Composite oxide particulate material and method for producing the same, filler, filler-containing slurry composition, and filler-containing resin composition

Abstract

To provide a composite oxide particle material composed of zinc molybdate with high purity and high circularity.SOLUTION: A composite oxide particle material is composed of a complex oxide of molybdenum and zinc with an average particle size of 0.1 μm or more and 5.0 μm or less, a BET specific surface area of 1 m2 / g or more and 20 m2 / g or less, (XRD 26.6° peak intensity) / (XRD 24.2° peak intensity) of 1.20 or more, an impurity concentration of 1 mass% or less, and a circularity of 0.90 or more. XRD is measured with CuKα rays.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a composite oxide particulate material containing molybdenum and zinc, a method for producing the same, a filler, a filler-containing slurry composition, and a filler-containing resin composition. [Background technology]

[0002] As semiconductor devices become faster and higher in frequency, it is necessary to reduce the dielectric constant and dissipation factor of the materials that make up the devices.

[0003] For example, while silica and alumina are primarily used as fillers in semiconductor devices, zinc molybdate can be used in combination as a flame retardant aid or to improve processability. However, because zinc molybdate has a high dielectric constant and dielectric loss tangent, it is necessary to keep them as low as possible.

[0004] Known methods for producing zinc molybdate include a method in which an aqueous solution of sodium molybdate is mixed with zinc chloride and reacted, and a method in which molybdenum oxide and zinc oxide are heated in water to cause a reaction.

[0005] Considering the packing properties as a filler, a spherical shape is preferable, but zinc molybdate produced by a wet synthesis method has low circularity. A method in which metal particles are introduced into a high-temperature oxidizing atmosphere and oxidized (VMC method) is a manufacturing method suitable for producing spherical particle materials, and a method for manufacturing zinc molybdate has also been disclosed (Patent Document 1). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-082668 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the method of Patent Document 1 contains a large amount of unreacted raw materials and by-products (molybdenum oxide, zinc oxide), making it unsuitable for practical use.

[0008] The present invention was completed in view of the above-mentioned circumstances, and aims to provide a composite oxide particulate material made of zinc molybdate with high purity and high circularity, a method for producing the same, and a filler, a filler-containing slurry composition, and a filler-containing resin composition each containing such a composite oxide particulate material. [Means for solving the problem]

[0009] The inventors conducted extensive research to solve the above problems and discovered that zinc molybdate can have a low dielectric constant and dielectric loss tangent by having a crystal structure in which the XRD peak intensity at 26.6° / peak intensity at 24.2° is 1.20 or more, and that adopting the VMC method and increasing the amount of oxygen used in the reaction are effective ways to achieve this crystal structure. They discovered that by improving the VMC method, not only could the XRD peak intensity at 26.6° / peak intensity at 24.2° be increased to 1.20 or more, but also the amounts of unreacted and by-reacted materials could be reduced, leading to the completion of the present invention.

[0010] That is, the composite oxide particle material of the present invention, which solves the above-mentioned problems, has an average particle size of 0.1 μm or more and 5.0 μm or less, a BET specific surface area of ​​1 m 2 / g or more, 20m 2 / g or less, (XRD peak intensity at 26.6°) / (peak intensity at 24.2°) is 1.20 or more, impurity concentration is 1 mass % or less, and circularity is 0.90 or more. XRD is measured using CuKα radiation.

[0011] The dielectric constant is preferably 16 or less. In addition, the dielectric constant is preferably (dielectric loss tangent) / (BET specific surface area (m 2)) is preferably 0.0030 or less. Furthermore, it is preferable that the surface is treated with an organosilicon compound.

[0012] The method for producing a composite oxide particulate material of the present invention, which solves the above-mentioned problems, is a method for producing a composite oxide particulate material of the present invention, and comprises a raw particle material preparation step of preparing one or more raw particle materials that contain metallic molybdenum and metallic zinc as a whole, and a composite oxide particulate material production step of continuously feeding the raw particle materials, while dispersed in a carrier, into a flame in an oxidizing atmosphere and burning them to produce a composite oxide particulate material.

[0013] In particular, it is preferable that the ratio (R / T) of the amount of oxygen per unit time T required to completely oxidize the raw particle material and the combustible gas to the amount of oxygen per unit time R introduced into the oxidizing atmosphere is 1.2 or more.

[0014] The filler of the present invention, which solves the above problems, is a filler used in a resin composition for electronic materials containing the composite oxide particulate material of the present invention, and may also contain other inorganic particulate materials.

[0015] The filler-containing slurry composition of the present invention, which solves the above problems, comprises the filler of the present invention and a dispersion medium for dispersing the filler.

[0016] The filler-containing resin composition of the present invention, which solves the above-mentioned problems, comprises the filler of the present invention and a resin material in which the filler is dispersed. [Effects of the Invention]

[0017] By having the above-mentioned components, the composite oxide particle material of the present invention can provide a composite oxide particle material made of zinc molybdate that has a low dielectric constant and dielectric loss tangent, good electrical properties, and few impurities. [Brief explanation of the drawings]

[0018] [Figure 1] 1 is an XRD chart of test samples of each example and comparative example. [Figure 2] 1 is an IR spectrum of Example 8. DETAILED DESCRIPTION OF THE INVENTION

[0019] The composite oxide particulate material and its manufacturing method of the present invention will be described in detail below with reference to the following embodiments. The composite oxide particulate material of this embodiment is a particulate material made of zinc molybdate, a composite oxide of molybdenum and zinc, and can be used as part or all of the filler contained in resin compositions used in semiconductor encapsulants, underfills, substrate materials, etc. When used in combination with other materials, it can be used together with silica particulate materials, alumina particulate materials, etc.

[0020] (Composite oxide particle material) The composite particle material of this embodiment is made of zinc molybdate and contains 1% by mass or less of impurities. The impurities refer to unreacted metallic molybdenum, metallic zinc, and molybdenum oxide and zinc oxide produced by the oxidation of molybdenum and zinc alone. The amounts of impurities are calculated based on a calibration curve obtained by XRD measurement of powders containing zinc molybdate, molybdenum oxide, zinc oxide, molybdenum, and zinc at different mixing ratios.

[0021] The composite oxide particulate material of this embodiment has a crystal structure in which (XRD 26.6° peak intensity) / (24.2° peak intensity) is 1.20 or more, and the lower limit thereof may be 1.22, 1.24, 1.26, 1.28, or 1.30.

[0022] To calculate peak intensities from an XRD chart, the baseline is set to a straight line connecting the intensity at a diffraction angle 2θ of 18° and the intensity at a diffraction angle 2θ of 45°, and the heights at the positions of 26.6° and 24.2° are taken as the respective peak intensities.

[0023] The composite oxide particle material of this embodiment has an average particle size of 0.1 μm or more and 5.0 μm or less, with lower limits of 0.15 μm, 0.20 μm, 0.25 μm, and 0.30 μm being examples, and upper limits of 4.5 μm, 4.0 μm, 3.5 μm, and 3.0 μm being examples. These lower and upper limits can be arbitrarily combined. The average particle size in this specification is the equivalent circle diameter. Specifically, the average value measured for 100 or more particles using image processing software (Asahi Kasei Engineering Corporation: A-zo-kun) is used.

[0024] The composite oxide particle material of this embodiment has a circularity of 0.90 or more, and examples of lower limit values ​​include 0.95, 0.98, 0.99, and 1.00. The circularity is measured by taking a photograph with an SEM and calculating the circularity from the area and perimeter of the observed particle, as follows: (Circularity) = {4π × (Area) ÷ (Perimeter)} 2 The closer it is to 1, the closer it is to a perfect sphere. Specifically, the average value measured for 100 or more particles using image processing software (Asahi Kasei Engineering Co., Ltd.: A-zo-kun) is used.

[0025] The composite oxide particle material of this embodiment has a BET specific surface area measured with nitrogen of 1 m 2 / g or more, 20m 2 / g or less, with a lower limit of 1.5m 2 / g, 2.0m 2 / g, 2.5m 2 / g can be exemplified, with an upper limit of 18m 2 / g, 16m 2 / g, 14m 2 These lower and upper limits can be combined in any desired manner.

[0026] The composite oxide particle material of this embodiment preferably has a relative dielectric constant of 16 or less, and examples of the upper limit thereof include 15.8, 15.5, 15.3, and 15.0. The relative dielectric constant of commercially available zinc molybdate and zinc molybdate synthesized by a wet synthesis method is greater than 16 and approximately 18 or less.

[0027] The lower the dielectric loss tangent (Df), the more preferable it is. For example, Df / (BET specific surface area) is preferably 0.0030 or less, with the upper limit being, for example, 0.0028, 0.026, 0.0024, 0.0022, or 0.0020.

[0028] The composite oxide particle material of this embodiment is preferably surface-treated with an organosilicon compound. As the organosilicon compound, a silane compound or a silazanes is preferably used, and examples of the silane compound include those having a phenyl group, an alkyl group, a vinyl group, a methacryl group, an epoxy group, a phenylamino group, an amino group, a styryl group, etc. Since OH groups present on the surface often react, the amount of remaining OH groups is preferably 2 / nm. 2 It is preferable that the density is less than 1 particle / nm. 2 It is more preferable that:

[0029] (Method of manufacturing composite oxide particle material) The method for producing a composite oxide particulate material of this embodiment is a method that can suitably produce the composite oxide particulate material of this embodiment, and specifically includes a raw material particle material preparation step, a composite oxide particulate material production step, and other steps selected as necessary.

[0030] The raw particle material preparation step is a step of preparing one or more raw particle materials that as a whole contain metallic molybdenum and metallic zinc.

[0031] The raw particle material to be prepared may be composed of one type of material, or may be composed of two or more types of particle materials with different compositions. The term "raw particle material containing metallic molybdenum and metallic zinc as a whole" means that when the raw particle material consisting of one or more types of particle materials is analyzed as a whole, it contains metallic molybdenum and metallic zinc. For example, it may be a mixture of a particle material consisting of metallic molybdenum and a particle material consisting of metallic zinc, or a particle material consisting of an alloy of molybdenum and zinc. It is particularly desirable for the raw particle material to contain metallic molybdenum and metallic zinc at high purity. The raw particle material may also be surface-treated with the aforementioned organosilicon compound. Surface treatment can improve the dispersion state in the carrier, as described below, and prevent aggregation.

[0032] The particle size of the raw particle material varies depending on the particle size of the composite oxide particle material to be produced, but can be about 1 μm to 30 μm. Reducing the particle size of the raw particle material tends to facilitate the oxidation reaction, which is preferable, but if the particle size is too small, the supplyability tends to deteriorate.

[0033] There are no particular limitations on the method for preparing the raw material particles. For example, metal molybdenum or metal zinc can be granulated by atomization, pulverization, etc. In particular, a method using a disk atomizer is preferred.

[0034] The composite oxide particulate material preparation process is a process for producing a composite oxide particulate material by introducing raw material particulate materials into a flame in an oxidizing atmosphere. By setting the conditions for introducing the raw material particulate materials and the conditions for generating the flame so that the composite oxide particulate material has the average particle size, BET specific surface area, and XRD chart of the composite oxide particulate material of this embodiment described above, not only can the amount of unreacted materials be suppressed but also the amount of by-reaction products can be reduced, thereby reducing the relative permittivity and dielectric loss tangent of the resulting composite oxide particulate material.

[0035] The average particle size of the resulting composite oxide particle material can be increased by increasing the raw material concentration in the oxidizing atmosphere. Conversely, the average particle size can be decreased by decreasing the raw material concentration in the oxidizing atmosphere. In particular, an excellent composite oxide particle material can be produced by increasing the amount of oxygen introduced into the oxidizing atmosphere, as described below, beyond the theoretically required amount.

[0036] The raw material particles are dispersed in a carrier and introduced into the flame. The carrier can be a gas or a liquid, such as air, nitrogen, oxygen, or argon, or a liquid such as water or an alcohol such as isopropanol.

[0037] When the raw material particles are introduced into the flame, oxygen is simultaneously introduced into the oxidizing atmosphere. The introduction of oxygen into the oxidizing atmosphere can be achieved by using oxygen as part or all of the carrier, or by introducing oxygen in a flow independent of the carrier. Oxygen can be introduced alone or together with nitrogen (including air) or other inert gases. It is preferable to form the oxidizing atmosphere in a furnace that is somewhat sealed, since this allows for precise control of the amount of oxygen introduced and the flame temperature.

[0038] The ratio (R / T) of the amount of oxygen theoretically required to completely oxidize the raw material particles and combustible gases introduced into the flame per unit time, T, to the actual amount of oxygen introduced into the oxidizing atmosphere per unit time, R, is preferably 1.2 or greater. By using an amount of oxygen that is sufficiently in excess of the theoretically required amount, it is possible to form a crystal structure in which (XRD 26.6° peak intensity) / (24.2° peak intensity) is 1.20 or greater, and it is also possible to further suppress the remaining of unreacted materials and reduce the amount of by-reactants.

[0039] The obtained composite oxide particulate material can be subjected to the surface treatment described above for the composite oxide particulate material of this embodiment. The surface treatment can be carried out by contacting the surface of the composite oxide particulate material with a surface treatment agent as is, by contacting the surface of the composite oxide particulate material with the surface of the composite oxide particulate material in a state in which the surface treatment agent is dissolved or dispersed in an appropriate solvent (a solvent capable of dispersing the composite oxide particulate material, such as isopropanol or methyl ethyl ketone (MEK)), or by contacting the surface of the composite oxide particulate material in a vaporized state. The reaction of the surface treatment agent can also be promoted by heating after contact.

[0040] The amount of the surface treatment agent is not particularly limited, but can be selected from any amount ranging from an amount less than the amount corresponding to the OH groups present on the surface of the composite oxide particulate material immediately after preparation in the composite oxide particulate material preparation step to an excess amount.

[0041] The amount of surface treatment agent is determined based on the unit surface area (m ) calculated using the BET specific surface area after surface treatment. 2 The lower limit of the amount of organosilicon compounds per 2 , 0.3 μmol / m 2 , 0.4 μmol / m 2 can be exemplified, with the upper limit being 20 μmol / m 2 , 18 μmol / m 2 , 16 μmol / m 2 These lower limit values ​​and upper limit values ​​can be combined arbitrarily.

[0042] (Filler, filler-containing slurry, filler-containing resin composition) The filler of this embodiment is a filler used in a resin composition for electronic materials, and contains the composite oxide particle material of this embodiment. If necessary, the filler may further contain an inorganic particle material. Examples of inorganic particle materials include silica particle materials and alumina particle materials. The resin composition for electronic materials can be used as an encapsulant, underfill, substrate material, or the like for semiconductor devices.

[0043] The filler-containing slurry of this embodiment is a slurry in which the filler is dispersed in a dispersion medium. The dispersion medium is not particularly limited except that it is a liquid, and examples thereof include organic solvents such as MEK and precursors of resin materials (monomers, prepolymers, etc.: resin precursors). The filler content is not particularly limited, but it is preferable to increase the filler content within a range that maintains the fluidity of the slurry.

[0044] The filler-containing resin composition of this embodiment is a composition in which the filler is dispersed in a resin material. The resin material is not particularly limited and may be in a liquid or solid state.

[0045] There are no particular limitations on the resin material that can be used, and ordinary resin materials such as thermoplastic resins and thermosetting resins can be selected, including, for example, epoxy resin, polyimide, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, vinyl chloride, polypropylene, polyethylene, and polyphenylene ether.

[0046] The method for dispersing the particulate material in the resin material is not particularly limited. For example, when a thermoplastic resin is used as the resin material, a resin composition can be obtained by mixing and kneading a heated and melted resin material with a particulate material, or by mixing a resin precursor with a particulate material and then carrying out a polymerization reaction. When the resin material is a thermosetting resin, the resin precursor and the particulate material can be mixed and then cured. Note that a composition using a liquid resin precursor as the resin material is also a filler-containing resin composition of this embodiment. [Example]

[0047] The composite oxide particulate material of the present invention will be described in detail below with reference to examples. <Preparation of test samples> Examples 1 to 7 and Comparative Example 1 (manufactured by the VMC method) Metallic molybdenum powder with an average particle size of 3 μm and a purity of 99.9% or more and metallic zinc powder with an average particle size of 30 μm and a purity of 99% or more were mixed in a molar ratio of molybdenum:zinc = 1:1 to prepare raw particle material (raw particle material preparation process).

[0048] The raw material particles were placed in an oxidizing flame in an oxidizing atmosphere formed in a reactor. The raw material particles were placed in air as a carrier at a temperature of 4 kg / m 3 The composite oxide particle material, which is the test sample of this example, consisting of a composite oxide of molybdenum and zinc (zinc molybdate) was obtained by dispersing the material so as to have a concentration of 1000 ppm and burning it (composite oxide particle material preparation step).

[0049] At this time, air was introduced into the reactor so that the ratio (R / T) of the amount of oxygen required to completely oxidize the raw material particles and combustible gases (theoretical O amount T) to the amount of oxygen actually introduced (introduced O amount R) was the value shown in Table 1.

[0050] Example 8 The test sample obtained in Example 3 was surface-treated with phenylaminosilane (KBM-573) as a surface treatment agent to obtain the test sample of this example. The surface treatment amount was determined based on the unit surface area (m2) measured by BET specific surface area. 2 The surface treatment was confirmed by IR spectroscopy. -1 The presence of a C—H stretching vibration peak derived from phenylaminosilane in the vicinity confirmed that phenylaminosilane was bonded to the surface. An example of an IR spectrum is shown in Figure 2.

[0051] Example 9 The test sample of this example was obtained by the same procedure as in Example 8, except that the test sample of Example 4 was used instead of the test sample of Example 3.

[0052] Example 10 A test sample of this example was obtained in the same manner as in Example 8, except that vinylsilane (KBM-1003) was used as the surface treatment agent instead of phenylaminosilane.

[0053] Example 11 A test sample of this example was obtained in the same manner as in Example 8, except that methacrylsilane (KBM-503) was used as the surface treatment agent instead of phenylaminosilane.

[0054] Comparison Example 2 A commercially available reagent (manufactured by Mitsuwa Chemical Co., Ltd.) was used as the test sample in this comparative example.

[0055] Comparative Example 3 A composite oxide particle material was produced by a wet synthesis method and used as a test sample for this comparative example. Specifically, the synthesis procedure was as follows: First, 10.3 g of molybdenum oxide (manufactured by Kishida Chemical Co., Ltd.) was added to 500 g of ion-exchanged water, and the mixture was heated and stirred at 80°C. 5.8 g of zinc oxide (manufactured by Kishida Chemical Co., Ltd.) was added to the mixture and stirred for 4 hours. After that, the solid content was separated into solid and liquid, dried, and calcined at 550°C for 8 hours to obtain a composite oxide particle material made of zinc molybdate.

[0056] <Evaluation> The equivalent circle diameter, specific surface area, circularity, amount of unreacted material and by-product, relative permittivity, dielectric loss tangent, dielectric loss tangent / specific surface area, (XRD peak intensity at 26.6°) / (peak intensity at 24.2°), and amount of O2 input / theoretical amount of O2 were measured or calculated. The results are shown in Table 1. For reference, the XRD charts of the test samples of each Example and Comparative Example are shown in Figure 1.

[0057] ·Relative permittivity, dielectric loss tangent The dielectric constant at 1 GHz was measured using a network analyzer (Keysight, E5071C) and a cavity resonator perturbation method in accordance with ASTM D2520 (JIS C2565).

[0058] Amount of unreacted material and by-products Mixed powders containing zinc molybdate, molybdenum oxide, zinc oxide, metallic molybdenum, and metallic zinc were prepared by varying the compounding ratio, and XRD measurements were performed. From the resulting chart, the diffraction intensities at the diffraction angles (2θ) of each substance were read to create calibration curves. Using the created calibration curves, the contents of unreacted materials and by-products contained in the test samples of each example and comparative example were calculated.

[0059] The values ​​used for the peak around 27° for zinc molybdate, the peak around 23° for molybdenum oxide, the peak around 32° for zinc oxide, the peak around 40° for metallic molybdenum, and the peak around 43° for metallic zinc were used.

[0060] [Table 1]

[0061] As is clear from the table, the test samples of Examples 1 to 11 and Comparative Example 1 produced by the VMC method were found to have a high degree of circularity. Additionally, Examples 1 to 11 were found to have high purity (low amounts of unreacted materials and by-reacted products).

[0062] Furthermore, the test samples of Examples 1 to 11 and Comparative Example 1, in which the (XRD peak intensity at 26.6°) / (peak intensity at 24.2°) was 1.20 or more, had a relative dielectric constant of 16 or less and a dielectric loss tangent / specific surface area of ​​0.0030 or less, and were found to have excellent electrical properties.

[0063] It was found that Examples 1 to 11, in which the ratio of input O2 / theoretical O2 was 1.2 or more, had significantly lower amounts of unreacted materials and by-reactants, and also had smaller dielectric loss tangents / specific surface areas, than Comparative Example 1, in which the ratio was a low 1.1. Here, the amounts of unreacted materials and by-reactants may contain an error of about 0.1 to 0.2%, but the value of 5.6% in Comparative Example 1 was clearly larger than the values ​​in Examples 1 to 11. The test samples of Comparative Examples 2 and 3 had low circularity and large dielectric loss tangents / specific surface areas.

[0064] Therefore, it was found that when the (XRD peak intensity at 26.6°) / (peak intensity at 24.2°) ratio is 1.20 or more, the electrical properties are excellent and the amount of unreacted and by-reacted materials is small. When preparing such composite oxide particle materials, it was found that it is effective to set the ratio of input O2 / theoretical O2 amount to 1.2 or more.

Claims

1. The average particle size is 0.1 μm or more and 5.0 μm or less, BET specific surface area is 1m ２ / g or more, 20m ２ / g or less, A composite oxide particle material comprising a composite oxide of molybdenum and zinc, having an impurity concentration of 1 mass % or less and a circularity of 0.90 or more.

2. 2. The composite oxide particulate material according to claim 1, which has a relative dielectric constant of 16 or less.

3. (dielectric loss tangent) / (BET specific surface area (m ２ 3. The composite oxide particulate material according to claim 1, wherein the value of (a) is 0.0030 or less.

4. 4. The composite oxide particulate material according to claim 1, wherein (XRD peak intensity at 26.6°) / (peak intensity at 24.2°) is 1.20 or more.

5. 5. The composite oxide particulate material according to claim 1, which is surface-treated with an organosilicon compound.

6. A method for producing the composite oxide particulate material according to any one of claims 1 to 5, comprising: a raw particle material preparation step of preparing one or more raw particle materials comprising metallic molybdenum and metallic zinc as a whole; a composite oxide particle material production step in which the raw material particle material is dispersed in a carrier and continuously introduced into a flame in an oxidizing atmosphere for combustion to produce a composite oxide particle material; and A method for producing a composite oxide particle material, in which the ratio (R / T) of the amount of oxygen per unit time T required to completely oxidize the raw particle material and the flammable gas to the amount of oxygen per unit time R introduced into the oxidizing atmosphere is 1.2 or more.

7. A filler for use in a resin composition for electronic materials, comprising the composite oxide particulate material according to any one of claims 1 to 5.

8. The filler of claim 7 containing other inorganic particulate materials.

9. The filler according to claim 7 or 8; a dispersion medium for dispersing the filler; A filler-containing slurry composition comprising:

10. The filler according to claim 7 or 8; a resin material in which the filler is dispersed; A filler-containing resin composition comprising:

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