK Chemie; EFKA series 4008, 4009, 4010, 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4340, 4400, 4401, 4402, 4403, 4406, 4800, 5010, 5044, 5054, 5055, 5063, 5064, 5065, 5066, 5070, 5244, which are commercially available from BASF Japan; Solsperse series 3000, 5000, 11200, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000SC, 24000GR, 26000, 28000, 31845, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 36000, 36600, 37500, 38500, 39000, 53095, 54000, 55000, 56000, 71000, which are commercially available from Lubrizol; DISPARLON series 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, which are commercially available from Nippon Kasei Kogyo Co., Ltd.; Ajisper series PB-711, PB-821, PB-822, PN-411, PA-111, which are commercially available from Ajinomoto Co., Inc.; Surfynol series 104A, 104C, 104E, 104H, 104S, 104BC, 104DPM, 104PA, 104PG-50, 420, 440, DF110D, DF110L, DF37, DF58, DF75, DF210, CT111, CT121, which are commercially available from Air Products and Chemicals, Inc.CT131, CT136, GA, TG, TGE, STG of the olefin series commercially available from Nissin Chemical Industry Co., Ltd., E1004, 70, 2120, 2190 of the SN sparse series manufactured by San Nopco Ltd., Adeka Cole and Adeka Tol series commercially available from ADEKA Corporation, Sun Nonic series, Naroa Acti CL series, Emalmin series, Newpole PE series, Ionet M series, Ionet D series, Ionet S series, Ionet T series, Sun Separator 100, etc. can be mentioned.

[0036] The content of the dispersant is preferably large, for example, in terms of facilitating the uniform dispersion of the inorganic filler in the liquid composition. On the other hand, the content of the dispersant is preferably small in terms of making it difficult for the thermal expansion coefficient to increase due to phase separation between the inorganic filler and resins such as epoxy resins. Therefore, since it is easy to fill the liquid composition into a narrow space and it is easy to obtain a low thermal expansion coefficient after curing, the content of the dispersant is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 0.1% by mass or more and 25% by mass or less with respect to the total amount of the composition.

[0037] <Method for producing zeolite> Known methods can be applied to the method for producing zeolite. For example, when producing CHA-type zeolite, it can be produced with reference to the method described in JP-A-2009-097856. More specifically, an aluminum atom raw material, a silica atom raw material, an organic structure directing agent, etc. are mixed to prepare an aqueous gel. The mixing order is usually to mix the aluminum atom raw material in water, and then mix the silica atom raw material and the organic structure directing agent thereto. Next, the prepared aqueous gel is hydrothermally synthesized, the product is separated, washed with water, dried, and the contained organic substances are removed by methods such as calcination to obtain 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 this zeolite has 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. Further, the method for producing this zeolite preferably further has a firing step. As the firing conditions, they can be appropriately determined according to the type of zeolite to be produced or according to conditions such as hydrothermal synthesis. For example, in the case of the CHA-type zeolite suitable in the present invention, the range of 500 to 700 °C is preferable, and the range of 550 to 650 °C is more preferable. As the firing time, 3 to 10 hours is preferable, 4 to 8 hours is more preferable, and 5 to 7 hours is even more preferable. The firing atmosphere is not particularly limited, and it may be in air or in a nitrogen atmosphere. In addition, if necessary, a desired zeolite (hereinafter, may be 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, tetraethyl orthosilicate, aluminosilicate gel, and zeolite can be used. These may be used alone, or two or more kinds may be used in combination at an arbitrary combination and ratio.

[0040] <<Aluminum atom raw material>> As the aluminum atom raw material, it is preferable to use a water-soluble raw material. Further, aluminum hydroxide is preferable in that it has a low alkali metal content.

[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-adamantammonium hydroxide (TMAdaOH) is preferable. The usage amount of the organic structure-directing agent is 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 in terms of the molar ratio to silicon (Si) contained in the raw material composition. On the other hand, it is usually 1 or less, preferably 0.6 or less, more preferably 0.55 or less, and further preferably 0.5 or less. By using it within this range, it is considered that high-purity spherical zeolite with few by-products is likely to grow.

[0042] <<Water>> From the viewpoint that crystals are likely to form, when using the seed crystal zeolite described later, the usage amount of water is usually 5 or more, preferably 7 or more, more preferably 9 or more, and further 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. By setting it within this range, it is preferable because crystals are likely to form. Also, when hydrothermally synthesizing zeolite under the condition of increasing the amount of water to dilute the raw material concentration, zeolite with a large particle size is likely to be obtained. Also, from the viewpoint of easily obtaining the cost reduction effect for waste liquid treatment, it is usually 50 or less, preferably 40 or less, more preferably 30 or less, and further preferably 25 or less in terms of the molar ratio to silicon (Si).

[0043] <<Alkali metal atom raw material>> For the production of zeolite, an alkali metal atom raw material may be used. The alkali metal atom in the case of using an alkali metal atom raw material is not particularly limited, and known ones used in the synthesis of zeolite can be used, but at least one kind of alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium is preferable. Note that a plurality of kinds of alkali metal atoms may be used.

[0044] <<Seed crystal zeolite>> In the method for producing this zeolite, zeolite serving as a seed crystal may be used. When using seed crystal zeolite, one kind may be used alone, or two or more kinds may be used in combination at an arbitrary combination and ratio.

[0045] <<Mixing of Raw Materials (Preparation of Raw Material Composition before Reaction)>> The raw material composition can usually be obtained by mixing a silicon atom raw material, an aluminum atom raw material, an organic structure-directing agent, and water, and adding seed 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 in an arbitrary step as necessary.

[0046] <<Aging>> The raw material composition prepared as described above may be hydrothermally synthesized immediately after preparation. However, in order to obtain zeolite with higher crystallinity, it is preferable to age for a certain period of time under predetermined temperature conditions. Particularly when scaling up the reaction, since the stirrability is improved and the raw materials are more easily made into a uniform state, it is preferable to age while stirring the raw materials for a certain period. The temperature for aging is usually 100 °C or lower, preferably 95 °C or lower, more preferably 90 °C or lower. The lower limit is not particularly limited, but the temperature for aging is usually 0 °C or higher, preferably 10 °C or higher. The aging temperature may be constant during aging, or may be changed stepwise or continuously. The aging time is not particularly limited, but is usually 2 hours or longer, preferably 3 hours or longer, more preferably 5 hours or longer. On the other hand, it is usually 30 days or shorter, preferably 10 days or shorter, more preferably 4 days or shorter.

[0047] <<Hydrothermal Synthesis>> Next, the obtained raw material composition is hydrothermally synthesized. Hydrothermal synthesis is usually carried out by putting the raw material composition prepared as described above or the aqueous gel obtained by aging it into a pressure-resistant container, and maintaining a predetermined temperature under self-generated pressure or under gas pressurization to such an extent that crystallization is not inhibited, with stirring, or while rotating or oscillating the container, or in a static state. 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 it is usually 2 hours or longer, preferably 3 hours or longer, more preferably 5 hours or longer, and on the other hand, it is usually 30 days or shorter, preferably 10 days or shorter, more preferably 7 days or shorter, and even more preferably 5 days or shorter. The reaction temperature may be constant during the reaction or may be changed stepwise or continuously.

[0048] <Epoxy resin> The resin composition of the present invention contains an epoxy resin. The epoxy resin used in the present invention is characterized by containing a polyvalent glycidyl ether of an aliphatic polyhydric alcohol having 3 to 30 carbon atoms (hereinafter, may be simply referred to as "glycidyl ether compound").

[0049] (Glycidyl ether compound) The glycidyl ether compound in the present invention is obtained by epoxidizing the carbon-carbon double bond of a polyvalent allyl ether of an aliphatic polyhydric alcohol having 3 to 30 carbon atoms with an oxidizing agent. Specifically, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, tricyclodecanedimethanol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, ditrimethylolpropane tetraglycidyl ether, diglycerin tetraglycidyl ether, erythritol tetraglycidyl ether, xylitol pentaglycidyl ether, dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, sorbitol hexaglycidyl ether, inositol pentaglycidyl ether, inositol hexaglycidyl ether, etc. can be exemplified. Among these, from the viewpoints of the viscosity of the compound and the heat resistance of the cured product, 1,4-cyclohexanedimethanol diglycidyl ether, tricyclodecanedimethanol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, ditrimethylolpropane tetraglycidyl ether, diglycerin tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, and sorbitol hexaglycidyl ether are preferable, and 1,4-cyclohexanedimethanol diglycidyl ether, tricyclodecanedimethanol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, and pentaerythritol tetraglycidyl ether are particularly preferable.

[0050] The glycidyl ether compound contained in the resin composition of the present invention is a compound that is liquid at 25°C and substantially does not contain a carbon-chlorine bond in the molecule. The glycidyl ether compounds used in conventional resin compositions are mainly produced by the condensation reaction of aliphatic alcohols or phenols with epichlorohydrin. However, at that time, compounds having a terminal group containing a carbon-chlorine bond represented by the formula (1) in the molecule are produced as by-products. When using a glycidyl ether compound contaminated with these by-products, the viscosity of the resin composition increases, and the resulting cured product has a low glass transition temperature and poor heat resistance.

[0051]

Chemical formula

[0052] In the present invention, "substantially free of carbon-chlorine bonds" means that no peaks corresponding to compounds containing carbon-chlorine bonds and their fragments are observed in the mass spectrum of the glycidyl ether compound. Specifically, in the mass spectrum of the glycidyl ether compound, no peaks corresponding to compounds containing carbon-chlorine bonds and their fragments that are by-produced when producing the glycidyl ether compound by the epichlorohydrin method using an aliphatic alcohol as a raw material are observed.

[0053] As a method for producing a glycidyl ether compound that does not generate the above by-products, a method of oxidizing the carbon-carbon double bond of the allyl group of the allyl ether compound with an oxidizing agent can be mentioned. Specifically, for example, it can be produced by the following method. 1) A method of oxidizing the carbon-carbon double bond of the allyl ether compound using a peracid such as peracetic acid as an oxidizing agent (for example, Japanese Patent Laid-Open No. 7-145221) 2) A method of oxidizing the carbon-carbon double bond of the allyl ether compound using hydrogen peroxide as an oxidizing agent and using a catalyst such as tungsten or zeolite (for example, Japanese Patent Laid-Open No. 60-60123) 3) A method of oxidizing the carbon-carbon double bond of an allyl ether compound in a basic atmosphere in the coexistence of acetonitrile using hydrogen peroxide as an oxidizing agent (for example, Japanese Patent Laid-Open No. 59-227872)

[0054] The glycidyl ether compound obtained by the above method is preferably purified by distillation, treatment with an adsorbent, etc. and used as needed.

[0055] The glycidyl ether compound used in the present invention is liquid at 25°C. The viscosity of the glycidyl ether compound at 25°C is preferably in the range of 1 mPa·s to 1000 mPa·s, more preferably 5 mPa·s or more, and even more preferably 10 mPa·s or more. Also, it is preferably 500 mPa·s or less, and even more preferably 300 mPa·s or less. The method for measuring the viscosity of the epoxy resin is defined in JIS K7233 (1986), and the single-cylinder rotational viscometer method is suitable. The viscosity of the epoxy resin used in the present invention at 23°C is preferably measured using a B-type rotational viscometer (「LVDV-1 Pri」, manufactured by Brookfield, spindle: S62), which is one of the single-cylinder rotational viscometer methods.

[0056] The epoxy equivalent of the glycidyl ether compound is preferably in the range of 80 to 300 g / equivalent, and more preferably in the range of 90 to 200 g / equivalent. When the epoxy equivalent is at least the above lower limit value, the impact resistance of the cured product becomes sufficient. On the other hand, when it is at most the above upper limit value, the viscosity when adding a curing agent does not become too high, and the handleability is excellent. The epoxy resin may be used alone, or two or more kinds may be mixed and used in any combination and ratio, but the epoxy equivalent in the case of mixing is the equivalent of the mixture.

[0057] In the present resin composition, the content of the epoxy resin is preferably small in terms of making it easier to lower the coefficient of thermal expansion due to the relatively large content of inorganic fillers such as zeolite. On the other hand, it is preferably large in terms of maintaining the excellent physical properties of the epoxy resin. As described above, from the viewpoint of achieving both the maintenance of the excellent physical properties of the resin and the heat resistance (difficulty of thermal expansion) of the cured resin composition, specifically, it 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 30% by mass or less, and particularly preferably 20% by mass or less.

[0058] (Curing agent) The resin composition of the present invention preferably further contains a curing agent. A curing agent refers to a substance that contributes to the cross-linking reaction between the cross-linking groups of the epoxy resin. There are no particular restrictions on the curing agent, and those generally known as epoxy resin curing agents can be used. For example, phenolic curing agents, amine-based curing agents such as aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, acid anhydride-based curing agents, amide-based curing agents, tertiary amines, imidazole and its derivatives, organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan-based curing agents, isocyanate-based curing agents, blocked isocyanate-based curing agents, dicyandiamide compounds, etc. can be mentioned. From the viewpoints of imparting fluidity and rapid curability, an acid anhydride-based curing agent is preferred as the curing agent.

[0059] 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 novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cresol novolak, xylenol novolak, 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, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allylated or polyallylated products of the above dihydroxynaphthalenes, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, allylated pyrogallol, etc.

[0060] Specific examples of amine curing agents include, as aliphatic amines, ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra(hydroxyethyl)ethylenediamine, and the like. Examples of polyetheramines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propylamine), polyoxypropylene diamine, polyoxypropylene triamines, and the like. Examples of alicyclic amines include isophoronediamine, metaxylylenediamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, norbornenediamine, and the like. 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'-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, α,α'-bis(4-aminophenyl)-p-diisopropylbenzene, and the like.

[0061] Specific examples of the acid anhydride-based curing agent include dodecenyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyloctadecanedioic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, anhydrous methyl hymic acid, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, methylcyclohexenetetracarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bistrimellitate dianhydride, anhydrous het acid, anhydrous nadic acid, anhydrous methyl nadic acid, hydrogenated nadic acid, hydrogenated methyl nadic acid, 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-naphthalenesuccinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, and the like.

[0062] Examples of the amide-based curing agent include dicyandiamide, polyamide resin, and the like. Examples of the tertiary amine include 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, and the like. Examples of 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, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resins and the above imidazoles or polymer-encapsulated imidazoles, etc.

[0063] Examples of organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, etc. Examples of phosphonium salts include tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, tetrabutylphosphonium tetrabutylborate, etc. Examples of tetraphenylborate salts include 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate, etc. These curing agents may be used alone, or two or more of them may be mixed and used in any combination and ratio.

[0064] When the resin composition of the present invention contains a curing agent, the content of the curing agent is preferably in the range of 0.8 to 2.0 in terms of the equivalent ratio of the functional group in the curing agent to the epoxy group in the epoxy resin (functional group in the curing agent / epoxy group in the epoxy resin) because it is difficult for the influence of the residual unreacted epoxy group or the functional group of the curing agent to occur. More preferably, it is used in the range of 0.8 to 1.5.

[0065] When the curing agent is an amide-based curing agent, a tertiary amine, imidazole and its derivatives, organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan-based curing agents, isocyanate-based curing agents, blocked isocyanate-based curing agents, etc., it is preferably used in an amount of 0.1 part by mass or more, more preferably 0.5 part by mass or more, based on 100 parts by mass of the epoxy resin. On the other hand, it is preferably used in an amount of 20 parts by mass or less, more preferably 10 parts by mass or less. In the case of a dicyandiamide compound, it is preferably used in an amount of 0.1 part by mass or more, more preferably 0.5 part by mass or more, based on 100 parts by mass of the epoxy resin. On the other hand, it is preferably used in an amount of 10 parts by mass or less, more preferably 6 parts by mass or less.

[0066] (Reactive diluent) When the present resin composition is in a liquid state, the present resin composition may contain a reactive diluent. The reactive diluent is not particularly limited as long as it contains at least one monofunctional epoxy compound. The monofunctional epoxy compound is an epoxy compound having one epoxy group, and has conventionally been used for adjusting the viscosity of an epoxy resin composition as a reactive diluent. The monofunctional epoxy compound is roughly classified into an aliphatic monofunctional epoxy compound and an aromatic monofunctional epoxy compound, and is preferably an aromatic monofunctional epoxy compound from the viewpoint of viscosity.

[0067] (Other additives) In addition to the above, the present resin composition may appropriately contain other additives selected from coupling agents, ultraviolet absorbers, antioxidants, plasticizers, flame retardants, colorants, fluidity improvers, defoamers, ion trap agents, and the like.

[0068] When the present resin composition is in a liquid state, the present resin composition is preferably a solvent-free system. By making it a solvent-free system, it is possible to prevent the generation of voids and the like due to the volatilization of the solvent when the liquid composition is heat-cured. Here, the solvent is a volatile component, and in this specification, it is a term including water and organic solvents. The solvent-free liquid composition substantially does not contain a solvent. For example, with respect to the total amount of the liquid composition, 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.

[0069] (Method for Producing the Present Resin Composition) The present resin composition can be obtained by mixing and kneading an epoxy resin, zeolite, a curing agent used as required, other inorganic fillers, a dispersant, a reactive diluent, and other additive components using a vacuum mixer, a mixing roll, a planetary mixer, etc., and defoaming as required. The blending order of these components is arbitrary as long as there are no particular problems such as reactions or precipitates occurring. Among the constituent components, any two components or three or more components may be mixed in advance, and then the remaining components may be mixed, or all the components may be mixed at once.

[0070] (Physical Properties of the Present Resin Composition) (Coefficient of Thermal Expansion (CTE)) When the resin composition is cured to a gel fraction of 80% or more, the average coefficient of thermal expansion (CTE) of the cured product at 25 to 100 °C is preferably 0 ppm / K or more, more preferably 2 ppm / K or more, still more preferably 4 ppm / K or more, and particularly preferably 10 ppm / K or more. On the other hand, it is preferably 100 ppm / K or less, more preferably 50 ppm / K or less, still more preferably 30 ppm / K or less. Such an epoxy resin composition is useful as a material requiring various heat resistances because of its low average coefficient of thermal expansion at temperatures below the glass transition temperature, and is particularly effective for application to electronic devices.

[0071] The average coefficient of thermal expansion may be measured by thermomechanical analysis for the cured product obtained by curing the resin composition to a gel fraction of 80% or more. Specific measurement conditions are as described in the examples.

[0072] (Viscosity) This resin composition is preferably a composition having fluidity at room temperature (23 °C). The viscosity of this resin composition is preferably low in terms of easy filling of the composition even in a narrow space. On the other hand, it is preferably high in terms of difficulty in occurrence of dripping and the like during composition filling. The viscosity of this resin composition at 23 °C is preferably 0.1 Pa·s or more, more preferably 1 Pa·s or more, still more preferably 5 Pa·s or more, and particularly preferably 10 Pa·s or more. On the other hand, it is preferably 250 Pa·s or less, more preferably 150 Pa·s or less, particularly preferably 50 Pa·s or less, and most preferably 10 Pa·s or less.

[0073] The viscosity at 23 °C may be measured using a B-type rotational viscometer, which is one of the single-cylinder rotational viscometer methods. For example, the B-type rotational viscometer described in the examples may be used.

[0074] <Use> This resin composition can be used, for example, in catalyst modules, molecular sieve membrane modules, optical members, moisture-absorbing members, foods, building members, and components and packaging members of electronic devices, etc., and is preferably used in electronic devices among them. An electronic device is a device that has two or more electrodes and controls the current flowing between the electrodes or the generated voltage by electricity, light, magnetism, chemical substances, etc., or generates light, an electric field, or a magnetic field by an applied voltage or current. Specifically, resistors, rectifiers (diodes), switching elements (transistors, thyristors), amplifying elements (transistors), memory elements, or chemical sensors, etc., or devices in which these elements are combined or integrated can be mentioned. In addition, 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 can also be mentioned. The electronic device is preferably a semiconductor device. The semiconductor device preferably has at least a semiconductor substrate, and examples include devices in which semiconductor chips are mounted on the substrate, and devices in which semiconductor chips and semiconductor substrates are laminated in multiple layers.

[0075] [Liquid encapsulant] When this resin composition is in a liquid state, it is preferably used as a liquid encapsulant, and in that case, the liquid composition is cured to become an encapsulating material. The liquid encapsulant may be filled in the gaps formed in the constituent members and then cured to be used as an encapsulating material that fills the gaps. Note that a method for manufacturing an encapsulating material having a step of curing the resin composition after filling it in the gaps is also within the scope of the present invention. In addition, the liquid encapsulant may be used, for example, after being applied on various constituent members, another constituent member is overlaid on the liquid encapsulant, and then appropriately cured to fill the gaps between the constituent members. At this time, the liquid encapsulant may be appropriately cured and B-staged before another constituent member is overlaid. Among these, the resin composition of the present invention, particularly the liquid composition in which the present resin composition is liquid, is preferably used for applications where it is filled into gaps and cured. That is, it is preferable to produce a sealing material by filling the resin composition of the present invention into gaps and then curing it.

[0076] The resin composition of the present invention is preferably used as a liquid sealing agent, 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 example, for filling gaps formed between a substrate and a semiconductor chip, between substrates, between semiconductor chips, etc. As the substrate, known substrates can be used, and it is advisable to use substrates made of organic materials such as epoxy resin substrates and phenolic resin substrates. Further, the semiconductor chip is preferably formed from a semiconductor substrate such as a silicon substrate. The cured product of the resin composition of the present invention has a low coefficient of thermal expansion. By using it as an underfill material, the difference from the coefficient of thermal expansion of a semiconductor substrate, etc. becomes small, so the thermal cycle resistance, etc. is improved.

[0077] The underfill material is preferably used, for example, as a sealing material that fills the gap between a substrate and a semiconductor chip in a laminate in which a semiconductor chip is mounted on the substrate and is then cured by heating to seal the space between the substrate and the chip. At this time, the semiconductor chip is preferably joined to the surface of the substrate on which a wiring pattern has been formed via bumps, for example, by reflow, before the underfill material is filled.

[0078] 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, an 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 such that the surface on which the underfill layer is formed faces the substrate. Next, by heating, pressurizing, etc., the underfill layer is cured to become a sealing material, and the semiconductor chip is joined to the surface of the substrate on which the wiring pattern is formed via the bumps.

[0079] Also, in the pre-apply method, an underfill layer may be formed by applying an underfill material on the surface of a substrate on which a wiring pattern is formed. Here, the applied underfill layer may be B-staged as necessary. Thereafter, the semiconductor chip on which the bumps are formed may be placed on the substrate on which the underfill layer is formed such that the surface on which the bumps are formed faces the surface of the substrate on which the underfill layer is formed. Thereafter, by heating, pressurizing, etc., the underfill layer is cured to become a sealing material, and the semiconductor chip is joined to the surface of the substrate on which the wiring pattern is formed via the bumps.

[0080] In the above description, an example in which the underfill material is used as a sealing material for filling the gap between the substrate and the semiconductor chip has been described. However, the use of the underfill material is not particularly limited, and it may fill the gap between semiconductor chips or may be used as a sealing material for filling the gap between substrates. Further, the substrate is not limited to a substrate made of an organic material and may be a semiconductor substrate or the like.

Examples

[0081] Hereinafter, the present invention will be described in more detail using examples and comparative examples. However, the present invention is not limited to the following examples and comparative examples as long as the gist thereof is not deviated from.

[0082] <Physical Property Evaluation> The physical property evaluation was carried out as follows.

[0083] (Gel fraction) The gel fraction of the cured product was measured by the following procedure. After heat treatment at 80 °C for 2 hours, a cured product prepared under the curing conditions of 120 °C for 2 hours was cut out within the range of 0.5 to 0.6 g and placed on a wire mesh. The wire mesh was left standing for 24 hours while immersed in acetone. Then, the wire mesh was taken out of the acetone and vacuum dried. The ratio of the weight of the cured product after immersion to the weight before immersion was defined as the gel fraction.

[0084] (Coefficient of thermal expansion (CTE)) The coefficient of thermal expansion of the cured product when the resin composition was cured to a gel fraction of 80% or more was measured by thermomechanical analysis using a method conforming to JIS K7197 (2012). Using a thermomechanical analyzer (apparatus name: TMA SS7100, manufactured by SII NanoTechnology Inc.), measurement was carried out by the compression method. Specifically, when the resin composition was cured to a gel fraction of 80% or more, the cured product was cut out to a size of φ6 mm × 10 mm, and using a thermomechanical analyzer, the temperature was decreased from 200 °C to 20 °C at 5 °C / min by the compression method, the change in the sample length with respect to the temperature change at 25 to 200 °C was measured, and the slope of the tangent line was defined as the coefficient of thermal expansion (CTE).

[0085] (Viscosity) The viscosity of the resin composition at 23 °C was measured using a B-type rotational viscometer. As the B-type rotational viscometer, when the viscosity was in the range of 0.1 to 100 Pa·s, "LVDV-1 Pri" manufactured by Brookfield Engineering Laboratories, Inc., spindles: S64, S63 were used, and when the viscosity exceeded 100 Pa·s, "HBDV-E" manufactured by Brookfield Engineering Laboratories, Inc., spindle: S-07 was used. The value measured at 5 rpm was taken as the representative value of the viscosity of each sample.

[0086] Production Example 1 (Production of zeolite) To the container, as a structure directing agent (SDA), N,N,N-trimethyl-1-adamantylammonium hydroxide (TMAdaOH) manufactured by Seikem, "Kyoward 200S" manufactured by Kyowa Chemical Industry Co., Ltd. as aluminum hydroxide, and "AEROSIL 200" manufactured by Nippon Aerosil Co., Ltd. as silica were sequentially added. The composition and molar ratio of the obtained mixture were SiO 2 :Al 2 O 3 :TMAdaOH:H 2 O = 1.0:0.025:0.4:20. After thorough mixing, the obtained mixture was placed in a pressure-resistant container, and hydrothermal synthesis was carried out in an oven at 150 °C for 48 hours. After suction filtration and washing, it was dried. The obtained powder was calcined at 600 °C for 6 hours under air circulation to remove TMAdaOH, which is a structure directing agent (SDA), to obtain CHA-type zeolite. The obtained zeolite was zeolite with the particle size of each particle in the range of 1.0 μm or more and 10 μm or less, and its average primary particle size was 3.1 μm. The average primary particle size was the average value of the particle sizes of 50 randomly selected primary particles. Also, 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 / Al 2 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 proton type.

[0087] Next, examples of the resin composition of the present invention will be shown. <Blending components> The components used for preparing the resin composition are as follows.

[0088] <Epoxy resin> (A) p-aminophenol type epoxy resin: manufactured by Mitsubishi Chemical Corporation, product name "jER630", epoxy equivalent: 97 g / equivalent (B) Epoxidation reaction product of pentaerythritol tetraarylate with hydrogen peroxide: "Shoufree (registered trademark) PETG" manufactured by Resonac Co., Ltd. <Hardening agent> (C) Acid anhydride-based hardening agent: Acid anhydride (main component: hydrogenated methyl nadic anhydride): manufactured by Shin Nippon Rika Co., Ltd., product name "Rikacid HNA-100" (acid anhydride equivalent: 174-184) <Filler> (D) As the zeolite filler, the zeolite produced in Production Example 1 described above was used. (E) Additive: manufactured by BYK-Chemie Japan, wetting dispersant, product name "DISPERBYK-2152" (amino group-containing ultra-high molecular weight polyester, comb type, solvent-free)

[0089] Example 1 The epoxy resin, hardening agent, zeolite filler, and additive shown in Table 1 were blended in the blending amounts shown in Table 1. Then, using a vacuum mixer (manufactured by EME Co., Ltd., "V-mini 300"), they were mixed at 1500 rpm for 5 minutes to prepare a resin composition (liquid composition). The viscosity of this liquid composition was evaluated by the above method. The results are shown in Table 1. 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 it to a gel fraction of 80% or more, and then demolded to obtain a cured product. The CTE of this cured product was evaluated by the above evaluation method. The results are shown in Table 1.

[0090] Comparative Example 1 In Example 1, except that component (B) was replaced with component (A) as the epoxy resin and the blending amount was changed as described in Table 1, a resin composition (liquid composition) and a cured product were obtained in the same manner as in Example 1. The results of evaluation in the same manner as in Example 1 are shown in Table 1.

[0091] Comparative Example 2 In Example 1, except that no zeolite filler was used and component (B) was replaced with component (A) and the blending amount was changed as described in Table 1, a resin composition (liquid composition) and a cured product were obtained in the same manner as in Example 1. The results of evaluation in the same manner as in Example 1 are shown in Table 1.

[0092] Comparative Example 3 In Example 1, a resin composition (liquid composition) and a cured product were obtained in the same manner as in Example 1, except that no zeolite filler was used and the blending amounts were changed as described in Table 1. The results of evaluation in the same manner as in Example 1 are shown in Table 1.

[0093]

Table 1

[0094] From the results of Example 1 and Comparative Example 1, in comparison with the resin composition using the conventionally used epoxy resin, the resin composition of the present invention has a small average thermal expansion coefficient (CTE) when formed into a cured product and a low viscosity, so that good injectability can be expected when used as an underfill material. On the other hand, as shown in Comparative Examples 2 and 3, when no zeolite filler is used, a low-viscosity resin composition can be obtained, but it can be seen that the CTE is high.

Industrial Applicability

[0095] According to the present invention, it is possible to provide a resin composition having a low thermal expansion coefficient after curing and a low viscosity. That is, the present invention is useful as a liquid sealant, and particularly useful as an underfill material.

Claims

1. A resin composition comprising a zeolite and an epoxy resin, wherein the epoxy resin contains a polyvalent glycidyl ether of an aliphatic polyhydric alcohol having 3 to 30 carbon atoms.

2. The resin composition according to claim 1, wherein the zeolite has d6r as CBU.

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

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

5. The resin composition according to claim 1, wherein the sphericity of the zeolite is 0.7 or more.

6. The resin composition according to claim 1, wherein the circularity of the zeolite is 0.800 or more.

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

8. The resin composition according to claim 1, further containing a curing agent, wherein the curing agent contains an acid anhydride-based curing agent.

9. The resin composition according to claim 1, wherein the epoxy resin is liquid at 25°C.

10. The resin composition according to claim 1, wherein the epoxy resin substantially does not contain a carbon-chlorine bond.

11. The resin composition according to claim 1, wherein the total amount of the all-inorganic filler containing the zeolite is 30 to 95% by mass.

12. A liquid encapsulant comprising the resin composition according to any one of claims 1 to 11.

13. A sealing material obtained by filling a gap with the resin composition according to any one of claims 1 to 11 and then curing it.

14. 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 11 and then curing it.

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