Zeolite, method for producing zeolite, composition, liquid composition, liquid sealant, resin composite material, sealing material, method for producing sealing material, and device

Abstract

The present invention relates to a liquid composition which is a liquid composition containing a resin and an inorganic filler. The above-mentioned inorganic filler contains zeolite with a particle size of 1.0 μm or more and 10 μm or less, and an inorganic filler with a particle size of 0.1 μm or more and less than 1.0 μm. The present invention can provide a liquid composition capable of reducing the coefficient of thermal expansion of the cured product while also reducing the viscosity.

Description

Technical Field

[0001] The present invention relates to a zeolite, a method for manufacturing a zeolite, a composition, a liquid composition, a liquid sealant, a resin composite material, a sealing material, a method for manufacturing a sealing material, and an electronic device. Background Art

[0002] For a liquid sealant used as an underfill material, excellent injectability, adhesiveness, curability, storage stability, etc. are required, and no voids are generated. In addition, for a portion sealed with the liquid sealant, excellent moisture resistance, heat cycle resistance, reflow soldering resistance, crack resistance, warpage resistance, etc. are required. In order to meet the above requirements, a liquid sealant mainly composed of an epoxy resin is widely used as the liquid sealant for underfill.

[0003] In addition, in order to improve the moisture resistance and heat cycle resistance, particularly the heat cycle resistance, of a portion sealed with the liquid sealant, the following method is known to be effective (see Patent Document 1): By adding a filler containing an inorganic substance such as a silica filler (hereinafter referred to as "inorganic filler") to the liquid sealant, the difference in thermal expansion coefficient between a substrate made of an organic material such as an epoxy resin and a semiconductor element is controlled; and the bump electrodes are strengthened.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2007-56070 Summary of the Invention

[0007] Problems to be Solved by the Invention

[0008] The thermal expansion coefficient of a liquid sealant using an inorganic filler such as a silica filler is not low enough, and from the viewpoint of heat cycle resistance, etc., it is required to further reduce the thermal expansion coefficient. In addition, as an inorganic filler having a relatively low thermal expansion coefficient, zeolite is known. However, a liquid composition containing zeolite has a tendency to have a high viscosity, and the injectability when used as an underfill material is reduced. Therefore, it is difficult to obtain a liquid sealant having a good injectability while reducing the thermal expansion coefficient of the cured product.

[0009] Therefore, an object of the present invention is to provide a liquid composition capable of reducing the thermal expansion coefficient of the cured product and also reducing the viscosity, and an epoxy resin composite material obtained by curing the liquid composition.

[0010] In addition, another object of the present invention is to provide a liquid composition capable of preventing an increase in viscosity in a liquid composition containing zeolite, and an epoxy resin composite material obtained from the liquid composition.

[0011] Furthermore, the object of the present invention is also to provide a zeolite with a lower coefficient of thermal expansion, considering that if the zeolite has a lower coefficient of thermal expansion, a smaller amount can reduce the coefficient of thermal expansion of the resin composite material, and an increase in viscosity caused by the use of zeolite can be expected to be suppressed. In addition, the object of the present invention is also to provide various applications that require suppression of the thermal expansion of resin substrates and the like using zeolites with a lower coefficient of thermal expansion.

[0012] Technical means for solving the problem

[0013] The gist of the present invention is as follows.

[0014] [1] A liquid composition, which is a liquid composition containing a resin and an inorganic filler, and the inorganic filler contains zeolite with a particle size of 1.0 μm or more and 10 μm or less, and an inorganic filler with a particle size of 0.1 μm or more and less than 1.0 μm.

[0015] [2] The liquid composition according to [1] above, which further contains a dispersant having at least one of the functional groups of amino group and amine salt.

[0016] [3] The liquid composition according to [1] or [2] above, and the zeolite has d6r as CBU.

[0017] [4] The liquid composition according to any one of [1] to [3] above, and the zeolite is aluminosilicate.

[0018] [5] The liquid composition according to any one of [1] to [4] above, and the resin is epoxy resin.

[0019] [6] The liquid composition according to any one of [1] to [5] above, the resin is epoxy resin, and the viscosity of the liquid composition at 23 °C is 0.1 Pa·s or more and 250 Pa·s or less.

[0020] [7] A liquid sealant, which contains the liquid composition according to any one of [1] to [6] above.

[0021] [8] A resin composite material, which is obtained by curing the liquid composition according to any one of [1] to [6] above to a gel fraction of 80% or more.

[0022] [9] A resin composite material, which is a resin composite material containing a resin and an inorganic filler, and the inorganic filler contains zeolite with a particle size of 1.0 μm or more and 10 μm or less, and an inorganic filler with a particle size of 0.1 μm or more and less than 1.0 μm.

[0023]

[10] The resin composite material according to [9] above, which further contains a dispersant having at least one of the functional groups of amino group and amine salt.

[0024]

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

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

[0025]

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

[11] above, wherein the zeolite is an aluminosilicate.

[0026]

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

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

[0027]

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

[13] above, wherein the resin is an epoxy resin, and the average coefficient of thermal expansion of the resin composite material is 0 ppm / K or more and 200 ppm / K or less, obtained by the following method:

[0028] (wherein the average coefficient of thermal expansion is determined based on JIS K7197 (2012), by the compression method based on thermomechanical analysis, measuring the temperature change of the sample length change at 25 to 100 °C, and obtaining it from the slope of the tangent line).

[0029]

[15] A zeolite having a particle size of 1.0 μm or more and 10 μm or less, having d6r as the CBU, and being a spherical aluminosilicate.

[0030]

[16] A zeolite having a particle size of 1.0 μm or more and 10 μm or less, having d6r as the CBU, and the c-axis length of the lattice constant is as follows aluminosilicate.

[0031]

[17] A composition containing the zeolite as described in

[15] or

[16] above, and a resin.

[0032]

[18] The composition as described in

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

[0033]

[19] The composition as described in

[17] or

[18] above, further containing an inorganic filler having a particle size of 0.1 μm or more and less than 1.0 μm.

[0034]

[20] The composition as described in any one of

[17] to

[19] above, further containing a dispersant having at least one functional group of an amino group and an amine salt.

[0035]

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

[17] to

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

[0036]

[22] A resin composite material, which is a resin composite material containing the composition described in any one of

[17] to

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

[0037]

[23] A sealing material, which contains the resin composite material described in any one of [9] to

[14] and

[22] above.

[0038]

[24] An electronic device, which includes the resin composite material described in any one of [9] to

[14] and

[22] above.

[0039]

[25] A method for manufacturing a sealing material, which involves filling the liquid composition described in any one of [1] to [6] and

[21] above into a gap and then curing it.

[0040]

[26] A method for manufacturing a zeolite, characterized by having: a step of hydrothermally synthesizing a raw material composition containing a silicon atom raw material, a water-soluble aluminum atom raw material, an organic structure-directing agent, and water; and a subsequent step of firing. The content of alkali metal atoms other than the organic structure-directing agent in the above raw material composition is 0.05 mol or less relative to 1 mol of Si atoms.

[0041] Advantages of the Invention

[0042] In the present invention, a liquid composition and a resin composite material obtained by curing the liquid composition with a reduced thermal expansion coefficient can be provided. The liquid composition is less likely to have a high viscosity by using a combination of zeolites with specific particle sizes and inorganic fillers.

[0043] In addition, in the present invention, a liquid composition and a resin composite material obtained from the liquid composition can also be provided. The liquid composition prevents an increase in viscosity in a liquid composition containing zeolites by using a specific dispersant.

[0044] Furthermore, a zeolite with a relatively low thermal expansion coefficient suitable for suppressing the thermal expansion of a resin can also be provided. Description of the Drawings

[0045] Figure 1 Figure 1 It is a graph showing the particle size distribution of the zeolite in Example 1.​​

[0046] Figure 2 Figure 2 A graph showing the particle size distribution of the zeolite of Example 2.

[0047] Figure 3 Figure 3 A graph showing the particle size distribution of the zeolite of Comparative Example 2. Detailed Description of the Invention

[0048] Hereinafter, the present invention will be described with reference to the embodiments.

[0049] [First Embodiment]

[0050] <Zeolite>

[0051] The zeolite of the first embodiment of the present invention is an aluminosilicate having a particle size of 1.0 μm or more and 10 μm or less and containing d6r as a CBU.

[0052] One of the characteristics of the zeolite of the present invention is that the particle size is larger than that of ordinary zeolites, and the particle size is 1.0 μm or more and 10 μm or less.

[0053] Hereinafter, the zeolite of the first embodiment of the present invention will be described in detail. It should be noted that the zeolite having a particle size of 1.0 μm or more and 10 μm or less is sometimes hereinafter referred to as a "large particle size zeolite".

[0054] (Particle Size of Zeolite)

[0055] The particle size of the zeolite of the first embodiment of the present invention refers to the diameter of the largest circle (equivalent circle diameter) having an area equal to the projected area of the particle in the particle observation using a scanning electron microscope (SEM). In the zeolite of the first embodiment of the present invention, multiple zeolite particles may aggregate to form secondary particles. In this case, the particle size of the zeolite is the particle size of the primary particles.

[0056] From the viewpoint that the viscosity does not easily increase when added to a resin, it is preferable that the particle size of the zeolite of the first embodiment of the present invention is larger. On the other hand, from the viewpoints of easy uniform mixing with other components such as resins and easy increase in surface smoothness, it is preferable that the particle size is smaller. Specifically, it is preferably 1.5 μm or more, more preferably 2.0 μm or more. On the other hand, it is preferably 8 μm or less, more preferably 5 μm or less.

[0057] ​​​​In the case of using zeolites, usually not one zeolite particle is used, but a plurality of zeolite particle groups are used. That is, in one aspect of the present invention, it is preferably used in the form of a zeolite group containing at least the zeolite particles of the first embodiment of the present invention. Regarding such a zeolite in one aspect containing a plurality of zeolite particles, its average primary particle size is preferably in the range of 1.1 to 4.0 μm, more preferably 1.5 to 3.8 μm, and further preferably 2.0 to 3.5 μm. The average primary particle size of the zeolite is determined by randomly selecting 50 zeolites (powder, particles in the liquid composition or resin composite described later), measuring their particle sizes, and taking the average value.

[0058] In addition, as the particle size distribution of the zeolite based on volume basis, the median particle size (d50) is preferably in the range of 0.5 to 5.0 μm, more preferably in the range of 1.5 to 5.0 μm, and further preferably in the range of 2.0 to 4.0 μm. By having the median particle size within this range, the proportion of zeolites that exhibit the effects of the present invention increases, and it is easier to obtain the effects of the present invention with a smaller amount.

[0059] (Structure of Zeolite)

[0060] Zeolite is a compound composed of silicon or aluminum and oxygen, and having TO 4 units (T element is an element other than oxygen that constitutes the framework) as basic units. Specifically, zeolites include crystalline porous aluminosilicates, crystalline porous aluminum phosphates (ALPO), or crystalline porous silicoaluminophosphates (SAPO), etc. The zeolite of the first embodiment of the present invention is an aluminosilicate.

[0061] Zeolite is composed of structural units called composite building units (hereinafter sometimes referred to as "CBU") formed by connecting several (several to dozens of) TO 4 units. Therefore, it has regular channels (tubular pores) and cavities (voids).

[0062] Regarding this CBU and the crystal structure of the zeolite described later, it can be represented by the code for specifying the zeolite structure established by the International Zeolite Association (IZA, International Zeolite Association). It should be noted that the zeolite structure can be determined based on the X-ray diffraction pattern obtained by an X-ray structure analysis device (for example, the desktop X-ray diffractometer D2PHASER manufactured by BRUKER Corporation) using the zeolite structure database 2018 version (http: / / www.iza-structure.org / databases / ).

[0063] (Framework of Zeolite)

[0064] The framework of the zeolite according to the first embodiment of the present invention contains d6r as a CBU. By including d6r, it is easy to obtain a resin composite material with a lower coefficient of thermal expansion, which will be described in detail below.

[0065] Examples of zeolites having d6r as a CBU 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.

[0066] Among them, from the viewpoint of easy control of particle size, zeolites having a structure of up to an eight-membered oxygen ring are particularly preferred. Examples of zeolites having a structure of up to an eight-membered oxygen ring include zeolites of AEI, AFT, AFX, CHA, ERI, KFI, SAT, SAV, SFW, and TSC type structures. Among them, from the viewpoint of structural stability even when shape control is performed, zeolites of AEI, AFX, CHA, and ERI type structures are further preferred, and zeolites having a CHA structure are most preferred. It should be noted that in this specification, a structure having an eight-membered oxygen ring means a structure in which the number of oxygen elements is 8 when the number of oxygen elements is the largest in the pores formed by oxygen and T elements (elements other than oxygen constituting the framework) forming the zeolite framework.

[0067] (Average coefficient of thermal expansion of zeolite)

[0068] From the viewpoint of easily reducing the average coefficient of thermal expansion of the liquid composition and the resin composite material described below with a small amount, the average coefficient of thermal expansion of the zeolite according to the first embodiment of the present invention is preferably low. In addition, since it is a small amount, various physical properties of the resin are not easily changed due to the addition of zeolite, so it is also preferred. In particular, from the aspect of suppressing the increase in viscosity of the following liquid composition, it is also preferably low. 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, further preferably -5 ppm / K or less, particularly preferably -6 ppm / K or less, and most preferably -8 ppm / K or less.

[0069] On the other hand, considering the following liquid composition containing zeolite and resin and resin composite material, from the viewpoint of a smaller difference in the average thermal expansion coefficient from the resin and less likely peeling between the zeolite and the resin, the average thermal expansion coefficient of the zeolite is preferably higher. Therefore, the average thermal expansion coefficient of the zeolite is generally -1000 ppm / K or more, preferably -900 ppm / K or more, more preferably -800 ppm / K or more, further preferably -700 ppm / K or more, particularly preferably -500 ppm / K or more, and especially preferably -300 ppm / K or more. And especially in the case of applications for contact with other materials such as sealing materials and substrates, it is preferably higher. Specifically, it is preferably -100 ppm / K or more, more preferably -50 ppm / K or more, further 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.

[0070] It should be noted that the average thermal expansion coefficient of the zeolite can be measured by calculating the lattice constant using the X-ray diffraction device "D8 ADVANCE" manufactured by BRUKER Corporation and the X-ray diffraction analysis software "JADE". Here, in order to eliminate the influence of moisture detachment, the zeolite is measured in a dry state.

[0071] The measurement of the average thermal expansion coefficient of the zeolite is generally carried out in the range of 50 to 100 °C. That is, the average thermal expansion coefficient of the zeolite is a value representing the displacement of the lattice constant per 1 °C starting from the average lattice constant at 50 °C and the average lattice constant at 100 °C when the zeolite is heated. Here, the average lattice constant at each temperature is the average of the lattice constants of the a-axis, b-axis, and c-axis. It should be noted that the measurement of the average thermal expansion coefficient is carried out by slowly heating after waiting for the lattice constant to stabilize.

[0072] Generally, the thermal expansion coefficient of the resin tends to increase in the high-temperature region. Therefore, the average thermal expansion coefficient of the zeolite is particularly preferably lower during the heating process to the high-temperature region. Specifically, the average thermal expansion coefficient (high-temperature region) 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 further preferably -12.5 ppm / K or less. It should be noted that the average thermal expansion coefficient (high-temperature region) of the zeolite here is a value representing the displacement of the lattice constant per 1 °C starting from the average lattice constant at 50 °C and the average lattice constant at 350 °C when the zeolite is heated.

[0073] (Shape of zeolite)

[0074] From the aspect of being easy to contain while suppressing the increase in viscosity, the shape of the zeolite according to the first embodiment of the present invention is preferably spherical. Specifically, the following true sphericity and roundness are preferred.

[0075] <<True sphericity>>

[0076] The true sphericity of the zeolite is preferably 0.6 or more, more preferably 0.65 or more, and particularly preferably 0.70 or more. In addition, the upper limit of the true sphericity is not particularly limited and may be 1 or less. It should be noted that zeolites are usually cubic, and in this case, the true sphericity is 0.58.

[0077] In this specification, "true sphericity" is defined as "the ratio of the minimum diameter of the particle to the maximum diameter". The maximum diameter and the minimum diameter can be obtained by observing with a scanning electron microscope (SEM), respectively.

[0078] <<Roundness>>

[0079] The roundness of the zeolite according to the first embodiment of the present invention is preferably 0.786 or more, more preferably 0.790 or more, further preferably 0.795 or more, further more preferably 0.800 or more, further preferably 0.805 or more, particularly preferably 0.810 or more, especially preferably 0.815 or more, and most preferably 0.820 or more. In addition, the upper limit of the roundness is not particularly limited and may be 1 or less. It should be noted that zeolites are usually cubic, and in this case, the roundness is 0.785.

[0080] In this specification, "roundness" is defined as "4×π×area / (circumference) 2 ". The area and the circumference can be obtained by observing with a scanning electron microscope (SEM), respectively.

[0081] (c-axis length of the zeolite)

[0082] The c-axis length of the lattice constant of the zeolite according to the first embodiment of the present invention is preferably shorter. Since the c-axis length is shorter, it is considered that the lattice vibration in the lateral direction becomes larger, negative thermal expansion occurs, and the average thermal expansion coefficient is likely to be low. Specifically, the c-axis length is preferably The following, more preferably The following, further preferably The following, particularly preferably The following, especially preferably The following, most preferably The following.

[0083] It should be noted that in this specification, the c-axis length refers to the c-axis length at room temperature (23 °C). The lattice constants of the zeolite can be measured using the X-ray diffractometer "D8 ADVANCE" manufactured by BRUKER, and calculated by the least squares method using the X-ray diffraction analysis software "JADE".

[0084] (Framework density of zeolite)

[0085] The framework density of the zeolite of the first embodiment of the present invention is not particularly limited as long as it does not impair the effects of the present invention. From the viewpoints of facilitating the occurrence of the structural vibration of the zeolite and easily reducing the average thermal expansion coefficient, the framework density of the zeolite is preferably low. Therefore, the framework density of the zeolite is preferably Hereinafter, more preferably Hereinafter.

[0086] On the other hand, from the viewpoint of easily increasing the structural stability of the zeolite, the framework density of the zeolite is preferably high. The framework density of the zeolite is preferably Above, more preferably Above, further preferably Above. If the framework density is within the above range, the zeolite can be used as a stable filler.

[0087] It should be noted that the framework density represents the number of T atoms present in the zeolite per unit volume, and it is a value determined by the structure of the zeolite. In this specification, the values described in the 2017 version of the zeolite structure database of IZA (http: / / www.iza-structure.org / databases / ) can be used.

[0088] As an example of a zeolite having a framework density greater than and being below, zeolites of ERI, LTL, LTN, MOZ, OFF, SAT, SSF, and -WEN type structures can be cited.

[0089] As an example of a zeolite having a framework density greater than and being below, zeolites of AEI, AFT, AFV, AFX, AVL, EAB, GME, LEV, MWW, and SFW type structures can be cited.

[0090] As an example of a zeolite having a framework density greater than and being below, zeolites of CHA, KFI, SAS, and SAV type structures can be cited.

[0091] As an example of a zeolite having a framework density present in Examples of zeolites within the following range include zeolites of EMT, FAU, JSR, SBS, SBT, and TSC type structures.

[0092] (Molar ratio of silica to alumina (SAR) of zeolite)

[0093] The molar ratio of silica to alumina of the zeolite of the first embodiment of the present invention (sometimes referred to as "SAR", "Si / Al 2 molar ratio", or "Si / Al 2 ratio") is not particularly limited as long as it does not impair the effects of the present invention. From the viewpoints of the high moisture resistance of the resin composite material described later and the easy control of the amount of counter cations, the SAR (Si / Al 2 ratio) of the zeolite is preferably high. 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, further preferably 4 or more, particularly preferably 4.5 or more, and most preferably 5 or more.

[0094] On the other hand, from the viewpoint of easy manufacture at low cost, the SAR (Si / Al 2 ratio) of the zeolite is preferably low. 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 further preferably 100 or less. If the Si / Al 2 ratio is within the above range, it is easy to control the amount of counter cations, and in addition, the manufacturing cost of the zeolite can also be low.

[0095] (Counter cations of zeolite)

[0096] The counter cations of the zeolite of the first embodiment of the present invention are not particularly limited as long as they do not impair the effects of the present invention. The counter cations of the zeolite are usually protons, alkali metal ions, and alkaline earth metal ions. Protons and alkali metal ions are preferred, and protons, Li ions, Na ions, and K ions are more preferred. When they are alkali metal ions or alkaline earth metal ions, the smaller their size, the easier it is for the zeolite to exhibit an average thermal expansion coefficient of less than 0 ppm / K, so it is preferred. Among them, when the counter cation of the zeolite is a proton, it is easy to reduce the average thermal expansion coefficient of the resin composite material, so it is preferred. That is, as the zeolite, a proton type and an alkali metal type are preferred, a proton type, a Li type, a Na type, and a K type are more preferred, and a proton type is particularly preferred.

[0097] (Crystallinity of zeolite)

[0098] The crystallinity of the zeolite according to the first embodiment of the present invention is not particularly limited as long as the effects of the present invention are not impaired. It is presumed that the reason is that the Composite Building Unit (CBU) has a greater influence on the average coefficient of thermal expansion of the epoxy resin composite than the structure determined by the IZA code. It should be noted that the crystallinity of the zeolite can be determined by comparing it with the X-ray diffraction peak of the zeolite based on a certain X-ray diffraction peak obtained using an X-ray diffraction apparatus (for example, the benchtop X-ray diffraction apparatus D2PHASER manufactured by BRUKER Corporation). As a specific calculation example, the crystallinity of the LTA-type zeolite in Scientific Reports 2016, 6, Article number: 29210 can be cited.

[0099] (Surface treatment of zeolite)

[0100] The zeolite can be surface-treated such as silylation within the range that does not impair the effects of the present invention. This surface treatment is not limited to physical treatment or chemical treatment.

[0101] (Manufacturing method of zeolite)

[0102] A known method can be used for the manufacturing method of the zeolite. For example, in the case of manufacturing a CHA-type zeolite, the method described in Japanese Unexamined Patent Application Publication No. 2009-097856 can be referred to for manufacturing. In the case of manufacturing a zeolite with a larger particle size, it is only necessary to appropriately control the types and ratios of raw materials, synthesis time, temperature, etc. for hydrothermal synthesis. Specifically, for example, a zeolite with a larger particle size can be manufactured by the method described in Microporous and Mesoporous Materials 21 (1998) 24. under the conditions of increasing the amount of water during synthesis and diluting the raw material concentration.

[0103] In addition, the above-mentioned particularly preferred zeolite can be manufactured by the following method (hereinafter sometimes referred to as "the manufacturing method of the zeolite of the present invention").

[0104] The manufacturing method of the zeolite of the present invention includes: a step of hydrothermally synthesizing a raw material composition containing a silicon atom raw material, a water-soluble aluminum atom raw material, an organic structure-directing agent, and water; and a step of firing thereafter.

[0105] Here, the content of alkali metal atoms other than the organic structure-directing agent in the above raw material composition is 0.05 mol or less per 1 mol of Si atoms. It should be noted that a required zeolite (hereinafter sometimes referred to as "seed zeolite") can be used as needed.

[0106] <<Silicon atom raw material>>

[0107] As the silicon atom raw material used in the present invention, there is no particular limitation, and various known substances can be used. For example, colloidal silica, amorphous silica, sodium silicate, trimethylethoxysilane, tetraethyl orthosilicate, aluminosilicate gel, and zeolite can be used. Among them, from the viewpoint of less alkali metal coordination, amorphous silica is preferred. They can be used alone or two or more of them can be used in any combination and ratio.

[0108] <<Aluminum atom raw material>>

[0109] The aluminum atom raw material uses a water-soluble raw material. In addition, from the viewpoint of less alkali metal content, aluminum hydroxide is preferred, and in order to prevent ripening and grow zeolite into spherical shape, water-soluble amorphous aluminum hydroxide is particularly preferred.

[0110] <<Alkali metal atom raw material>>

[0111] The alkali metal atom raw material may not be used. In the case of use, the content of alkali metal atoms other than the organic structure directing agent is set to 0.05 mol or less relative to 1 mol of Si atoms. The alkali metal atoms in the case of using the alkali metal atom raw material are not particularly limited, and known alkali metal atoms used in the synthesis of zeolite can be used, and at least one alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium is preferred. The usage amount of the alkali metal is preferably 0.045 or less, more preferably 0.04 or less, further preferably 0.035 or less, and particularly preferably 0.03 or less in terms of the molar ratio to silicon (Si) contained in the raw material composition. Since the alkali metal atom raw material is less, the zeolite is liable to grow into spherical shape, the c-axis length of the crystal lattice is shorter, and the average thermal expansion coefficient is liable to become larger in the negative direction.

[0112] <<Organic structure directing agent>>

[0113] As the organic structure directing agent, various known substances such as tetraethylammonium hydroxide (TEAOH) and tetrapropylammonium hydroxide (TPAOH) can be used. Among them, N,N,N-trimethyl-1-adamantylammonium hydroxide (TMAdaOH) is preferred.

[0114] The usage amount of the organic structure directing agent is usually 0.01 or more, preferably 0.02 or more, further 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. It is considered that high-purity spherical zeolite with less by-products is liable to grow within this range.

[0115] <<Seed zeolite>>

[0116] In the production method of the present invention, zeolite can be used as a seed. When using seed zeolite, one kind can be used alone, or two or more kinds can be used in any combination and ratio.

[0117] <<Water>>

[0118] Regarding the amount of water used, from the viewpoint of easy crystal formation, when using seed zeolite, the molar ratio to silicon (Si) contained in the raw material composition other than the seed zeolite is usually 5 or more, preferably 7 or more, more preferably 9 or more, and further preferably 10 or more. By setting it within this range, crystal formation is easier, so it is preferred. In addition, it is considered that by synthesizing under the condition of increasing the amount of water to dilute the raw material concentration, it is easy to produce zeolite with a larger particle size. In order to fully obtain the effect of reducing the cost of waste liquid treatment, the molar ratio to silicon (Si) is usually 50 or less, preferably 40 or less, more preferably 30 or less, and further preferably 20 or less.

[0119] <<Mixing of raw materials (preparation of raw material composition before reaction)>>

[0120] 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 when using seed zeolite.

[0121] It should be noted that in the present invention, in addition to the above components, components such as an acid component that promotes the reaction and a metal stabilizer such as polyamine can be added in any process as needed.

[0122] <<Aging>>

[0123] The raw material composition prepared by the above operation can be subjected to hydrothermal synthesis immediately after preparation. In order to obtain zeolite with higher crystallinity, it is preferred to age for a certain time under specified temperature conditions. Especially when the reaction scale is enlarged, from the viewpoint of better stirring performance and easier to make the raw materials in a more uniform state, it is preferred to age the raw materials while stirring for a certain time. The temperature during aging is usually 100 °C or lower, preferably 95 °C or lower, more preferably 90 °C or lower, and its lower limit is not particularly set, usually 0 °C or higher, preferably 10 °C or higher. The aging temperature can be fixed during the aging process, or can be changed stepwise or continuously. The aging time is not particularly limited, usually 2 hours or more, preferably 3 hours or more, more preferably 5 hours or more. On the other hand, usually 30 days or less, preferably 10 days or less, and further preferably 4 days or less.

[0124] <<Hydrothermal synthesis>>

[0125] Next, hydrothermal synthesis is performed on the obtained raw material composition.

[0126] Hydrothermal synthesis is generally carried out as follows: The raw material composition prepared by the above-described operations or the aqueous gel obtained by ripening it is placed in a pressure-resistant container, and under autogenous pressure or gas pressurization to an extent that does not hinder crystallization, stirring is performed, or the container is rotated or shaken, or maintained at a specified temperature in a static state.

[0127] To accelerate the reaction rate, the reaction temperature during hydrothermal synthesis is generally 120 °C or higher, preferably 130 °C or higher, more preferably 140 °C or higher, and particularly preferably 150 °C or higher. On the other hand, it is generally 230 °C or lower, preferably 220 °C or lower, more preferably 200 °C or lower, and further preferably 190 °C or lower. The reaction time is not particularly limited, and is generally 2 hours or longer, preferably 3 hours or longer, more preferably 5 hours or longer. On the other hand, it is generally 30 days or shorter, preferably 10 days or shorter, more preferably 7 days or shorter, and further preferably 5 days or shorter. The reaction temperature can be fixed during the reaction, or can be changed stepwise or continuously.

[0128] The reason for being able to manufacture a particularly preferred zeolite by the method for manufacturing a zeolite of the present invention is presumed as follows. When manufacturing a zeolite, an alkali metal is generally used to dissolve the raw material components. In contrast, in the method for manufacturing a zeolite of the present invention, an alkali metal is not used, or even when an alkali metal is used, it is below a certain amount. As a result, in the raw material composition, crystallization easily grows starting from the organic structure-directing agent, and the crystallization easily grows into a spherical shape starting from this starting point. And it is presumed that during the process of the crystallization growing into a spherical shape, lattice strain is generated, and the strain is fixed by firing. The shorter c-axis length of the lattice in Examples 1 to 3 (manufactured by the method for manufacturing a zeolite of the present invention) described later than in Comparative Example 1 (without firing) and 2 (using sodium hydroxide) also supports this presumption.

[0129] And it is presumed that due to the presence of the strain generated in the lattice, the average coefficient of thermal expansion of the zeolite of the first embodiment of the present invention is likely to be low. That is, it is considered that due to the presence of the strain generated in the lattice, the strain is eliminated during heating, and thus contraction occurs. In addition, it is presumed that for the same reason, in particular, the average coefficient of thermal expansion of the zeolite of the first embodiment of the present invention is more likely to be low in the high-temperature region (in the range of 50 to 350 °C). The lower average coefficient of thermal expansion of Examples 1 to 3 with a shorter c-axis length of the lattice in the comparison with Comparative Examples 1 and 2 described later than that of Comparative Examples 1 and 2 also supports this presumption.

[0130] [Second Embodiment]

[0131] [Composition]

[0132] The composition of the second embodiment of the present invention is a composition containing the zeolite of the above-mentioned first embodiment and a resin. As described later, the average thermal expansion coefficient of the zeolite of the first embodiment is easy to become extremely low. Therefore, by containing this zeolite, the thermal expansion of the composite material comprising the composition of the second embodiment can be suppressed.

[0133] From the viewpoint of reducing the thermal expansion coefficient while suppressing the viscosity increase, the content of the zeolite of the first embodiment contained in the resin composition is preferably 25% by mass or more, more preferably 30% by mass or more, further preferably 35% by mass or more, further more preferably 40% by mass or more, particularly preferably 45% by mass or more, and particularly preferably 50% by mass or more relative to the total amount of the composition. In addition, on the other hand, it is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 75% by mass or less, and particularly preferably 70% by mass or less.

[0134] In addition, from the viewpoint that the viscosity increase of the resin kneading is small and the thermal expansion coefficient of the cured product is easily reduced, when the resin composition contains a filler other than the zeolite of the first embodiment, the content of the zeolite of the present invention in all the fillers is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, further more preferably 70% by mass or more, and most preferably 90% by mass or more.

[0135] (resin)

[0136] The resin used for the composition of the second embodiment of the present invention is not particularly limited as long as it is within the scope of the effect of the present invention. From the viewpoint of further exerting the effect as a composite material, it is preferably at least one selected from the group consisting of epoxy resin and polyimide resin. In particular, in the case of being used as a useful liquid composition such as a sealant, epoxy resin is preferably used. In addition, in the case of being used as a useful composition such as a substrate, polyimide resin is preferably used.

[0137] From the viewpoint of maintaining the excellent physical property of the resin and the heat resistance (not easy to occur property of thermal expansion) of the resin composition obtained by curing, the amount of the resin contained in the composition of the present invention is preferably more than 5% by mass relative to the total amount of the composition, and more preferably more than 10% by mass. On the other hand, it is preferably less than 50% by mass, more preferably less than 25% by mass, and particularly preferably less than 15% by mass.

[0138] <<Epoxy Resin>>

[0139] The epoxy resin used in the present invention will be described in detail in the fifth embodiment of the present invention described later.

[0140] <<Polyimide resin>>

[0141] The polyimide resin used in the present invention is preferably a polyimide obtained from tetracarboxylic dianhydride and a diamine, and particularly preferably an aromatic polyimide obtained from an aromatic tetracarboxylic dianhydride and an aromatic diamine, from the viewpoint that the thermal expansion coefficient of the resin composite material is easily reduced and the heat resistance, mechanical strength, electrical properties, solvent resistance and other properties are excellent.

[0142] More specifically, it is preferred that a polyimide resin powder obtained by polymerizing and imidizing an aromatic tetracarboxylic acid component and p-phenylenediamine is sprayed with a polyimide precursor solution to granulate the polyimide powder, and the polyimide powder is compounded with a filler to prepare a resin composite material.

[0143] It should be noted that the polyimide powder is formed by combining the particles of the polyimide powder with each other by a polyimide precursor and granulating them, and in the aggregate, the polyimide precursor acts as a binder. As the polyimide precursor, for example, polyamic acid is used, and the polyimide precursor solution used as a raw material uses water and / or an alcohol solvent as a reaction solvent, and tetracarboxylic dianhydride and diamine are reacted in the presence of an alkaline compound with a pKa of 7.5 or more to produce polyamic acid.

[0144] As a preferred mode of the second embodiment, the following liquid resin composition can be listed, which is a liquid resin composition using epoxy resin as a resin and containing the zeolite of the first embodiment, wherein the viscosity is greater than 1 Pa·s and less than 30 Pa·s, and the content of the zeolite is 40 to 70% by mass.

[0145] The liquid resin composition can be used as an underfill material (hereinafter sometimes referred to as a "liquid sealant"), and can reduce the average thermal expansion coefficient after curing, and is suitable as a sealant.

[0146] In addition, as another preferred embodiment of the second embodiment, the following composite material can be listed, which is a composite material using epoxy resin as a resin and containing the zeolite of the first embodiment, wherein the zeolite content is 40 to 70% by mass, and the average thermal expansion coefficient of the composite material at 25 to 100°C is 10 to 30 ppm / K.

[0147] Since the composite material has a low average thermal expansion coefficient at a temperature below the glass transition temperature, it can be used as a variety of materials and is particularly effective for electronic devices.

[0148] [Third Embodiment]

[0149] <Composition>

[0150] The composition of the third embodiment of the present invention is a composition containing the zeolite of the first embodiment, a resin, and an inorganic filler having a particle size of 0.1 μm or more and 1.0 μm (hereinafter also referred to as a small-particle-size inorganic filler).

[0151] (Inorganic filler)

[0152] In the case of a liquid composition, from the viewpoint of being easy to fill the liquid composition even in a narrow space, the particle size of the inorganic filler is preferably smaller. On the other hand, from the viewpoint of preventing the viscosity of the liquid composition from becoming less likely to increase, it is preferably larger. When a filler with a smaller specific surface area and a larger specific surface area are used together, the larger specific surface area increases the interaction between the filler and the resin, and the viscosity of the liquid composition tends to become higher. Therefore, in order to reduce the viscosity of the liquid composition, it is preferred that the filler has a smaller specific surface area. Regarding the specific surface area, the smaller the particle size, the easier it is to increase. In addition, the specific surface area also varies depending on the shape of the filler, and the specific surface area becomes the smallest when it is spherical. Therefore, from the viewpoint of reducing the viscosity, the inorganic filler is preferably close to spherical and has a larger particle size. Therefore, in particular, with regard to large-diameter zeolite, its specific surface area is preferably 1×10 -6 ( / m) or less, more preferably 0.8×10 -6 ( / m) or less.

[0153] In the present invention, by using a small particle size and a large particle size filler in combination, the small particles enter the gap between the large particles, the filling amount can be varied, the thermal expansion coefficient can be reduced, and the viscosity increase can also be suppressed. Therefore, from the viewpoint that the thermal expansion coefficient is easy to become low, the composition of the present invention preferably contains a large particle size zeolite and a small particle size inorganic filler.

[0154] The particle size of the inorganic filler is measured in the same manner as the zeolite of the first embodiment. That is, the particle size of the inorganic filler refers to the diameter (circle equivalent diameter) of the circle with the largest diameter having an area equal to the projected area of ​​the particle in particle observation using a scanning electron microscope (SEM). In addition, the particle size is the particle size of the primary particle.

[0155] Examples of the inorganic filler used in the composition of the present invention include zeolite and inorganic fillers other than zeolite.

[0156] Zeolite is an inorganic filler with a low thermal expansion coefficient, and can reduce the thermal expansion coefficient of the epoxy resin composite material as a cured product of the liquid composition, which is one of the preferred embodiments of the present invention. However, since it has a porous structure, the specific surface area is large, and if it is mixed in large quantities, the viscosity of the liquid composition tends to increase. In the present invention, various studies have been conducted, and it has been found that by making the liquid composition contain a small-particle-size inorganic filler in addition to the large-particle-size zeolite such as the zeolite of the first embodiment, for example, the thermal expansion coefficient of the liquid epoxy resin composite material can be reduced, and the viscosity can be prevented from increasing, thereby achieving a low viscosity of the liquid composition.

[0157] As inorganic fillers other than zeolite, at least one selected from the group consisting of metal, carbon, metal carbide, metal oxide and metal nitride can be cited. As examples of metals, silver, copper, aluminum, gold, nickel, iron and titanium can be cited. As examples of carbon, carbon black, carbon fiber, graphite, fullerene, diamond and the like can be cited. As examples of metal carbides, silicon carbide, titanium carbide, tungsten carbide and the like can be cited. As examples of metal oxides, silicon oxides such as magnesium oxide, aluminum oxide (aluminum trioxide), silicon dioxide, calcium oxide, zinc oxide, yttrium oxide, zirconium oxide, cerium oxide, ytterbium oxide, sialon (ceramic containing silicon, aluminum, oxygen and nitrogen) and the like can be cited. As examples of metal nitrides, boron nitride, aluminum nitride, silicon nitride and the like can be cited.

[0158] (Content of large-size zeolite)

[0159] In the composition of the third embodiment of the present invention, when the resin composition is a liquid composition, the content of the zeolite of the first embodiment in the composition is preferably 20% by mass or more, more preferably 25% by mass or more, further preferably 30% by mass or more, particularly preferably 40% by mass or more, and most preferably 45% by mass or more, relative to the total amount of the liquid composition, from the viewpoint of suppressing the increase in viscosity and reducing the thermal expansion coefficient. In addition, on the other hand, it is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 75% by mass or less, and particularly preferably 70% by mass or less.

[0160] In addition, from the viewpoint of less viscosity increase during resin kneading and easier reduction of thermal expansion coefficient of cured product, the content of zeolite (large particle size zeolite) in all fillers is preferably 10 mass % or more, more preferably 30 mass % or more, further preferably 50 mass % or more, further more preferably 70 mass % or more, and most preferably 90 mass % or more.

[0161] (Small particle size inorganic filler)

[0162] The small-particle inorganic filler may be zeolite or an inorganic filler other than zeolite. Specific examples of the inorganic filler other than zeolite are as described above.

[0163] From the viewpoint of reducing the thermal expansion coefficient, the small-particle-size inorganic filler is preferably zeolite, metal nitride, metal oxide, or the like.

[0164] From the viewpoint of being easy to fully show the use effect of the filler, the content of the small-particle-diameter inorganic filler is preferably more. On the other hand, from the viewpoint of improving the fluidity of the liquid composition in the case of a liquid composition and being easy to fill in a narrow space, it is preferably less. In particular, since the small-particle-diameter inorganic filler has a large specific surface area and the viscosity is easy to increase, it is easy to improve the fluidity by reducing the amount used.

[0165] In the composition of the third embodiment of the present invention, the content of the small-particle inorganic filler is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more relative to the total amount of the composition. On the other hand, it is preferably 50% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less.

[0166] (Shape of small particle size inorganic filler)

[0167] The shape of the small particle size inorganic filler is not particularly limited as long as the composition and the resin composite material exhibit preferred properties, and may be spherical, whisker-like, fibrous, plate-like, or aggregates thereof, and is preferably spherical from the viewpoint of suppressing viscosity increase while containing.

[0168] The sphericity of the small-particle inorganic filler is preferably 0.6 or more, more preferably 0.65 or more, and particularly preferably 0.70 or more. The upper limit of the sphericity is not particularly limited, but may be 1 or less.

[0169] Therefore, in the third embodiment of the present invention, the true sphericity of the large-diameter zeolite and the small-diameter inorganic filler is preferably 0.6 or more, more preferably 0.65 or more, and particularly preferably 0.70 or more. In addition, the small-diameter inorganic filler preferably has a higher true sphericity than the large-diameter zeolite.

[0170] In addition, the roundness of the small-particle inorganic filler is preferably 0.786 or more, more preferably 0.790 or more, further preferably 0.795 or more, further more preferably 0.800 or more, further preferably 0.805 or more, particularly preferably 0.810 or more, particularly preferably 0.815 or more, and most preferably 0.820 or more. In addition, the upper limit of the roundness is not particularly limited, and can be 1 or less. It should be noted that the determination method of true sphericity and roundness is as described above.

[0171] (Total inorganic filler content)

[0172] From the viewpoint of being easy to show the effect as filling material, the total content of all inorganic fillers (all inorganic fillers) contained in the composition is preferably more. On the other hand, from the viewpoint that fluidity is higher in the case of liquid composition, it is also easy to fill even in a narrow space, it is preferably less. Specifically, in the composition of the 3rd embodiment of the present invention, the total content of all inorganic fillers is preferably more than 30 mass % relative to the total amount of the composition, more preferably more than 35 mass %, particularly preferably more than 40 mass %. On the other hand, it is preferably less than 95 mass %, more preferably less than 90 mass %, particularly preferably less than 85 mass %.

[0173] [Fourth embodiment]

[0174] <Composition>

[0175] The composition of the fourth embodiment of the present invention contains a resin, a zeolite, and a dispersant having at least one functional group of an amino group and an amine salt. The zeolite is preferably the zeolite (large particle size zeolite) of the first embodiment described above.

[0176] The inventors of the present invention have found that, when the composition having epoxy resin and zeolite filler is in a liquid state, a dispersant having at least an amino group or an amine salt is excellent from the viewpoint of reducing viscosity. Therefore, from the viewpoint that viscosity is easy to reduce, the composition of the present invention preferably contains a dispersant having at least an amino group or an amine salt. That is, the dispersant used in the fourth embodiment of the present invention uses a dispersant having at least any functional group of an amino group and an amine salt. In addition, from the viewpoint of reducing viscosity when the composition is in a liquid state, the dispersant preferably has an amino group at the end. Amine salts can be modified by acid groups such as phosphoric acid. In the fourth embodiment of the present invention, by using a specific dispersant, zeolite can be used as an inorganic filler while preventing the viscosity of the liquid composition from becoming high.

[0177] (Dispersant)

[0178] In order to improve the dispersibility of inorganic fillers such as zeolite, the composition of the fourth embodiment of the present invention contains a dispersant. The dispersant used in the composition containing the resin and the filler is mainly added to the liquid composition containing the resin and the filler with a large polarity difference to improve the interface state of the two and improve the compatibility. As a result, it is possible to show effects in terms of reducing viscosity, improving the dispersibility of the filler, and preventing the aggregation and sedimentation of the filler.

[0179] As the dispersant in the 4th embodiment, for example, acrylic acid dispersants and polymer dispersants etc. can be cited. Here, "polymer dispersant" refers to a dispersant with a weight average molecular weight of more than 1,000. In addition, the main chain skeleton of the polymer dispersant is not particularly limited, and polyurethane skeleton, polyacrylic acid skeleton, polyester skeleton, polyamide skeleton, polyimide skeleton, polyurea skeleton etc. can be cited. From the viewpoint of storage stability, polyurethane skeleton, polyacrylic acid skeleton, polyester skeleton are preferably used. In addition, the structure of the polymer dispersant is not particularly limited either, and random structure, block structure, comb-type structure, star-shaped structure etc. can be cited. Similarly, from the viewpoint of storage stability, block structure or comb-type structure are preferably used.

[0180] It is known that polymer dispersants have structures with polar groups at the terminal and in the molecular structure, and their effects vary depending on the surface polarity of the inorganic filler. Examples of polar groups at the terminal include carboxyl, amino, phosphoric acid, and hydroxyl groups, and examples of intramolecular structures include esters and fatty acid amides.

[0181] The dispersant is preferably a solvent-free dispersant, particularly a solvent-free polymer dispersant. The dispersant does not contain a solvent, so that the dispersant can be prevented from volatilizing and generating voids when the composition is heated and cured.

[0182] In this embodiment, from the viewpoint of reducing viscosity, the dispersant is preferably a dispersant having at least an amino group or an amine salt. The details of the dispersant having at least an amino group or an amine salt are described in the sixth embodiment described later.

[0183] Commercially available products may also be used as dispersants. Commercially available products of polymer-based dispersants include: DISPERBYK series of wetting dispersants sold by BYK-Chemie, 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; The EFKA series sold by Japan include 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, 5080 66, 5070, 5244; 3000, 5000, 11200, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000SC, 24000GR, 26000, 28000, 31845, 32000, 32500, 32550 of the Solsperse series sold by Lubrizol , 32600, 33000, 34750, 35100, 35200, 36000, 36600, 37500, 38500, 39000, 53095, 54000, 55000, 56000, 71000; DISPARLON series sold by Kusumoto Chemicals Co., Ltd. 1210, 1220, 1831, 1850, 1860, 2100, 2150, 2200, 7004, KS-260, KS-273N, KS-860, KS-873N, PW-36, DN-900, DA-234, DA-325, DA-375, DA-550, DA-1200, DA-1401, DA-7301; PB-711, PB-821, PB-822, PN-411, PA-111 of the Ajisper series sold by Ajinomoto Co., Ltd.;Surfynol series 104A, 104C, 104E, 104H, 104S, 104BC, 104DPM, 104PA, 104PG-50, 420, 440, DF110D, DF110L, DF37, DF58, DF75, DF210, CT111, CT121, CT131, CT136, GA, TG, TGE sold by Air Products; Olfine series STG, E1004 sold by Nissin Chemical Industry Co., Ltd.; SN SPERSE series 70, 2120, 2190 manufactured by San Nopco Co., Ltd.; ADEKACOL and ADEKA TOL series sold by ADEKA Co., Ltd.; Sannonic series, NAROACTY CL series, Emulmin series, NEWPOL PE series, IONET M series, IONET VI series sold by Sanyo Chemical Industries, Ltd. D series, IONET S series, IONET T series, Sanseparer 100, etc. ;

[0184] In the fourth embodiment, for example, from the viewpoint of being easy to make the inorganic filler uniformly dispersed when the composition is liquid, the content of the dispersant is preferably more. On the other hand, from the viewpoint of being difficult to occur the rise in the thermal expansion coefficient caused by the phase separation of the inorganic filler and the resin such as the epoxy resin, it is preferably less. From the viewpoint of being easy to fill the liquid composition in a narrow space and being easy to be cured to be a low thermal expansion coefficient, the content of the dispersant is preferably 0.1 mass % or more and 30 mass % or less relative to the total amount of the composition, more preferably 0.1 mass % or more and 25 mass % or less.

[0185] In each of the above embodiments, when the composition is a liquid composition, the viscosity of the liquid composition is preferably low from the viewpoint of being easy to fill the composition even in a narrow space. On the other hand, from the viewpoint of not easily generating dripping when filling the composition, it is preferably high. The viscosity of the liquid composition at 23°C is preferably 0.1 Pa·s or more, more preferably 1 Pa·s or more, further preferably 5 Pa·s or more, and particularly preferably 10 Pa·s or more. On the other hand, it is preferably 250 Pa·s or less, more preferably 200 Pa·s or less, further preferably 150 Pa·s or less, and particularly preferably 30 Pa·s or less.

[0186] As a preferred embodiment of the above-mentioned composition, a liquid composition using epoxy resin as the resin and the zeolite of the first embodiment as the zeolite is preferred. Here, the viscosity is preferably 1 Pa·s or more and 30 Pa·s or less. In addition, the content of zeolite is preferably 40 to 70% by mass.

[0187] The liquid composition can be used as an underfill material and is suitable as a sealant because it can reduce the average thermal expansion coefficient after curing.

[0188] When the composition of each of the second to fourth embodiments is in a liquid state, it can be made into a resin composite material by curing it. For example, when the resin is an epoxy resin, the resin composite material is an epoxy resin composite material. The details of the epoxy resin composite material are as follows. In addition, when the resin is a polyimide resin, the resin composite material is a polyimide resin composite material.

[0189] The average thermal expansion coefficient of the resin composite material at 25 to 100°C is preferably 0 ppm / K or more, more preferably 2 ppm / K or more, further 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, further preferably 100 ppm / K or less, and particularly preferably 30 ppm / K or less.

[0190] In particular, when an epoxy resin is used as the resin in the composition of the second embodiment and the zeolite of the first embodiment is used as the zeolite, the content of the zeolite is preferably 40 to 70% by mass, and the average thermal expansion coefficient of the resin composite material at 25 to 100° C. is preferably 10 to 30 ppm / K.

[0191] Such a resin composite material has a low average thermal expansion coefficient at a temperature below the glass transition temperature and can therefore be used as a variety of materials requiring heat resistance, and can be effectively applied to electronic devices in particular.

[0192] <Resin composite materials>

[0193] In one embodiment of the present invention, the resin composite material can be obtained by curing the above-mentioned composition (composition of the second to fourth embodiments). For example, when the resin is an epoxy resin, an epoxy resin composite material can be obtained. When the resin is an epoxy resin, the composition is preferably a liquid composition. The manufacturing method of the epoxy resin composition and the epoxy resin composite material is described in detail in the fifth embodiment of the invention described later.

[0194] When the resin is a polyimide resin, a polyimide resin composite material can be obtained. The method for producing the polyimide resin composite material may be carried out, for example, by the method described below.

[0195] (Method for producing polyimide resin composite material)

[0196] The molding of the polyimide resin composite material can use various known thermoplastic resin molding presses. The heating temperature during molding is also affected by the properties of the resin used, and is not particularly limited, but is usually 250°C or more, preferably 300°C or more, more preferably 350°C or more, and further preferably 390°C or more. In addition, from the viewpoint that resin degradation is not likely to occur during the heating and pressing process, it is preferred to use a vacuum pressing device that can reduce the amount of oxygen in the pressing machine during the heating process, or a pressing device equipped with a nitrogen replacement device.

[0197] [Fifth embodiment]

[0198] <Liquid Composition>

[0199] The liquid composition according to the fifth embodiment of the present invention contains an epoxy resin and an inorganic filler.

[0200] (Inorganic filler)

[0201] In the liquid composition of the fifth embodiment, zeolite and inorganic fillers other than zeolite are used as inorganic fillers. As inorganic fillers other than zeolite, the same fillers as those used in the third embodiment are preferred, and the above ranges are also preferred with respect to the preferred ranges.

[0202] The inorganic filler contained in the liquid composition of the fifth embodiment of the present invention includes zeolite having a particle size of 1.0 μm to 10 μm (large particle size zeolite) and an inorganic filler having a particle size of 0.1 μm to less than 1.0 μm (small particle size inorganic filler).

[0203] Zeolite is an inorganic filler with a low thermal expansion coefficient, and can reduce the thermal expansion coefficient of the epoxy resin composite material as a cured product of the liquid composition. However, it has a large specific surface area, and if it is mixed in large quantities, the viscosity of the liquid composition tends to increase. In the present invention, various studies have been conducted, and as a result, it has been found that by making the liquid composition contain a small-particle-size inorganic filler in addition to the large-particle-size zeolite, the thermal expansion coefficient of the epoxy resin composite material can be reduced, and at the same time, the viscosity can be prevented from increasing, thereby achieving a low viscosity of the liquid composition.

[0204] From the viewpoint of making it easy to fill the liquid composition even in a narrow space, the particle size of the inorganic filler is preferably smaller. On the other hand, from the viewpoint of preventing the viscosity of the liquid composition from increasing, the particle size of the inorganic filler is preferably larger. When a filler with a smaller specific surface area and a filler with a larger specific surface area are used together, the larger specific surface area increases the interaction between the filler and the resin, and the viscosity of the liquid composition tends to increase. Therefore, in order to reduce the viscosity of the liquid composition, the filler preferably has a smaller specific surface area. Regarding the specific surface area, the smaller the particle size, the easier it is to increase. In addition, the specific surface area also varies depending on the shape of the filler, and the specific surface area becomes the smallest when it is spherical. Therefore, from the viewpoint of reducing the viscosity, the inorganic filler is preferably close to a spherical shape and has a larger particle size. Therefore, in particular, with regard to large-diameter zeolite, its specific surface area is preferably 1×10 -6 ( / m) or less, more preferably 0.8×10 -6 ( / m) or less.

[0205] In the present invention, by using a small-diameter filler and a large-diameter filler together, the small particles can enter the gaps between the large particles, the filling amount can be increased, the thermal expansion coefficient can be reduced, and the viscosity increase can also be reduced.

[0206] The particle size of an inorganic filler such as zeolite is the particle size of each particle, which refers to the diameter of the largest circle (circle equivalent diameter) having an area equal to the projected area of ​​the particle when observing the particles using a scanning electron microscope (SEM). In addition, the particle size is the particle size of the primary particle.

[0207] (Content of large-size zeolite)

[0208] In the liquid composition of the 5th embodiment of the present invention, from the viewpoint of being easy to show the effect of reducing the average thermal expansion coefficient, the content of large-particle diameter zeolite is preferably more. On the other hand, from the viewpoint of improving the fluidity of the liquid composition, being easy to fill even in a narrow space, the content of large-particle diameter zeolite is preferably less. Specifically, relative to the total amount of the liquid composition, the content of large-particle diameter zeolite is preferably more than 20 mass %, more preferably more than 25 mass %, and particularly preferably more than 30 mass %. In addition, the content of large-particle diameter zeolite is preferably less than 80 mass %, more preferably less than 75 mass %, and particularly preferably less than 70 mass %.

[0209] (Small particle size inorganic filler)

[0210] The small-particle inorganic filler may be zeolite or an inorganic filler other than zeolite. Specific examples of the inorganic filler other than zeolite are as described above.

[0211] From the viewpoint of reducing the thermal expansion coefficient, the small-particle-size inorganic filler is preferably zeolite, metal nitride, metal oxide, or the like.

[0212] From the viewpoint of being easy to fully demonstrate the use effect of the filler, the content of the small-particle-diameter inorganic filler is preferably large. On the other hand, from the viewpoint of improving the fluidity of the liquid composition and being easy to fill in a narrow space, the content of the small-particle-diameter inorganic filler is preferably small. In particular, since the small-particle-diameter inorganic filler has a large specific surface area and the viscosity is easy to increase, it is easy to improve the fluidity by reducing the amount used.

[0213] In the liquid composition of the fifth embodiment of the present invention, the content of the small particle size inorganic filler is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more relative to the total amount of the liquid composition. On the other hand, it is preferably 50% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less.

[0214] (Zeolite)

[0215] The zeolite used in the present invention is described in more detail below.It should be noted that, in the following description, as long as not specifically stated, it is the description about the large-particle diameter zeolite, and when using the zeolite other than the large-particle diameter zeolite as the inorganic filler, it is preferred to have the following characteristics except the particle diameter.For example, when using zeolite as the small-particle diameter inorganic filler, the zeolite used as the small-particle diameter inorganic filler also preferably has the following characteristics.In addition, the zeolite in the 6th and 7th embodiments described later is also the same.

[0216] In addition, as the large-diameter zeolite, the zeolite of the above-mentioned first embodiment is preferable.

[0217] (Structure of Zeolite)

[0218] Zeolite is composed of silicon or aluminum and oxygen and is 4 A compound having a unit (T element is an element other than oxygen constituting the skeleton) as a basic unit. Specifically, zeolite includes crystalline porous aluminosilicate (aluminosilicate), crystalline porous aluminophosphate (ALPO), or crystalline porous silicoaluminophosphate (SAPO).

[0219] Zeolite consists of several (several to dozens) TO 4 The units are connected to form a structure called a composite building unit (hereinafter sometimes referred to as "CBU"), and therefore have regular channels (tubular pores) and cavities (holes).

[0220] The crystal structure of CBU and the zeolite described later can be represented by the code for the zeolite structure established by the International Zeolite Association (IZA). It should be noted that the zeolite structure can be determined based on the X-ray diffraction pattern obtained by an X-ray structure analysis device (for example, a desktop X-ray diffraction device "D2PHASER" manufactured by BRUKER) using the Zeolite Structure Database 2018 Edition (http: / / www.iza-structure.org / databases / ).

[0221] (Composition of Zeolite)

[0222] The zeolite of the present invention is not particularly limited as long as it does not impair the effects of the present invention. From the perspective of being advantageous for use as a filler, it is preferably an aluminosilicate containing at least an aluminum atom and a silicon atom in the framework structure. Zeolite may be used alone or in any combination and ratio.

[0223] (Zeolite framework)

[0224] As long as the liquid composition and the epoxy resin composite material obtained by curing the liquid composition described later show preferred properties, the skeleton of the zeolite is not particularly limited. From the perspective of easily obtaining an epoxy resin composite material with a low thermal expansion coefficient by curing the liquid composition, the skeleton of the zeolite preferably contains at least one structure of D6R and MTW as CBU, and more preferably has D6R. Specifically, the liquid composition and the epoxy resin composite material preferably contain a zeolite of the above-mentioned preferred structure as (CBU) at 1% by mass or more, and an epoxy resin.

[0225] As zeolites having d6r as CBU, there can be listed 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 structure zeolites, etc.

[0226] Examples of zeolites having mtw as CBU include zeolites of *BEA, BEC, CSV, GON, ISV, ITG, *-ITN, IWS, MSE, MTW, SFH, SFN, SSF, *-SSO, UOS, and UOV type structures.

[0227] In order to have a three-dimensional interaction with a part of the epoxy group contained in the epoxy resin, a zeolite having a three-dimensional channel is more preferred. For example, AEI, AFT, AFX, *BEA, BEC, CHA, EMT, ERI, FAU, GME, ISV, ITG, *-ITN, IWS, JSR, KFI, MOZ, MSE, OFF, SAT, SAV, SBS, SBT, SFW, SZR, TSC, UOS, UOV, and -WEN type zeolites can be mentioned.

[0228] Among them, from the viewpoint of being easy to control particle size, it is particularly preferred that the zeolite of the structure below the oxygen eight-membered ring. About the zeolite of the structure below the oxygen eight-membered ring, AEI, AFT, AFX, CHA, ERI, KFI, SAT, SAV, SFW and TSC type structure zeolite etc. can be listed. Among them, from the viewpoint of structural stability even if shape control is carried out, it is further preferred that the zeolite of AEI, AFX, CHA, ERI type structure, the most preferred zeolite is the zeolite with CHA structure. It should be noted that in this specification, the structure with oxygen eight-membered ring refers to the structure in which the oxygen number of the oxygen element number in the case of the maximum number of oxygen is 8 in the pores composed of oxygen and T elements (elements other than oxygen constituting the skeleton) forming the zeolite skeleton.

[0229] (Average thermal expansion coefficient of zeolite)

[0230] As long as the liquid composition and the epoxy resin composite material obtained by curing the liquid composition present preferred performance, the average thermal expansion coefficient of zeolite is not particularly limited. From the viewpoint of being easy to reduce the average thermal expansion coefficient of the liquid composition and the epoxy resin composite material with a small amount, the average thermal expansion coefficient of zeolite is preferably relatively low. In addition, from the viewpoint of suppressing the viscosity rise of the liquid composition caused by the addition of fillers, it is also preferably relatively low. Therefore, the average thermal expansion coefficient of zeolite is usually less than 0ppm / K, preferably below -2ppm / K, more preferably below -3ppm / K, further preferably below -5ppm / K, particularly preferably below -6ppm / K, and most preferably below -8ppm / K.

[0231] On the other hand, from the viewpoint that the difference with the average thermal expansion coefficient of resin is small and zeolite and resin are not easy to peel off, the average thermal expansion coefficient of zeolite is preferably higher. Therefore, the average thermal expansion coefficient of zeolite is usually more than -1000ppm / K, preferably more than -900ppm / K, more preferably more than -800ppm / K, further preferably more than -700ppm / K, particularly preferably more than -500ppm / K, most preferably more than -300ppm / K.

[0232] That is, if the average thermal expansion coefficient of zeolite is within the above range, the viscosity increase of the liquid composition can be suppressed, the gap between various components can be easily filled, and the average thermal expansion coefficient of the epoxy resin composite material after curing can be reduced. It should be noted that the average thermal expansion coefficient of zeolite can be measured by calculating the lattice constant using an X-ray diffraction device "D8ADVANCE" manufactured by BRUKER and X-ray diffraction analysis software "JADE".

[0233] (Shape of zeolite)

[0234] The shape of the zeolite is not particularly limited as long as the liquid composition and the epoxy resin composite material exhibit preferred properties, and may be spherical, whisker-like, fibrous, plate-like, or aggregates thereof, and is preferably spherical from the viewpoint of being easy to contain while suppressing viscosity increase.

[0235] The true sphericity of the zeolite is preferably 0.6 or more, more preferably 0.65 or more, and particularly preferably 0.70 or more. The upper limit of the true sphericity is not particularly limited, but may be 1 or less.

[0236] It should be noted that in this specification, "true sphericity" is defined as "the ratio of the minimum diameter of the particle to the maximum diameter". 50 zeolites contained in the liquid composition and epoxy resin composite material were randomly selected, the true sphericity was measured, and the average value was taken. The maximum diameter and the minimum diameter can be obtained by observation using a scanning electron microscope (SEM). It should be noted that the true sphericity is as described in the first embodiment above, and the true sphericity of the large-particle zeolite is preferably within the above range.

[0237] (Skeleton density of zeolite)

[0238] The skeleton density of the zeolite is not particularly limited as long as it does not impair the effects of the present invention. From the viewpoint that the structural vibration of the zeolite is likely to occur and the average thermal expansion coefficient is likely to be low, the skeleton density of the zeolite is preferably low. Therefore, the skeleton density of the zeolite is preferably The following are more preferably the following.

[0239] On the other hand, from the viewpoint that the structural stability of the zeolite tends to be high, the framework density of the zeolite is preferably higher. The framework density of the zeolite is preferably More preferably The above, more preferably If the framework density is within the above range, the zeolite can be used as a stable filler.

[0240] In addition, the framework density represents the number of T atoms present in the zeolite per unit volume, and is a value determined by the structure of the zeolite. In this specification, the values ​​described in the 2017 edition of the IZA Zeolite Structure Database (http: / / www.iza-structure.org / databases / ) may be used.

[0241] As the skeleton density is greater than And for Examples of the following zeolites include zeolites of CSV, ERI, ITG, LTL, LTN, MOZ, MSE, OFF, SAT, SFH, SFN, SSF, *-SSO, and -WEN type structures.

[0242] As the skeleton density is greater than And for Examples of the following zeolites include AEI, AFT, AFV, AFX, AVL, *BEA, BEC, EAB, GME, *-ITN, LEV, MWW, and SFW type structure zeolites.

[0243] As the skeleton density is greater than And for Examples of the following zeolites include zeolites of CHA, ISV, IWS, KFI, SAS, and SAV type structures.

[0244] As the skeleton density exists in Examples of zeolites within the following range include EMT, FAU, JSR, SBS, SBT, and TSC type zeolites.

[0245] (Silica / alumina molar ratio (SAR) of zeolite)

[0246] The silica / alumina molar ratio (sometimes referred to as "SAR", "Si / Al 2 molar ratio of Si / Al 2 The SAR (Si / Al2O3) of the zeolite is not particularly limited as long as it is a mode that does not impair the effects of the present invention. From the viewpoint that the moisture resistance of the epoxy resin composite material is improved and the amount of counter cations is easily controlled, the SAR (Si / Al2O3) of the zeolite is preferably 0.0447 W / m2. 2 Therefore, the SAR (Si / Al) of zeolite is preferably higher. 2 The ratio) is usually 2 or more, preferably 3 or more, more preferably 3.5 or more, further preferably 4 or more, particularly preferably 4.5 or more, and most preferably 5 or more.

[0247] On the other hand, from the viewpoint of easy and low-cost production, the SAR (Si / Al 2Therefore, the SAR (Si / Al) of the zeolite is preferably lower. 2 The ratio of Si / Al is usually 2000 or less, preferably 1000 or less, more preferably 500 or less, and further preferably 100 or less. 2 When the ratio is within the above range, it is easy to control the amount of counter cations and the production cost of the zeolite can also be low.

[0248] It should be noted that when gallium, iron, boron, titanium, zirconium, tin, zinc, phosphorus and other elements are used to replace silicon and aluminum, the molar ratio of the oxide of the element used as the replacement can be converted as the molar ratio of aluminum oxide or silicon dioxide. Specifically, when gallium is used to replace aluminum, the molar ratio of gallium oxide can be converted into the molar ratio of aluminum oxide.

[0249] Si / Al of zeolite 2 The ratio can be adjusted according to the types and ratios of the silicon-containing compound and the aluminum-containing compound of 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.

[0250] (Counter cation of zeolite)

[0251] The counter cation of zeolite is not particularly limited as long as it is a mode that does not damage the effect of the present invention. The counter cation of zeolite is generally a structure directing agent, a proton, an alkali metal ion, an alkaline earth metal ion, preferably a structure directing agent, a proton, an alkali metal ion, and more preferably a structure directing agent, a proton, a Li ion, a Na ion, and a K ion. In the case where the counter cation of zeolite is a structure directing agent, zeolite is more likely to present an average thermal expansion coefficient less than 0ppm / K due to its flexibility compared with alkali metal ions and alkaline earth metal ions, so it is preferred. In addition, the smaller the size of the alkali metal ion and the alkaline earth metal ion, the easier it is for the zeolite to present an average thermal expansion coefficient less than 0ppm / K, so it is preferred. Among them, the counter cation of zeolite is easy to reduce the average thermal expansion coefficient of the resin composite material when it is a proton, so it is preferred. That is, as a zeolite, it is preferably as-made (original) (containing a structure directing agent type), a proton type, an alkali metal type, and more preferably as-made, a proton type, a Li type, a Na type, and a K type. It should be noted that the structure directing agent refers to the template used in the manufacture of the zeolite.

[0252] (Crystallinity of zeolite)

[0253] The crystallinity of zeolite is not particularly limited as long as it is a mode that does not impair the effect of the present invention. It is speculated that the reason is that, compared with the structure determined by IZA through coding, Composite Building Unit (CBU) is a factor that has a greater influence on the average thermal expansion coefficient of epoxy resin composite materials. It should be noted that the crystallinity of zeolite can be obtained by comparing the X-ray diffraction peak of zeolite obtained using an X-ray diffraction device (for example, a desktop X-ray diffraction device "D2PHASER" manufactured by BRUKER) with a certain X-ray diffraction peak as a reference. As a specific calculation example, the crystallinity of LTA zeolite in Scientific Reports 2016, 6, Article number: 29210 can be cited.

[0254] (Surface treatment of zeolite)

[0255] Zeolite may be subjected to surface treatment such as silylation treatment within a range that does not impair the effects of the present invention. The surface treatment is not limited to physical treatment or chemical treatment.

[0256] (Method for producing zeolite)

[0257] The manufacturing method of zeolite can apply known methods. For example, in the case of manufacturing CHA type zeolite, it can be manufactured with reference to the method described in Japanese Patent Publication No. 2009-097856. In the case of manufacturing a zeolite with a larger particle size, it is possible to carry out hydrothermal synthesis by appropriately controlling the type and ratio of raw materials, synthesis time, temperature, etc. Specifically, for example, it can be synthesized under the conditions of increasing the amount of water during synthesis and diluting the raw material concentration by the method described in Microporous and Mesoporous Materials 21 (1998) 24., thereby manufacturing a zeolite with a larger particle size.

[0258] (Shape of small particle size inorganic filler)

[0259] As long as the liquid composition and the resin composite material exhibit preferred properties, the shape of the small particle size inorganic filler is not particularly limited, and may be spherical, whisker-like, fibrous, plate-like, or aggregates thereof. From the perspective of suppressing viscosity increase while containing, spherical is preferred.

[0260] The sphericity of the small-particle inorganic filler is preferably 0.6 or more, more preferably 0.65 or more, and particularly preferably 0.70 or more. The upper limit of the sphericity is not particularly limited, but may be 1 or less.

[0261] Therefore, in the fifth embodiment of the present invention, the sphericity of both the large-diameter zeolite and the small-diameter inorganic filler is preferably 0.6 or more, more preferably 0.65 or more, and particularly preferably 0.70 or more.

[0262] In addition, it is preferred that the small-diameter inorganic filler have a higher true sphericity than the large-diameter zeolite.

[0263] (Total inorganic filler content)

[0264] From the viewpoint of being easy to show the effect as filling material, the total content of all inorganic fillers (all inorganic fillers) contained in the liquid composition is preferably more. On the other hand, from the viewpoint that the fluidity of the liquid composition is higher, even in a narrow space, it is also easy to fill, it is preferably less. Specifically, in the liquid composition of the 5th embodiment of the present invention, the total content of all inorganic fillers is preferably more than 30 mass % relative to the total amount of the composition, more preferably more than 35 mass %, particularly preferably more than 40 mass %. On the other hand, it is preferably less than 95 mass %, more preferably less than 90 mass %, particularly preferably less than 85 mass %.

[0265] (Epoxy resin)

[0266] As the epoxy resin used in the present invention, an epoxy compound having an aromatic ring such as a bisphenol A skeleton, a bisphenol F skeleton, or a biphenyl skeleton is preferably used from the viewpoint of easily lowering the thermal expansion coefficient of the epoxy resin composite material obtained by curing the liquid composition. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, epoxy resin containing a naphthalene ring, epoxy resin having a dicyclopentadiene skeleton, phenol novolac type epoxy 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. can be illustrated. Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, epoxy resin containing a naphthalene ring, aminophenol type epoxy resin are preferred, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy resin containing a naphthalene ring, aminophenol type epoxy resin, and biphenyl type epoxy resin are more preferred.

[0267] Consider from the viewpoint that the glass transition temperature of the epoxy resin composite material obtained by thermally curing the liquid composition is easy to become high, preferably use multifunctional epoxy resin.As multifunctional epoxy resin, preferably glycidyl ether type multifunctional epoxy resins such as epoxy resins manufactured by various phenols, various phenolic compounds and epihalohydrin, various phenols are 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 etc., various phenolic compounds are polyphenol resins etc. obtained by the condensation reaction of various aldehydes such as various phenols and hydroxybenzaldehyde, crotonaldehyde, glyoxal.

[0268] From the viewpoint of fluidity, the viscosity of the epoxy resin used in the present invention at 23°C is preferably 5 Pa·s or less, and more preferably 0.1 to 3 Pa·s. The viscosity determination method of the epoxy resin is specified by JIS K7233 (1986), and the single cylinder rotation viscometer method is more suitable. The viscosity of the epoxy resin used in the present invention at 23°C can be measured using a B-type rotational viscometer ("LVDV-1Pri", manufactured by Brookfield, spindle: S62), which is one of the single cylinder rotational viscometer methods.

[0269] From the viewpoint of viscosity control, the epoxy equivalent of the epoxy resin is preferably 50 g / equivalent or more and 500 g / equivalent or less, and more preferably 90 g / equivalent or more and 150 g / equivalent or less. From the viewpoint of excellent heat resistance, the epoxy equivalent is preferably higher. On the other hand, from the viewpoint that the filling property of the liquid composition becomes good due to the lower melting point of the epoxy resin or the lower viscosity, and the bonding property based on the filling is easy to become higher, the epoxy equivalent is preferably lower.

[0270] The epoxy resin may be used alone or in combination of two or more thereof in any combination and ratio. In the case of a mixture, the epoxy equivalent refers to the equivalent of the mixture.

[0271] From the viewpoint that the content of inorganic fillers etc. becomes relatively more and the thermal expansion coefficient is easily reduced, the content of epoxy resin in the liquid composition of the present invention is preferably less. On the other hand, from the viewpoint that it is easy to maintain the excellent physical properties of epoxy resin, it is preferably more. Specifically, relative to the total amount of the composition, it is preferably 5% by mass or more, more preferably 10% by mass or more. On the other hand, it is preferably 50% by mass or less, more preferably 25% by mass or less, and particularly preferably 15% by mass or less.

[0272] (Curing agent)

[0273] The liquid composition of the present invention preferably further contains a curing agent. The curing agent is a substance that assists the crosslinking reaction between crosslinking groups of the epoxy resin.

[0274] As the curing agent, there is no particular limitation, and substances generally known as epoxy resin curing agents can be used. For example, amine curing agents such as phenolic curing agents, aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, anhydride curing agents, amide curing agents, tertiary amines, imidazoles and derivatives thereof, organic phosphines, phosphonium salts, tetraphenylborate, organic acid dihydrazide, halide boron amine complexes, polythiol curing agents, isocyanate curing agents, blocked isocyanate curing agents, dicyandiamide compounds, etc. can be listed. From the viewpoint of fluidity imparting and rapid curing, as the curing agent, anhydride curing agents are preferably used.

[0275] Specific examples of the phenolic curing agent include bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 1,4-bis(4-hydroxyphenoxy)benzene, 1,3-bis(4-hydroxyphenoxy)benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolac, bisphenol A novolac, o-cresol novolac, m-cresol novolac, p-cresol novolac, xylenol novolac, polyparahydroxystyrene, hydroquinone, resorcinol, catechol, tert-butylcatechol, tert-butylhydroquinone, fluoroglycinol, pyrogallol, tert-butylpyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2,4-pyrogallol, 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 novolac, allylated pyrogallol, and the like.

[0276] Specific examples of amine curing agents include aliphatic amines such as ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, and tetrakis(hydroxyethyl)ethylenediamine.

[0277] Examples of the polyetheramines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propylamine), polyoxypropylene diamine, and polyoxypropylene triamine.

[0278] Examples of the alicyclic amines include isophoronediamine, menthanediamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, and norbornenediamine.

[0279] Examples of the aromatic amines include tetrachloro-p-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, m-aminophenol, m-aminobenzylamine, dimethylbenzylamine, 2-dimethylaminomethylphenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl)ethylamine, diaminodiethyldimethyldiphenylmethane, and α,α'-bis(4-aminophenyl)-p-diisopropylbenzene.

[0280] Specific examples of the acid anhydride curing agent include dodecenylsuccinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyloctadecane dioic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhumic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, and the like. Carboxylic anhydride, ethylene glycol trimellitic anhydride, chlorobridged anhydride, nadic anhydride, methyl nadic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dimethyl-6-(2-methyl-1-propenyl)-4-cyclohexene-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic anhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic anhydride, etc.

[0281] Examples of the amide-based curing agent include dicyandiamide and polyamide resins.

[0282] Examples of the tertiary amine include 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, dimethylbenzylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol.

[0283] Examples of imidazole and its 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.

[0284] Examples of the organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine. Examples of the phosphonium salts include tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, and tetrabutylphosphonium tetrabutylborate. Examples of tetraphenylborates include 2-ethyl-4-methylimidazolium tetraphenylborate and N-methylmorpholine tetraphenylborate.

[0285] These curing agents may be used alone or in combination of two or more in any ratio.

[0286] Regarding the content of the curing agent in the case where the liquid composition of the present invention contains a curing agent, from the viewpoint of not easily causing the influence caused by the unreacted epoxy group and the functional group of the curing agent remaining, when the curing agent is a phenol-based curing agent, an amine-based curing agent, or an acid anhydride-based curing agent, it is preferably used in a manner to be in the range of 0.8 to 2.0 in terms of the equivalent ratio of the epoxy group in the epoxy resin to the functional group in the curing agent (functional group in the curing agent / epoxy group in the epoxy resin), and more preferably in the range of 0.8 to 1.5.

[0287] When the curing agent is an amide curing agent, a tertiary amine, imidazole and its derivatives, an organic phosphine, a phosphonium salt, a tetraphenyl borate, an organic acid dihydrazide, a halogenated boron amine complex, a polythiol curing agent, an isocyanate curing agent, a blocked isocyanate curing agent, etc., preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the epoxy resin. On the other hand, preferably 20 parts by mass or less, more preferably 10 parts by mass or less.

[0288] In the case of a dicyandiamide compound, it is preferably used in an amount of 0.1 parts by mass or more, more preferably 0.5 parts 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.

[0289] (Dispersant)

[0290] In order to improve the dispersibility of the inorganic filler, the liquid composition of the fifth embodiment of the present invention may contain a dispersant. The dispersant used in the liquid composition containing the resin and the filler is mainly added to the liquid composition containing the resin and the filler with a large polarity difference to improve the interface state of the two and improve the compatibility. As a result, it is possible to show effects in terms of reducing viscosity, improving the dispersibility of the filler, and preventing the aggregation and sedimentation of the filler.

[0291] As the dispersant, the same dispersant as that used in the composition of the fourth embodiment can be used, and the preferred range and commercially available items are also the same.

[0292] In the fifth embodiment, from the viewpoint of making it easy to evenly disperse the inorganic filler in the liquid composition, the content of the dispersant is preferably more. On the other hand, from the viewpoint of not being easy to cause the increase in the thermal expansion coefficient caused by the phase separation of the inorganic filler and the epoxy resin, the content of the dispersant is preferably less. From the viewpoint of being easy to fill the liquid composition in a narrow space and being easy to be cured to have a low thermal expansion coefficient, the content of the dispersant is preferably 0.1 mass % to 30 mass % relative to the total amount of the liquid composition, and more preferably 0.1 mass % to 25 mass %.

[0293] (Reactive diluent)

[0294] The liquid composition of the present invention may contain a reactive diluent. The reactive diluent is not particularly limited as long as it contains at least one monofunctional epoxy compound. A monofunctional epoxy compound is an epoxy compound having one epoxy group, and has been used as a reactive diluent to adjust the viscosity of an epoxy resin composition. Monofunctional epoxy compounds are roughly divided into aliphatic monofunctional epoxy compounds and aromatic monofunctional epoxy compounds. From the viewpoint of viscosity, aromatic monofunctional epoxy compounds are preferred.

[0295] (Other additives)

[0296] The liquid composition may appropriately contain other additives selected from coupling agents, ultraviolet inhibitors, antioxidants, plasticizers, flame retardants, colorants, fluidity improvers, defoaming agents, ion scavengers, and the like in addition to the above-mentioned additives.

[0297] In addition, in the present embodiment, the liquid composition is preferably a solvent-free system. By being set to a solvent-free system, it is possible to prevent the solvent from volatilizing and generating gaps when the liquid composition is heated and solidified. It should be noted that the solvent is a volatile component, and in this specification, it is a term comprising water and an organic solvent. The liquid composition of the solvent-free system is substantially free of solvent, for example, relative 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.

[0298] (Viscosity of liquid composition)

[0299] The liquid composition is a composition that has fluidity at room temperature (23°C). From the viewpoint of being easy to fill the composition even in a narrow space, the viscosity of the liquid composition of the fifth embodiment of the present invention is preferably lower. On the other hand, from the viewpoint of being less likely to produce dripping when filling the composition, it is preferably higher. The viscosity of the liquid composition at 23°C is preferably 0.1 Pa·s or more, more preferably 1 Pa·s or more, further preferably 5 Pa·s or more, and particularly preferably 10 Pa·s or more. On the other hand, it is preferably 250 Pa·s or less, more preferably 200 Pa·s or less, further preferably 150 Pa·s or less, and particularly preferably 30 Pa·s or less.

[0300] The viscosity of the liquid composition can be measured in the same manner as the viscosity measurement method of the epoxy resin. The viscosity of the liquid composition used in the present invention at 23°C can 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 can be used.

[0301] (Average thermal expansion coefficient)

[0302] From the viewpoint that the epoxy resin composite material is not easily deformed by the surrounding temperature environment, heat generation, etc., the average thermal expansion coefficient (CTE1) when the liquid composition of the fifth embodiment of the present invention is made into a cured product is preferably low. On the other hand, from the viewpoint that it is not easy to cause damage caused by the difference in the average thermal expansion of the surrounding components, it is preferably close to the average thermal expansion coefficient of the surrounding components. Therefore, when the liquid composition is used as an underfill material and used in the manufacture of semiconductor devices, it is preferably close to the average thermal expansion coefficient of the semiconductor substrate (for example, 3 to 4 ppm / K).

[0303] From the above viewpoints, the average thermal expansion coefficient (CTE1) when the liquid composition of the fifth embodiment of the present invention is made into a cured product is preferably 0 ppm / K or more, more preferably 2 ppm / K or more, further 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, further preferably 100 ppm / K or less, and particularly preferably 30 ppm / K or less.

[0304] It should be noted that, regarding the average thermal expansion coefficient of the cured product obtained by curing the liquid composition and the glass transition temperature (Tg) described later, the average thermal expansion coefficient of the epoxy resin composite material (cured product) obtained by curing the liquid composition to a gel fraction of 80% or more can be measured. The average thermal expansion coefficient (CTE1) is determined by the temperature change of the sample length change at 25 to 100°C by a compression method based on thermomechanical analysis in accordance with JIS K7197 (2012), and is obtained from the slope of the tangent. The specific measurement conditions of the average thermal expansion coefficient are described in the examples.

[0305] (Glass transition temperature)

[0306] The glass transition temperature (Tg) of the epoxy resin composite material obtained by making the liquid composition of the fifth embodiment of the present invention into a cured product is not particularly limited. For example, when the Tg is high as the bottom filling material, the bump protection of the part sealed by the bottom filling material at high temperature is high, and the heat cycle resistance is excellent, so it is preferred (for example, with reference to Japanese Patent Publication No. 2017-110146). From this point of view, the glass transition temperature (Tg) of the cured product when the liquid composition of the fifth embodiment is made into a cured product is preferably 50°C or more, more preferably 80°C or more.

[0307] In addition, if the glass transition temperature is 150°C or less, the warpage at room temperature (23°C) tends to be less likely to increase, so the glass transition temperature (Tg) is preferably 50 to 150°C, and more preferably 80 to 150°C. It should be noted that the glass transition temperature (Tg) can be measured by a thermomechanical analyzer (TMA). Specifically, it can be measured by the method described in the Examples.

[0308] (Method for producing liquid composition)

[0309] The liquid composition of the fifth embodiment of the present invention can be generally obtained by mixing and kneading epoxy resin, inorganic filler, curing agent, dispersant, reactive diluent, and other additive components as needed using a vacuum mixer, mixing roll, planetary mixer, etc., and defoaming as needed. As long as there are no special problems such as reaction and precipitation, the order of mixing these components is arbitrary, and any two or more components of the constituent components can be mixed in advance, and then the remaining components can be mixed, or all of them can be mixed at once.

[0310] In addition, for example, by using zeolite with a particle size of 1.0 μm to 10 μm and an inorganic filler with a particle size of 0.1 μm to less than 1.0 μm as raw materials for manufacturing a liquid composition, the liquid composition can contain large-particle zeolite and small-particle inorganic filler produced by the above method, or the liquid composition can contain large-particle zeolite and small-particle inorganic filler produced by other methods.

[0311] <Epoxy resin composite material>

[0312] The epoxy resin composite material of the fifth embodiment of the present invention can be obtained by curing the above-mentioned liquid composition. The epoxy resin composite material of the fifth embodiment is an epoxy resin composite material containing epoxy resin and inorganic filler, and the inorganic filler contains zeolite (large particle size zeolite) with a particle size of 1.0 μm or more and 10 μm or less and inorganic filler (small particle size inorganic filler) with a particle size of 0.1 μm or more and less than 1.0 μm. The epoxy resin composite material of the fifth embodiment can be manufactured by a liquid composition having a low viscosity and a low thermal expansion coefficient by containing large particle size zeolite and small particle size inorganic filler.

[0313] In the epoxy resin composite material of the fifth embodiment of the present invention, the epoxy resin and the inorganic filler are as described above. In addition, the epoxy resin composite material may also appropriately contain the components contained in the liquid composition in addition to the epoxy resin and the inorganic filler. And, except that the total amount of the epoxy resin composite material replaces the total amount of the liquid composition as a reference, the content of each component in the epoxy resin composite material is as described above. Furthermore, the epoxy resin composite material is preferably cured to a gel fraction of 80% or more, preferably cured by a curing agent contained in the above-mentioned liquid composition.

[0314] Regarding the average thermal expansion coefficient (CTE1) and the glass transition temperature of the epoxy resin composite material of the fifth embodiment of the present invention, from the same viewpoint as above, the preferred ranges of the average thermal expansion coefficient (CTE1) and the glass transition temperature are the same as the preferred ranges when the above-mentioned liquid composition is made into a cured product. In addition, the average thermal expansion coefficient and the glass transition temperature can be measured by the above-mentioned determination method for the epoxy resin composite material.

[0315] (Method for producing epoxy resin composite material)

[0316] The epoxy resin composite material can be obtained by curing the liquid composition. Curing is preferably performed by heating. As long as the epoxy resin composite material exhibits preferred properties, the method for producing the epoxy resin composite material is not particularly limited, and a known method can be used, which is appropriately performed according to the composition of the liquid composition.

[0317] The epoxy resin composite material is preferably filled with a liquid composition in the gap between the components of various products such as electronic equipment, and is cured to form. In addition, the epoxy resin composite material can also be applied to the components of various products by the liquid composition, and is cured to form.

[0318] In addition, it is also possible to solidify and shape the liquid composition in a desired shape under the state of, for example, being accommodated in a mold. In such molded body manufacturing, injection molding, injection compression molding, extrusion molding, or compression molding can be utilized. In addition, the shaping, i.e. solidification of epoxy resin composite materials can be carried out under respective curing temperature conditions. In addition, epoxy resin composite materials can also be obtained by cutting the cured product of the liquid composition into a desired shape.

[0319] The heating temperature during thermal curing is also affected by the curing agent used, etc., and is not particularly limited, but is usually 30° C. or higher, preferably 50° C. or higher, more preferably 60° C. or higher, and further 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 further preferably 250° C. or lower. If the curing temperature is within the above range, it is easy to obtain a high-quality resin composite material in a short time.

[0320] [Sixth embodiment]

[0321] Next, the sixth embodiment of the present invention is described. The liquid composition of the sixth embodiment of the present invention contains an epoxy resin, an inorganic filler, and a dispersant, and contains at least zeolite as an inorganic filler. The components contained in the liquid composition of the sixth embodiment of the present invention other than the epoxy resin, the inorganic filler, the zeolite, and the dispersant are the same as those of the composition of the fifth embodiment of the present invention. In this embodiment, a dispersant having at least one functional group of an amino group and an amine salt is used as the dispersant.

[0322] (Dispersant)

[0323] The inventors of the present invention have found that in a liquid composition having an epoxy resin and a zeolite filler, a dispersant having at least an amino group or an amine salt is excellent from the viewpoint of reducing viscosity. Therefore, the dispersant used in the sixth embodiment of the present invention uses a dispersant having at least any functional group of an amino group and an amine salt. In addition, from the viewpoint of reducing the viscosity of the liquid composition, the dispersant preferably has an amino group at the end. The amine salt can be modified by an acid group such as phosphoric acid. In the sixth embodiment of the present invention, by using a specific dispersant, in this embodiment, zeolite can be used as an inorganic filler while preventing the viscosity of the liquid composition from becoming high.

[0324] The dispersant is preferably a polymer dispersant, the details of which are as described above, and a block structure or a comb structure is particularly preferred from the viewpoint of storage stability. In addition, the dispersant is preferably a solvent-free dispersant, particularly a solvent-free polymer dispersant.

[0325] In the sixth embodiment, a commercially available product may be used as the dispersant. As the commercially available product, any dispersant having at least one functional group of an amino group and an amine salt among the dispersants listed in the fifth embodiment may be used.

[0326] The content of the dispersant is also the same as that of the fifth embodiment.

[0327] The zeolite in the liquid composition of the sixth embodiment is the same as the zeolite contained in the liquid composition of the fifth embodiment except for the particle size and the content.

[0328] The zeolite contained in the liquid composition is not particularly limited, but its particle size is preferably 0.1 μm to 10 μm, more preferably 1 μm to 10 μm. By increasing the particle size of the zeolite contained in the liquid composition, the increase in viscosity of the liquid composition can be further suppressed.

[0329] From the viewpoint of suppressing the increase in viscosity while reducing the thermal expansion coefficient, the content of zeolite in the liquid composition of the sixth embodiment is preferably 20 mass % or more, more preferably 25 mass % or more, further preferably 30 mass % or more, particularly preferably 40 mass % or more, and especially preferably 45 mass % or more, and is preferably 90 mass % or less, more preferably 80 mass % or less, further preferably 75 mass % or less, and particularly preferably 70 mass % or less.

[0330] It should be noted that the details of the epoxy resin and zeolite other than the above-mentioned content and particle size are as described in the fifth embodiment. Furthermore, as described above, the zeolite of the sixth embodiment preferably includes a large-diameter zeolite, and the content and other details of the large-diameter zeolite are the same as those of the fifth embodiment, so the detailed description thereof is omitted. In this embodiment, too, by containing a large-diameter zeolite of a predetermined amount or more, it is easy to prevent the viscosity of the liquid composition from becoming high.

[0331] The inorganic filler in the liquid composition may contain an inorganic filler other than zeolite. The details of the inorganic filler other than zeolite are the same as those in the fifth embodiment.

[0332] Furthermore, in the sixth embodiment, the inorganic filler preferably contains a large-diameter zeolite and a small-diameter inorganic filler, similarly to the fifth embodiment. The details of the large-diameter zeolite and the small-diameter inorganic filler in this case are as described in the fifth embodiment.

[0333] Further, the liquid composition of the sixth embodiment is preferably a solvent-free composition, and the details are as described above.

[0334] The epoxy resin composite material of the sixth embodiment of the present invention is obtained by curing the above-mentioned liquid composition to a gel fraction of 80% or more. More specifically, the epoxy resin composite material is an epoxy resin composite material containing an epoxy resin, a zeolite, and a dispersant having at least one functional group of an amino group and an amine salt. As described above, the epoxy resin composite material of this embodiment contains a dispersant, which can prevent the viscosity from becoming high in the liquid composition used to obtain the epoxy resin composite material.

[0335] In the epoxy resin composite material of the sixth embodiment of the present invention, the epoxy resin, zeolite, and dispersant are as described above. In addition, the epoxy resin composite material may also appropriately contain the components contained in the liquid composition of the sixth embodiment in addition to the epoxy resin, zeolite, and dispersant. And, except that the total amount of the epoxy resin composite material replaces the total amount of the liquid composition as a reference, the content of each component in the epoxy resin composite material is as described above. Furthermore, the epoxy resin in the epoxy resin composite material can be cured to a gel fraction of 80% or more, preferably by a curing agent contained in the above-mentioned liquid composition.

[0336] In the sixth embodiment, various physical properties of the liquid composition and the epoxy resin composite material and the method for producing the same are as described in the fifth embodiment. Therefore, the viscosity of the liquid composition in the sixth embodiment, the average thermal expansion coefficient and the glass transition temperature when the liquid composition is made into a cured product, and the average thermal expansion coefficient and the glass transition temperature of the epoxy resin composite material in the sixth embodiment are as described in the fifth embodiment.

[0337] [Seventh embodiment]

[0338] A seventh embodiment of the present invention relates to an epoxy resin composite material containing zeolite as an inorganic filler and having a low average thermal expansion coefficient. The seventh embodiment of the present invention will be described below.

[0339] Specifically, the epoxy resin composite material of the seventh embodiment is an epoxy resin composite material containing an epoxy resin and an inorganic filler, wherein the average thermal expansion coefficient of the epoxy resin composite material is 0 ppm / K or more and 200 ppm / K or less, and the inorganic filler contains zeolite. The average thermal expansion coefficient is as described above, more preferably 2 ppm / K or more, particularly preferably 4 ppm / K or more, and further preferably 100 ppm / K or less, particularly preferably 30 ppm / K or less.

[0340] In the 7th embodiment of the present invention, the inorganic filler contains zeolite, and the average thermal expansion coefficient can be reduced as described above. From such a viewpoint, the content of the zeolite of the 7th embodiment is preferably 20% by mass or more relative to the total amount of the epoxy resin composite material, more preferably 25% by mass or more, further preferably 30% by mass or more, further more preferably 40% by mass or more, and most preferably 45% by mass or more. In addition, from the viewpoint of suppressing the viscosity increase of the liquid composition for obtaining the epoxy resin composite material, the above content is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 75% by mass or less, and particularly preferably 70% by mass or less.

[0341] In addition, from the perspective of being easy to reduce the thermal expansion coefficient and maintaining the excellent physical properties of the epoxy resin, the epoxy resin in the epoxy resin composite material of the seventh embodiment is preferably 5% by mass or more, more preferably 10% by mass or more, relative to the total amount of the epoxy resin composite material. On the other hand, it is preferably 50% by mass or less, more preferably 25% by mass or less, and particularly preferably 15% by mass or less.

[0342] In addition, in the seventh embodiment of the present invention, a liquid composition for obtaining the above-mentioned epoxy resin composite material is also provided. Specifically, the liquid composition of the seventh embodiment is a liquid composition containing an epoxy resin and an inorganic filler, and the average thermal expansion coefficient when the composition is made into a cured product with a gel fraction of 80% or more is 0 ppm / K or more and 200 ppm / K or less, and the above-mentioned inorganic filler contains zeolite. The determination method and preferred range of the average thermal expansion coefficient are the same as those of the above-mentioned epoxy resin composite material.

[0343] In addition, the viscosity of the liquid composition of the seventh embodiment at 23°C is preferably 0.1 Pa·s or more and 250 Pa·s or less. This can reduce the thermal expansion coefficient of the cured product and achieve low viscosity. The preferred range of the viscosity of the liquid composition at 23°C is as described in the first embodiment above.

[0344] In the seventh embodiment, the details other than the contents of the epoxy resin and zeolite are the same as those described in the fifth embodiment. Furthermore, the inorganic filler of the seventh embodiment preferably includes large-diameter zeolite as described above, and the content and other details of the large-diameter zeolite are the same as those of the fifth embodiment, and the description thereof is omitted.

[0345] In addition, the inorganic filler may contain an inorganic filler other than zeolite. The details of the inorganic filler other than zeolite are the same as those of the fifth embodiment.

[0346] Further, the liquid composition of the 7th embodiment is similar to the 5th embodiment, preferably contains a curing agent, and may also contain a reactive diluent, or other additives, etc., and these components are as described above. In addition, the liquid composition of the 7th embodiment is also preferably a solvent-free system, and its details are as described above.

[0347] Further, in the 7th embodiment, the inorganic filler is the same as the 5th embodiment, preferably containing large-diameter zeolite and small-diameter inorganic filler. In addition, in the 7th embodiment, the liquid composition or epoxy resin composite material is the same as the 6th embodiment, preferably further containing a specific dispersant (a dispersant having at least any functional group of an amino group and an amine salt). These modes are described in the above-mentioned 5th and 6th embodiments.

[0348] (use)

[0349] The composition and resin composite material of the present invention can be used for example for catalyst modules, molecular sieve membrane modules, optical components, hygroscopic components, foods, building components, and components and packaging components of electronic devices, and are preferably used for electronic devices. Therefore, the present invention provides an electronic device containing a resin composite material as a preferred embodiment, and more preferably provides an electronic device containing an epoxy resin composite material.

[0350] An electronic device is a device having more than two electrodes, which controls the current flowing between the electrodes or the voltage generated by electricity, light, magnetism or chemical substances, or generates light, electric field, and magnetic field by the applied voltage or current. Specifically, resistors, rectifiers (diodes), switching elements (transistors, thyristors), amplifier elements (transistors), memory elements or chemical sensors, or devices obtained by combining or integrating these elements can be listed. In addition, photodiodes or photosensitive transistors 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 listed. The electronic device is preferably a semiconductor device. It is better that the semiconductor device has at least a semiconductor substrate. For example, a device with a semiconductor chip mounted on a substrate, a device with multiple layers of semiconductor chips or semiconductor substrates stacked, etc. can be listed.

[0351] The liquid composition of the present invention is preferably used as a liquid sealant. In this case, the epoxy resin composite material formed by curing the liquid composition can serve as a sealing material.

[0352] The liquid sealant can be used as a sealing material to fill the gap formed between the constituent members by filling the gap and then curing.

[0353] In addition, the liquid sealant can be applied to various components, and then another component is overlapped on the liquid sealant, and then appropriately cured, so as to be used as a sealing material to fill the gap between the components. In this case, the liquid sealant can be appropriately cured and B-staged before overlapping another component.

[0354] Among them, the liquid composition of the present invention is preferably used for filling in a gap and solidifying. That is, it is preferred to fill the liquid composition of the present invention in the gap and solidify it to manufacture a sealing material. The liquid composition of the present invention has achieved low viscosity, so it can be filled even in a narrow gap without generating a void.

[0355] Liquid composition of the present invention is preferably used as liquid sealing material, particularly preferably as bottom filling material. Bottom filling material is preferably used for manufacturing electrical equipment, particularly semiconductor equipment, for example, is preferably used for filling the purposes of the gap formed between substrate and semiconductor chip, between substrate, between semiconductor chip, etc. The substrate can use known substrate, can use the substrate of organic material system such as epoxy resin substrate, phenolic resin substrate, etc. In addition, semiconductor chip can be formed by semiconductor substrates such as silicon substrate.

[0356] The liquid composition of the present invention has a low thermal expansion coefficient in its cured product, and when used as an underfill material, the difference in thermal expansion coefficient with the semiconductor substrate or the like becomes small, thereby improving heat cycle resistance and the like.

[0357] The bottom filling material is preferably filled in the gap between the substrate and the semiconductor chip in a laminated body with a semiconductor chip mounted on the substrate, and then cured by heating to serve as a sealing material for sealing between the substrate and the chip. In this case, the semiconductor chip can be bonded to the surface of the substrate on which the wiring pattern is formed via bumps, such as by reflow soldering, before filling the bottom filling material.

[0358] The bottom fill material can be used in the manufacture of semiconductor devices using a pre-coating method. Specifically, on the surface of a semiconductor chip formed with a plurality of bumps, the bottom fill material is filled between the plurality of bumps to form a bottom fill layer. Here, the filled bottom fill material can be B-staged as needed. Then, the semiconductor chip formed with the bottom fill layer can be placed on the surface of the substrate in a manner such that the surface on the side formed with the bottom fill layer faces the substrate. Next, the bottom fill layer can be cured into a sealing material by heating and pressurizing, etc. In addition, the semiconductor chip can be bonded to the surface of the substrate formed with a wiring pattern via the bumps.

[0359] In addition, in the pre-coating method, an underfill material can be applied on the surface of the substrate on which the wiring pattern is formed to form an underfill layer. Here, the applied underfill layer can be B-staged as needed. Then, the semiconductor chip formed with the bumps can be placed on the substrate formed with the underfill layer in such a way that the surface of the side formed with the bumps faces the surface of the substrate formed with the underfill layer. Then, the underfill layer can be cured into a sealing material by heating and pressing, etc., and the semiconductor chip can be bonded to the surface of the substrate formed with the wiring pattern via the bumps.

[0360] It should be noted that, in the above description, the example of the bottom filling material being used as a sealing material to fill the gap between the substrate and the semiconductor chip is described, but the use of the bottom filling material is not particularly limited, and the gap between semiconductor chips can be filled, and it can also be used as a sealing material to fill the gap between substrates, etc. In addition, the substrate is not limited to a substrate made of organic material, and can also be a semiconductor substrate, etc.

[0361] Example

[0362] Hereinafter, the present invention will be described in more detail using Examples, Comparative Examples, and Reference Examples; however, the present invention is not limited to the following Examples, Comparative Examples, and Reference Examples unless it departs from the gist of the present invention.

[0363] <Synthesis of Zeolite>

[0364] [Example 1]

[0365] (Manufacturing of Zeolite Filler A1)

[0366] N,N,N-trimethyl-1-adamantanammonium hydroxide (TMAdaOH) manufactured by Sachem as a structure directing agent (SDA), "KYOWAAD 200S" manufactured by Kyowa Chemical Industry Co., Ltd. as aluminum hydroxide, and "AEROSIL200" manufactured by Nippon Aerosil Co., Ltd. as silicon dioxide were added to the container in sequence. 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 being fully mixed, the obtained mixture is placed in a pressure-resistant container and subjected to hydrothermal synthesis in an oven at 150°C for 48 hours. After being filtered and washed, it is dried. The obtained powder is calcined at 600°C for 6 hours under air circulation to remove TMAdaOH as a structure directing agent (SDA), thereby obtaining CHA-type zeolite. The obtained zeolite has the following properties: Figure 1 The particles with the particle size distribution shown are zeolites with a particle size of 1.0 μm or more and 10 μm or less, and the average primary particle size is 3.1 μm. It should be noted that the average primary particle size is the average of the particle sizes of 50 randomly selected primary particles. In addition, the average thermal expansion coefficient at 50 to 100°C is -9.0 ppm / K, the average thermal expansion coefficient at 50 to 350°C is -17.0 ppm / K, and the Si / Al 2 The ratio is 27.8, the true sphericity is 0.85, the true roundness is 0.845, and the c-axis length is The counter cation is protonated.

[0367] [Example 2]

[0368] (Manufacture of Zeolite Filler A2)

[0369] In Example 1, except that the hydrothermal synthesis was carried out while rotating the heat-resistant container in the hydrothermal synthesis step, the same operation as in Example 1 was carried out to obtain CHA-type zeolite. The obtained zeolite has the following Figure 2 The particles of the particle size distribution shown are within the range of 1.0 μm to 10 μm based on a volume basis of 99% of the particles. The average primary particle size is 2.4 μm. It should be noted that the measurement of the average primary particle size is carried out in the same manner as in Example 1. In addition, the average thermal expansion coefficient at 50 to 100°C is -9.0 ppm / K, the average thermal expansion coefficient at 50 to 350°C is -12.1 ppm / K, and the Si / Al 2 The ratio is 27.8, the true sphericity is 0.82, the true roundness is 0.829, and the c-axis length is The counter cation is protonated.

[0370] [Example 3]

[0371] (Manufacturing of Zeolite Filler A3)

[0372] In Example 2, the composition and molar ratio of the raw material mixture were set to SiO 2 :Al 2 O 3 :TMAdaOH:H 2 O=1.0:0.020:0.4:20, except for this, the same operation as in Example 2 was carried out to perform hydrothermal synthesis, drying and calcination to obtain CHA type zeolite. Regarding the obtained zeolite, the particle size of 81% of the particles based on the volume basis is in the range of 1.0μm to 10μm. Its average primary particle size is 1.2μm. It should be noted that the measurement of the average primary particle size is carried out in the same way as in Example 1. In addition, the average thermal expansion coefficient at 50-100°C is -13.7ppm / K, the average thermal expansion coefficient at 50-350°C is -12.9ppm / K, and Si / Al 2 The ratio is 28.2, the true sphericity is 0.84, the true roundness is 0.835, and the c-axis length is The counter cation is protonated.

[0373] [Comparative Example 1]

[0374] (Manufacture of Zeolite Filler A4)

[0375] N,N,N-trimethyl-1-adamantanammonium hydroxide (TMAdaOH) manufactured by Sachem and aluminum hydroxide manufactured by Fujifilm and Koho Pure Chemical Industries, Ltd. were sequentially added to the container as a structure directing agent (SDA), and after aging at 80°C for 12 hours, "CAB-O-SILM-5" manufactured by Cabot Corporation was added as silicon dioxide. The composition and molar ratio of the obtained mixture were SiO 2 :Al 2 O 3 :TMAdaOH:H 2O=1.0:0.025:0.4:20. After being fully mixed, the obtained mixture is placed in a pressure-resistant container and subjected to hydrothermal synthesis in an oven at 150°C for 48 hours. Filtration and washing are performed to obtain CHA-type zeolite. The obtained zeolite is a zeolite in which the particle size of each particle is in the range of 1.0 μm to 10 μm, and the average primary particle size is 3.1 μm. It should be noted that the determination of the average primary particle size is carried out in the same manner as in Example 1. In addition, the average thermal expansion coefficient at 50 to 100°C is -5.0 ppm / K. Since TMAdaOH is decomposed when heated to above 300°C, the average thermal expansion coefficient at 50 to 350°C cannot be measured. Si / Al 2 The ratio is 27.8, the true sphericity is 0.84, the true roundness is 0.840, and the c-axis length is

[0376] [Comparative Example 2]

[0377] (Manufacture of Zeolite Filler A5)

[0378] N,N,N-trimethyl-1-adamantanammonium hydroxide (TMAdaOH) manufactured by Sachem as a structure directing agent (SDA), sodium hydroxide manufactured by Kishida Chemical Co., Ltd., potassium hydroxide manufactured by Kishida Chemical Co., Ltd., aluminum hydroxide manufactured by Aldrich Co., Ltd., and "Snowtex 40" manufactured by Nissan Chemical Co., Ltd. as silicon dioxide were added to the container in sequence. The composition and molar ratio of the obtained mixture were SiO 2 :Al 2 O 3 :NaOH:KOH:TMAdaOH:H 2 O=1.0:0.033:0.1:0.06:0.07:20. Added relative to SiO 2 After the mixture was fully mixed with 2 mass % CHA zeolite as a seed, it was placed in a pressure-resistant container and subjected to hydrothermal synthesis for 48 hours in an oven at 160°C while rotating the heat-resistant container. The powder obtained by suction filtration and washing was calcined at 600°C for 6 hours under air circulation to remove the structure directing agent and obtain CHA zeolite. The obtained zeolite has the following properties: Figure 3 The particle size distribution of the particles shown is within the range of 1.0 μm to 10 μm based on a volume basis of 17% of the particles. The average primary particle size is 0.5 μm. It should be noted that the measurement of the average primary particle size is carried out in the same manner as in Example 1. In addition, the average thermal expansion coefficient at 50 to 100°C is -4.9 ppm / K, the average thermal expansion coefficient at 50 to 350°C is -5.87 ppm / K, and the Si / Al 2The ratio is 20.0, and the shape is cubic. The true sphericity is 0.59, the true roundness is 0.785, and the c-axis length is The counter cations are sodium and potassium.

[0379] The results of Examples 1 to 3 and Comparative Examples 1 and 2 are summarized in Table 1.

[0380] [Table 1]

[0381]

[0382] As can be seen from the results of Table 1, the average primary particle size of the zeolite of the first embodiment of the present invention is relatively large, and it is spherical as can be seen from the results of true sphericity and true roundness. In addition, it can be seen that the thermal shrinkage is relatively large because the thermal expansion coefficient is relatively large in the negative direction. Therefore, it is believed that by using the zeolite and the resin together, a resin composite material with suppressed thermal expansion can be obtained.

[0383] In addition, the c-axis length of the zeolite of Comparative Example 1, which was not calcined after hydrothermal synthesis, was about the same as that of the zeolite of Comparative Example 2 produced by a conventional production method, whereas the c-axis length of the zeolite of Example 1, which was produced by calcining after hydrothermal synthesis, was shorter. Therefore, it is presumed that the zeolite of the present invention has a lower thermal expansion coefficient due to its shorter c-axis length.

[0384] Next, examples related to the composition and resin composite material of the present invention are shown below.

[0385] <Combination ingredients>

[0386] The blending components used in the preparation of the liquid composition and the resin composite material are as follows.

[0387] <Inorganic filler>

[0388] As the zeolite fillers A1, A3 and A4, the zeolite fillers A1, A3 or A4 produced in the above-mentioned Examples were used.

[0389] The inorganic fillers other than the zeolite fillers A1 to A5 are as follows.

[0390] Silica filler A: manufactured by Ryzen Co., Ltd., product name "HL-3100" (average particle size 45 μm, true spherical silica filler)

[0391] Silica filler B: manufactured by Admatechs Co., Ltd., product name "SC2053-SQ" (silicon dioxide having an average particle size of 0.5 μm, a particle size of each particle being in the range of 0.1 μm or more and less than 1.0 μm, and a true sphericity of 0.95)

[0392] Zeolite filler B: (CHA zeolite with a particle size of less than 1.0 μm, an average primary particle size of 0.1 to 0.2 μm, and a true sphericity of 0.58)

[0393] <Epoxy resin>

[0394] Manufactured by Mitsubishi Chemical Corporation, product name "jER630" (p-aminophenol type epoxy resin, epoxy equivalent: 97 g / equivalent)

[0395] <Polyimide powder>

[0396] Ube Industries, Ltd., product name "UIP-R" (polyimide, average particle size: 7 μm, specific gravity 1.39)

[0397] <Curing Agent>

[0398] Anhydride curing agent: manufactured by Hitachi Chemical Co., Ltd., product name "HN-2200" (methyltetrahydrophthalic anhydride, amine equivalent 83 g / equivalent)

[0399] <Dispersant>

[0400] Dispersant A: manufactured by BYK-Chemie Japan, a wetting dispersant, product name "DISPERBYK-2152" (ultramolecular weight polyester containing amino groups, comb type, solvent-free)

[0401] Dispersant B: manufactured by BYK-Chemie Japan, a wetting dispersant, product name "DISPERBYK-145" (comb-shaped polymer polyester terminal phosphoric acid modified amine salt, solvent-free)

[0402] Dispersant C: BYK-Chemie Japan, a wetting dispersant, product name "BYK-W9010" (phosphoric acid polyester, solvent-free)

[0403] (Physical Property Evaluation)

[0404] Physical property evaluation was performed as follows.

[0405] (Gel fraction)

[0406] The gel fraction of the resin composite material is determined according to the following steps. The resin composite material sample prepared under the curing conditions of 80°C for 2 hours and 120°C for 2 hours is cut into pieces within the range of 0.5 to 0.6 g and placed on a metal mesh. The metal mesh is left to stand for 24 hours while being immersed in acetone. Then, the metal mesh is taken out from the acetone and vacuum dried. The ratio of the weight of the sample after immersion to the weight before immersion is set as the gel fraction.

[0407] (Viscosity of liquid composition)

[0408] The viscosity of the liquid composition at 23° C. was measured using a B-type rotational viscometer. As a B-type rotational viscometer, "LVDV-1Pri" (manufactured by Brookfield, spindle: S64, S63) was used when the viscosity was 0.1 to 100 Pa·s, and "HBDV-E" (manufactured by Brookfield, spindle: S-07) was used when the viscosity exceeded 100 Pa·s. It should be noted that the value measured at 20 rpm was set as a representative value of the viscosity of each sample.

[0409] (Average coefficient of thermal expansion (CTE1) of epoxy resin and epoxy resin composite)

[0410] The average thermal expansion coefficient of the epoxy resin composite material obtained by curing the liquid composition to a gel fraction of 80% or more is measured by thermomechanical analysis according to JIS K7197 (2012). The measurement is performed by compression method using a thermomechanical analyzer (device name: TMA SS7100, manufactured by SII Nano Technology). Specifically, the epoxy resin composite material is cut into a size of φ6mm×10mm, and the temperature is lowered from 200°C to 20°C at 5°C / min using a thermomechanical analyzer. The temperature change of the sample length change at 25-100°C is measured, and the slope of the tangent is set as the average thermal expansion coefficient (CTE1).

[0411] (Average coefficient of thermal expansion (CTE1) of polyimide resin and polyimide resin composite material)

[0412] The average thermal expansion coefficient of the polyimide resin composite material cured to a gel fraction of 80% or more was measured by thermomechanical analysis according to JIS K7197 (2012). A thermomechanical analyzer (device name: TMA SS7100, manufactured by SII Nano Technology) was used to measure by compression method. Specifically, the polyimide resin composite material was cut into a size of 10 mm in width, 6 mm in thickness, and 10 mm in height, and a thermomechanical analyzer was used to measure by compression method at 5 ° C / min from 200 ° C to 20 ° C, and the temperature change of the sample length change at 25 to 100 ° C was measured, and the slope of the tangent was set as the average thermal expansion coefficient (CTE1).

[0413] (Glass transition temperature of epoxy resin composites)

[0414] The glass transition temperature (Tg) of the epoxy resin composite material obtained by curing the liquid composition to a gel fraction of 80% or more is measured by a thermomechanical analyzer (TMA). Specifically, the measurement is carried out using the same device and conditions as the evaluation of the above-mentioned thermal expansion coefficient, and a graph is drawn with temperature as the X-axis and the linear expansion coefficient as the Y-axis. CTE'1 is determined by the slope of the tangent line at 15 to 75°C of the graph, CTE'2 is determined by the slope of the tangent line at 150 to 200°C, and the glass transition temperature Tg (°C) is determined by the intersection of CTE'1 and CTE'2.

[0415] [Example 4]

[0416] 13 g of epoxy resin, 17 g of curing agent, 59 g of zeolite filler A1, 10 g of silica filler B, and 1 g of dispersant A were weighed and mixed in a cup in a manner as shown in Table 2. Then, a vacuum mixer (manufactured by EME Co., Ltd., "V-mini 300") was used to mix at 1500 rpm for 5 minutes to prepare a liquid composition. The viscosity of the liquid composition at 23°C was measured using a rotational viscometer. Then, it was cast in a molding mold, heated at 80°C for 2 hours, and then heated at 120°C for 2 hours to solidify it to a gel fraction of more than 80%, and then demolded to obtain an epoxy resin composite material.

[0417] [Comparative Example 3]

[0418] 21 g of epoxy resin, 29 g of curing agent, and 50 g of silica filler A were weighed in a cup and mixed by hand to obtain the formulation shown in Table 2. A liquid composition and a resin composite material were obtained in the same manner as in Example 4 except for the formulation ratio.

[0419] [Comparative Example 4]

[0420] 17 g of epoxy resin, 23 g of curing agent, and 60 g of zeolite filler B were weighed in a cup and mixed by hand to obtain the formulation shown in Table 2. A liquid composition and a resin composite material were obtained in the same manner as in Example 4 except for the formulation ratio.

[0421] [Example 5]

[0422] 21 g of epoxy resin, 29 g of curing agent, and 50 g of zeolite filler A1 were weighed in a cup and mixed by hand to obtain the formulation shown in Table 2. A liquid composition and a resin composite material were obtained in the same manner as in Example 4 except for the formulation ratio.

[0423] [Example 6]

[0424] 17.2 g of epoxy resin, 23.2 g of curing agent, and 59.6 g of zeolite filler A1 were weighed in a cup and mixed by hand to obtain the formulation shown in Table 2. A liquid composition and a resin composite material were obtained in the same manner as in Example 4 except for the formulation ratio.

[0425] [Example 7]

[0426] 17 g of resin, 23 g of curing agent, 59 g of zeolite filler A1, and 1 g of dispersant C were weighed and mixed in a cup to obtain the formulation shown in Table 2. A liquid composition and a resin composite material were obtained in the same manner as in Example 4 except for the formulation ratio.

[0427] [Example 8]

[0428] 17 g of epoxy resin, 23 g of curing agent, 59 g of zeolite filler A1, and 1 g of dispersant A were weighed and mixed in a cup to obtain the formulation shown in Table 2. A liquid composition and a resin composite material were obtained in the same manner as in Example 4 except for the formulation ratio.

[0429] [Example 9]

[0430] 17 g of epoxy resin, 23 g of curing agent, 59 g of zeolite filler A1, and 1 g of dispersant B were weighed and mixed in a cup to obtain the formulation shown in Table 2. A liquid composition and a resin composite material were obtained in the same manner as in Example 4 except for the formulation ratio.

[0431] [Example 10]

[0432] 9.9 g of epoxy resin, 14.9 g of curing agent, 49.5 g of zeolite filler A1, 24.7 g of silica filler B, and 1 g of dispersant A were weighed and mixed by hand in a cup to obtain the formulation shown in Table 2. Except for the formulation ratio, the same operation as in Example 4 was carried out to obtain a liquid composition and a resin composite material.

[0433] The viscosity of the liquid compositions in Examples 4 to 10 and Comparative Examples 3 to 4 was measured, and the average thermal expansion coefficient (CTE1) and glass transition temperature Tg of the epoxy resin composite materials were measured.

[0434] The results are shown in Table 2.

[0435] [Table 2]

[0436]

[0437] [Comparative Example 5]

[0438] A liquid composition and a resin composite material were obtained in the same manner as in Example 6 except that no zeolite filler was used. The viscosity of the liquid composition was 0.4 Pa·s, and the average thermal expansion coefficient (CTE1) of the epoxy resin composite material was 64 ppm / K.

[0439] [Example 11]

[0440] A liquid composition and a resin composite material were obtained in the same manner as in Example 6 except that zeolite filler A3 was used instead of zeolite filler A1. The average thermal expansion coefficient (CTE1) of the epoxy resin composite material was 20 ppm / K.

[0441] [Reference Example 1]

[0442] A liquid composition and a resin composite material were obtained in the same manner as in Example 6 except that zeolite filler A4 was used instead of zeolite filler A1. The average thermal expansion coefficient (CTE1) of the epoxy resin composite material was 30 ppm / K.

[0443] According to Examples 5 to 11, it was confirmed that a low-viscosity liquid composition can be obtained by containing the zeolite of the present invention, and the thermal expansion coefficient of the resin composite material obtained by curing the liquid composition can be reduced. In particular, according to the comparison between Examples 5 and 11 containing the zeolite of Example 1 or 3 and Reference Example 1 containing the zeolite of Comparative Example 1, it was confirmed that a resin composite material with a low thermal expansion coefficient can be obtained by containing the zeolite of the present invention.

[0444] First, it can be seen from the results in Table 2 that the thermal expansion coefficients of the resin composite materials of Examples 5 and 6 containing the zeolite of the present invention are lower than those of the resin composite material of Comparative Example 3 containing a silica filler having a large particle size. In addition, the liquid compositions of Examples 5 and 6 containing the zeolite of the present invention have a lower viscosity than the liquid composition of Comparative Example 4 containing a zeolite having a small particle size. That is, it was confirmed that a liquid composition having a low viscosity can be obtained by containing the zeolite of the present invention, and the thermal expansion coefficient of the resin composite material obtained by curing the liquid composition can be reduced.

[0445] In Examples 4 and 10, the thermal expansion coefficient of the epoxy resin composite material obtained by curing the liquid composition was successfully reduced by using a large particle size zeolite and a small particle size inorganic filler, and the viscosity of the liquid composition was successfully reduced. In contrast, in Comparative Example 3, a large particle size silica filler was contained, and its content was set to the same level as that of the large particle size zeolite in Example 10. As a result, although the viscosity of the liquid composition was reduced, the average thermal expansion coefficient (CTE1) was increased.

[0446] In addition, although Examples 5 and 10 contain the same amount of large-diameter zeolite, both can reduce the average thermal expansion coefficient (CTE1) to a certain extent and also successfully reduce the viscosity. In particular, in Example 10, the average thermal expansion coefficient (CTE1) is lower than that in Example 5.

[0447] In Comparative Example 4 and Example 6, when the zeolite filler is contained and the content thereof is further increased compared to Comparative Example 3 and Example 5, the average thermal expansion coefficient (CTE1) is reduced. Here, in Example 6, the viscosity of the liquid composition is not increased compared to Comparative Example 4, so it is considered that it is suitable as an underfill material used to fill the gap. That is, it is confirmed that by using the large particle size zeolite of the present invention, a low viscosity liquid composition can be obtained, and by curing the liquid composition, a resin composite material with a low thermal expansion coefficient can be obtained.

[0448] As shown in Table 2, when Examples 8 and 9 are compared with Examples 6 and 7, it is confirmed that dispersants A and B containing an amino group or an amine salt are effective in reducing viscosity because the viscosity is reduced when dispersants A or B are added. In addition, it is confirmed that the glass transition temperature Tg of the resin composite materials of Examples 8 and 9 is very high and excellent in heat cycle resistance by adding the dispersant, and the average thermal expansion coefficient is also suitable for underfill materials.

[0449] [Example 12]

[0450] 21 g of polyimide powder and 9 g of zeolite filler A1 manufactured in Example 1 were weighed in a cup and mixed, and then densely spread on a pressing mold. The mold was set in a high-temperature vacuum pressing device (manufactured by Kitagawa Seiki Co., Ltd.), pressed at a pressing temperature of 390°C with a pressing surface pressure of 8 MPa for 30 minutes, and demolded to obtain a molded body with a length of 11 cm, a width of 2.5 cm, and a thickness of 6 mm. It was cut every 10 mm from the end, and the average thermal expansion coefficient was measured. The results are shown in Table 3.

[0451] [Comparative Example 6]

[0452] In Example 12, except that the zeolite filler A4 produced in Comparative Example 1 was used as zeolite, the same procedure as in Example 12 was carried out to produce a molded body, and the average thermal expansion coefficient thereof was measured.

[0453] [Comparative Example 7]

[0454] The results are shown in Table 3. A molded body was produced in the same manner as in Example 12 except that the zeolite filler was not used.

[0455] [Table 3]

[0456]

[0457] Table 3 shows that, also with regard to polyimide resin, a resin composite material having a low thermal expansion coefficient can be obtained by using the large-diameter zeolite of the present invention.

[0458] Industrial Applicability

[0459] According to the present invention, a low-viscosity liquid composition can be provided. In addition, by solidifying the liquid composition, a resin composite material with a low thermal expansion coefficient can be provided. That is, according to the composition of the present invention, a sealing material with excellent injectability and excellent heat resistance can be obtained, which can be particularly used as a bottom filling material.

[0460] Furthermore, the resin composite material having a low thermal expansion coefficient of the present invention can also be used as a sealing material produced by press molding or the like.

Claims

1. A liquid composition, which is a liquid composition containing a resin and an inorganic filler, the inorganic filler containing zeolite having a particle size of 1.0 μm or more and 10 μm or less, and an inorganic filler having a particle size of 0.1 μm or more and less than 1.0 μm, the zeolite being an aluminosilicate having d6r as a CBU, being spherical, and having a c-axis length of the lattice constant of less than the following, and having a roundness of 0.790 or more, the resin being at least 1 selected from the group consisting of an epoxy resin and a polyimide resin, and the inorganic filler having a particle size of 0.1 μm or more and less than 1.0 μm containing silica, Among them, The particle size refers to the diameter of the largest circle, i.e., the equivalent circle diameter, which has an area equal to the projected area of the particle in the particle observation using a scanning electron microscope (SEM), and the particle size is the particle size of the primary particle; in addition, the roundness is 4×π×area / (circumference). 2 , and the area and the circumference are obtained by observation using a scanning electron microscope (SEM), respectively.

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

3. The liquid composition according to claim 1 or 2, wherein the resin is an epoxy resin.

4. The liquid composition according to claim 1 or 2, wherein the resin is an epoxy resin, and the viscosity of the liquid composition at 23°C is 0.1 Pa·s or more and 250 Pa·s or less. Among them, The method for measuring the viscosity of the liquid composition at 23°C is specified by JIS K7233:1986, and the measurement is carried out using a B-type rotational viscometer as one of the single-cylinder rotational viscometer methods.

5. A liquid sealant comprising the liquid composition according to any one of claims 1 to 4.

6. A resin composite material obtained by curing the liquid composition according to any one of claims 1 to 4 to a gel fraction of 80% or more. Among them, The gel fraction of the resin composite material is measured according to the following steps: Cut the resin composite material sample prepared under the curing conditions of 80°C for 2 hours and 120°C for 2 hours into a range of 0.5 to 0.6 g, and place it on a metal mesh. Leave the metal mesh immersed in acetone for 24 hours, then take out the metal mesh from acetone and perform vacuum drying. The ratio of the weight of the sample after impregnation to the weight before impregnation is defined as the gel fraction.

7. A resin composite material, which is a resin composite material containing a resin and an inorganic filler, the inorganic filler contains zeolite with a particle size of 1.0 μm or more and 10 μm or less, and an inorganic filler with a particle size of 0.1 μm or more and less than 1.0 μm, the zeolite has d6r as the CBU, is spherical, and the c-axis length of the lattice constant is Less than, an aluminosilicate with a roundness of 0.790 or more, the resin is at least 1 selected from the group consisting of epoxy resin and polyimide resin, and the inorganic filler with a particle size of 0.1 μm or more and less than 1.0 μm contains silica Among them, The particle size refers to the diameter of the largest circle, i.e., the equivalent circle diameter, which has an area equal to the projected area of the particle in the particle observation using a scanning electron microscope (SEM), and the particle size is the particle size of the primary particle; in addition, the circularity is 4×π×area / (circumference). 2 , where the area and the circumference are respectively obtained by observation using a scanning electron microscope (SEM).

8. The resin composite material according to claim 7, further comprising a dispersant having at least one functional group of amino group and amine salt.

9. The resin composite material according to claim 7 or 8, wherein the resin is an epoxy resin, and the average thermal expansion coefficient of the resin composite material obtained by the following method is 0 ppm / K or more and 200 ppm / K or less. Among them, The average thermal expansion coefficient is determined according to JIS K7197:2012 by the compression method based on thermomechanical analysis, and the temperature change of the sample length change amount at 25 to 100°C is measured, and the slope of its tangent line is obtained.

10. A zeolite, which has a particle size of 1.0 μm or more and 10 μm or less, has d6r as the CBU, is spherical, has a c-axis length of the lattice constant of or less, and is an aluminosilicate with a circularity of 0.790 or more, Among them, The particle size refers to the diameter of the largest circle, i.e., the equivalent circle diameter, which has an area equal to the projected area of the particle in the particle observation using a scanning electron microscope (SEM), and the particle size is the particle size of the primary particle; in addition, the circularity is 4×π×area / (circumference). 2 , and the area and the circumference are obtained by observation using a scanning electron microscope (SEM), respectively.

11. A composition comprising the zeolite according to claim 10 and a resin, wherein the resin is at least one selected from the group consisting of an epoxy resin and a polyimide resin.

12. The composition according to claim 11, further comprising an inorganic filler having a particle size of 0.1 μm or more and less than 1.0 μm, and the inorganic filler having a particle size of 0.1 μm or more and less than 1.0 μm contains silica. Among them, The particle size refers to the diameter of the largest circle having an area equal to the projected area of the particle in the particle observation using a scanning electron microscope (SEM), that is, the equivalent circle diameter, and the particle size is the particle size of the primary particle.

13. The composition according to claim 11 or 12, further comprising a dispersant having at least one functional group of amino group and amine salt.

14. A liquid composition, which is the composition according to any one of claims 11 to 13, wherein the content of the zeolite is 40 to 70% by mass, the resin is an epoxy resin, and the viscosity of the liquid composition at 23 °C is 1 Pa·s or more and 30 Pa·s or less. Wherein, The method for measuring the viscosity of the liquid composition at 23 °C is specified by JIS K7233:1986, and the measurement is carried out using a B-type rotational viscometer, which is one of the single-cylinder rotational viscometer methods.

15. A resin composite material, which is a resin composite material containing the composition according to any one of claims 11 to 13, wherein the content of the zeolite is 40 to 70% by mass, the resin is an epoxy resin, and the average thermal expansion coefficient of the resin composite material at 25 to 100 °C is 10 to 30 ppm / K. Wherein, The average thermal expansion coefficient is determined according to JIS K7197:2012 by the compression method based on thermomechanical analysis, and is obtained from the slope of the tangent line of the temperature change of the sample length change amount measured at 25 to 100 °C.

16. A sealing material, which contains the resin composite material according to any one of claims 7 to 9 and 15.

17. An electronic device, which includes the resin composite material according to any one of claims 7 to 9 and 15.

18. Use of the liquid composition according to any one of claims 1 to 4 and 14 for filling a gap and curing.

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