Resin composition and method for producing the same

Abstract

The present invention provides a resin composition containing a high-purity particulate material and a method for producing the same. The resin composition of the present invention has a particulate material composed of silica surface-treated with a silane compound and a resin material dispersing the particulate material, a viscosity at a shear rate of 1 / sec of 5 Pa-s or more, and 1.0 or less of foreign matter having a length of 20 μm or more; an amount of Na in a liquid extracted from a sample of 30 g in 30 mL of ion exchange water under an environment of 121°C for 20 hours of 30 ppm or less; a BET specific surface area of a post-ashing particulate material obtained by ashing treatment at 800°C for 30 minutes in the atmosphere of 9 to 550 m 2 / g; and a total amount of Na in the post-ashing particulate material of 1000 ppm or less based on the total mass.

Description

Technical Field

[0001] This invention relates to a resin composition and a method for manufacturing the same. Background Technology

[0002] In the past, inorganic materials such as silica have been found to have superior thermal stability and other properties compared to resin materials. Resin compositions in which tiny particles formed from inorganic materials such as silica are dispersed in resin materials have been used for various applications.

[0003] As a method for dispersing particulate material in a resin material, there is a method for contacting and reacting a reactive silane coupling agent having reactive groups that are reactive with the resin material on the surface of the particulate material (see Patent Document 1). By introducing reactive groups that are reactive with the resin onto the surface of the particulate material, a resin composition with high stability can be obtained. Silane coupling agents are compounds that can bind to the surface of inorganic materials and can introduce reactive groups onto the surface of particulate materials.

[0004] For example, by controlling the overreactivity of the silane coupling agent for silica with nanoscale particle size, a stable resin composition containing silica with nanoscale particle size was produced without causing gelation (see Patent Document 2).

[0005] These resin compositions can be added to semiconductor sealing materials, adhesives, etc., or mixed with coatings, varnishes, and appropriate materials for curing and molding. They can be widely used in varnishes, prepregs, insulating films, etc. for electronic substrates.

[0006] However, in recent years, with the miniaturization and high performance of electronic devices such as personal computers and mobile phones, and the advancement of IC packaging micro-scale technology, the narrowing of the gap between bumps is developing. In particular, the spacing of small bumps used in TSV interposers and other three-dimensional high-integration technologies is generally 55μm, but it is expected that the size will be further reduced in the future, and it has been pointed out that the spacing length can be reduced to 20μm or 5μm.

[0007] From the above technical background, the performance requirements for the bottom filler material between the filler bumps are also increasing as the spacing decreases. For example, there is a strong demand to reduce the size and amount of foreign matter that may cause failure, as well as to reduce the composition (impurities) that corrode the bumps.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2009-155138

[0011] Patent Document 2: Japanese Patent Application Publication No. 11-43319 Summary of the Invention

[0012] As mentioned above, with the miniaturization of semiconductor IC packaging, the presence of problematic substances (micro-defects, bump corrosion components) that cause failures has become more problematic, and there is an increasingly strong demand to reduce them compared to the past.

[0013] However, resin compositions containing conventional particle materials with nanoscale particle sizes have high viscosity and poor workability, making it difficult to reduce problematic substances in subsequent processes after the resin composition is made.

[0014] The present invention was made in view of the above-mentioned facts, and the problem it aims to solve is to provide a resin composition containing high-purity particulate material and a method for manufacturing the same.

[0015] To solve the aforementioned problems, the inventors conducted in-depth research and, as a result, completed the following invention. Specifically, the resin composition of the present invention comprises a silica particle material whose surface is treated with a silane compound, and a resin material dispersing the particle material, having a viscosity of 5 Pa at a shear rate of 1 / sec. Foreign objects with a length greater than s and a major diameter greater than 20 μm are defined as less than 2.0 objects / 10g.

[0016] Add 50g of the sample to 50mL of ion-exchange water and extract at 121℃ for 20 hours. The Na content in the solution is below 30ppm.

[0017] The BET specific surface area of ​​the ashed particle material obtained by ashing at 800℃ for 30 minutes in the atmosphere is 9–550 m². 2 / g,

[0018] The total Na content, based on the total mass of the ashed particle material, is less than 1000 ppm, and the Al content is 20 to 3000 ppm.

[0019] By including Na and Al, the silica surface readily bonds chemically with the silane coupling agent, further enhancing the chemical bonding between the functional groups of the coupling agent and the resin. Consequently, the viscosity of the silica-containing resin decreases. As a resin material, it is preferable to use a resin material with a viscosity of 4.9 Pa at 25°C. Materials below s.

[0020] In particular, the mass of the ashed particle material, based on the total mass, is preferably 10-80% by mass. Furthermore, the content of foreign matter with a major diameter of 10 μm or more in the ashed particle material is preferably 9.0 particles / 10g or less. Moreover, the amount of Na in the PCT extract of the ashed particle material is preferably 30 ppm or less, and the total anion concentration is preferably 30 ppm or less.

[0021] The amount of foreign matter with a major diameter of 5 μm or more is less than 25.0 particles / 10g, and the FT-IR spectrum of the particle material is preferably in the range of 2900–3000 cm⁻¹. -1 There are peaks from aliphatic molecules, at 3000–3100 cm⁻¹ -1 There are peaks from the aromatic ring.

[0022] Furthermore, the method for manufacturing the resin composition of the present invention, which solves the above-mentioned problems, is a method for manufacturing the resin composition of the present invention, comprising: an ion removal step of contacting a raw material silica sol with an ion exchange resin to prepare a refined silica sol; a resin composition preparation step of mixing a resin material to prepare a resin composition while removing the dispersion medium of the refined silica sol; a removal step of filtering the raw material silica sol and / or the refined silica sol to remove foreign matter before the completion of the resin composition preparation step; and a surface treatment step of surface treating the raw material silica sol and / or the refined silica sol with a silane compound before the completion of the resin composition preparation step. Detailed Implementation

[0023] The resin composition and its manufacturing method of the present invention will be described in detail below based on embodiments.

[0024] The resin composition of this embodiment is suitable for use as a sealing material for semiconductor devices, a bottom filler, or other semiconductor-related filler material. The numerical values ​​described in this specification can be used, when corrected, to define a range in which the value is used as an upper or lower limit; this range may or may not include the value. Furthermore, the numerical range "x~y" described in this specification includes both the lower limit x and the upper limit y. Moreover, these upper and lower limits, as well as the numerical values ​​listed in the specification or examples, can be arbitrarily combined to form new numerical ranges. A new numerical range may also be a range that does not include one or both of the upper and lower limits. For example, a range greater than x or less than y can be used. Furthermore, a value arbitrarily selected from any of the above numerical ranges can be used as the upper or lower limit of a new numerical range.

[0025] (Resin composition)

[0026] The resin composition of this embodiment includes a particulate material and a resin material for dispersing the particulate material. Furthermore, the ashing particulate material, described later, has a total Na content of 1000 ppm or less, preferably 900 ppm or less, 800 ppm or less, or 700 ppm or less, based on total mass.

[0027] Furthermore, the total Al content of the ashed particulate material is 20–3000 ppm. Examples of lower limits for total Al content include 20 ppm, 50 ppm, and 100 ppm, while examples of upper limits include 3000 ppm, 2000 ppm, and 1500 ppm. These lower and upper limits can be combined arbitrarily.

[0028] The total Na and total Al content were determined by immersing the ashed particle material in hydrofluoric acid or similar solution to decompose the particle material, followed by overall measurement using an inductively coupled plasma (ICP) luminescence spectrophotometer. Furthermore, in addition to Na content, K content is preferably also included within the aforementioned range.

[0029] The resin composition of this embodiment has a lower limit viscosity of 5 Pa at a shear rate of 1 / sec. s or more, preferably 8 Pa s or more, 10 Pa s or more, 15Pa The upper limit is preferably 500 Pa or higher. Below s, 300Pa Below s, 200Pa Below s. The resin composition of this embodiment has a low number of foreign matter particles, even with high viscosity. Generally, viscosity increases by increasing the proportion of particulate material or increasing the molecular weight of the resin material. Therefore, this resin composition is characterized by a high concentration of silica particulate material, the use of a resin material with a large molecular weight, and a low number of foreign matter particles.

[0030] In the resin composition of this embodiment, the number of foreign objects with a major diameter of 20 μm or more is 2.0 or less per 10g, preferably 1.0 or less per 10g. Furthermore, the number of foreign objects with a major diameter of 10 μm or more is preferably 9.0 or less per 10g, more preferably 5 or less per 10g. Moreover, the number of foreign objects with a major diameter of 5 μm or more is preferably 25.0 or less per 10g, more preferably 20 or less per 10g.

[0031] The quantity of foreign matter is determined by the number of particles remaining on a sieve after the resin composition is dispersed in a suitable dispersion medium or after being prepared into ashed particles as described above, when passed through a sieve with a 20 μm pore size. Using a resin composition quantity greater than 10 g during the measurement allows for a more precise calculation of the foreign matter quantity.

[0032] Furthermore, for the resin composition, 30g of the sample is weighed and placed in a pressure-resistant container, then immersed in 30mL of ion-exchange water. The PCT (pressure cooker test) extract obtained after sealing and heating at 121°C for 20 hours preferably contains less than 30ppm of Na, less than 25ppm of Na, less than 20ppm of Na, and less than 10ppm of Na, and less than 30ppm of Na, less than 25ppm of Na, less than 20ppm of Na, and less than 10ppm of Na. If the resin composition is before curing, it is left as is; if it is after curing, it is refined to a size of less than 1mm before measurement. Furthermore, in addition to Na content, K content is preferably also included within the above ranges.

[0033] The particle material is composed of silicon dioxide. Here, "composed of silicon dioxide" means that, based on the total mass of the particle material, the silicon dioxide content is 50% or more, preferably 60% or more, 70% or more, 80% or more, 90% or more, 95% or more, 99% or more, or 100% (excluding unavoidable impurities).

[0034] The particle material is surface-treated with a silane compound. Examples of silane compounds include silane coupling agents and silazanes. Silane compounds that can introduce functional groups with high affinity to the contained resin composition are particularly preferred.

[0035] Compounds having functional groups such as epoxy, alkyl, phenyl, amino, methpropylene, and phenylamino can be cited as silane coupling agents. Hexamethyldisilazane can be cited as a silazane. The carbon derived from the silane compound used for surface treatment is bonded to the surface of the particle material; the amount of carbon, based on the mass of the particle material, is preferably 30% or less, 20% or less, or 15% or less.

[0036] Furthermore, the silica particle material is preferably chemically bonded to the resin using a silane coupling agent. The chemically bonded carbon content (A) of the silica treated only with the silane coupling agent and the chemically bonded carbon content (B) of the surface-modified silica mixed with the resin are considered to be bonded to the resin if B ÷ A is greater than 1.2. The chemically bonded carbon content is determined by washing with a solvent with high affinity for physically adsorbed organic components, heating and distilling off the solvent, and then measuring the carbon content. Examples of solvents include acetone, methyl ethyl ketone, propylene glycol monomethyl ether, toluene, ethyl acetate, butyl acetate, ethanol, and isopropanol, but are not limited to these.

[0037] In addition, FT-IR, Raman spectroscopy, and EGA-MS can also be used as evaluation methods for chemically bound organic compounds from silica after the removal of physically adsorbed organic components. In FT-IR, detection at 2900-3000 cm⁻¹ is preferred. -1 The peaks from aliphatic CH and 3000-3100 cm⁻¹ -1The peak originating from the aromatic ring CH. Additionally, the peak at 3740 cm⁻¹... -1 The disappearance of the peak from silanol indicates that the silanol was completely reacted by the surface treatment agent.

[0038] The particle size of the material is preferably above 2 nm and below 300 nm. The lower limit of the desired particle size can be 10 nm, 9 nm, 7 nm, 5 nm, or 3 nm, while the upper limit can be 80 nm, 100 nm, 150 nm, 200 nm, or 250 nm. These upper and lower limits can be combined arbitrarily.

[0039] Here, particle size refers to the D50 value of the circular equivalent diameter (SEM diameter) of each particle material present in a randomly selected field of view in an image obtained by SEM. D50 refers to the particle size that reaches 50% when the volume calculated from the circular equivalent diameter is accumulated, starting from the smallest particle material.

[0040] The sphericity of the particle material is preferably above 0.70, 0.80, 0.85, or 0.90. Sphericity is determined by SEM imaging, based on the observed particle area and perimeter, using the formula: (Sphericity) = {4π × (Area) ÷ (Perimeter)}. 2 The result is calculated as follows: the closer the result is to 1, the closer it is to a true sphere. Specifically, the average value of 100 particles is determined using image analysis software (Asahi Kasei Engineering Co., Ltd.: A-Image).

[0041] The BET specific surface area of ​​the ashed particle material remaining after ashing at 800°C for 30 minutes in atmosphere, measured with nitrogen, is 9–550 m². 2 / g. The lower limit of BET specific surface area can be 9m². 2 / g、14m 2 / g、18m 2 / g、27m 2 / g、34m 2 / g, with an upper limit of 450m 2 / g、390m 2 / g、303m 2 / g、273m 2 / g. These upper and lower limits can be combined arbitrarily.

[0042] The mass of the ashed particle material, based on the total mass of the resin composition, is preferably 10-80% by mass, with 70%, 60%, and 50% by mass as the upper limit and 15%, 20%, and 25% by mass as the lower limit. These upper and lower limits can be combined arbitrarily.

[0043] The preferred true specific gravity of the ashing particle material is 2.1 g / cm³. 3 Above, 2.15g / cm 3 Above, 2.17 g / cm 3 Above, 2.19 g / cm 3 Above, 2.21 g / cm 3 Above, 2.25g / cm 3 The above. True specific gravity is determined by calculation in a helium atmosphere.

[0044] Elemental analysis can be performed using inductively coupled plasma optical emission analysis (ICP-OES) and / or ion chromatography.

[0045] After the ashing particles are dissolved in hydrofluoric acid, the content of each element can be quantified by ICP-OES.

[0046] As a resin material, it includes polymers and other high-molecular materials that are melted upon heating, and precursors thereof before becoming high-molecular materials. Examples of high-molecular materials include polyimide resins, epoxy resins, urea-formaldehyde resins, or their precursors. Preferably, the resin material has an upper limit of 4.9 Pa in viscosity alone at 25°C. s, 4.0Pa s, 3.0Pa s, 2.0Pa The material of s.

[0047] In addition to adding liquid polymer materials, particulate polymer materials can also be dispersed in refined silica sol. Then, by removing the dispersion medium, a resin composition in which silica particulate materials are dispersed in the polymer material can be obtained. In this case, the appearance color after removing the dispersion medium preferably has transparency (transparent to white-transparent).

[0048] (Method for manufacturing resin composition)

[0049] The method for manufacturing the resin composition according to this embodiment includes an ion removal step, a resin composition preparation step, a removal step, a surface treatment step, and other steps selected as needed.

[0050] The ion removal process involves contacting the raw silica sol with both cation exchange resins and anion exchange resins to form a refined silica sol. Contact with the cation exchange resin removes cations such as sodium ions from the raw silica sol. Contact with the anion exchange resin removes anions such as chloride ions and sulfate ions from the raw silica sol. The order of treatment with the cation and anion exchange resins is not specifically defined.

[0051] Specific methods include passing a raw silica sol through a column filled with beads made of ion exchange resin, and separating the beads after dispersing them in the raw silica sol. The degree of removal of cations and anions is preferably reduced to a level that achieves the desired amount of cations and anions in the aforementioned resin composition. Furthermore, the term "silica sol" as used in this specification refers to a substance in which silica particles are dispersed in a dispersion medium.

[0052] The raw material is silica sol, such as water glass. Water glass is formed by dissolving metallic silicon or silica in an aqueous solution containing an alkaline substance. Preferably, the alkaline substance is free of metals, and examples include substances containing ammonia or ammonium salts. Silica can be naturally derived, derived from metallic silicon, derived from silicon tetrachloride, etc., and there is no particular limitation.

[0053] The resin composition preparation process involves obtaining the resin composition by replacing the dispersion medium of refined silica sol with a resin material. One method for replacing the dispersion medium is to dissolve the resin material after replacing the dispersion medium with an aqueous organic solvent, thereby removing the aqueous organic solvent. Alternatively, the process can be performed by adding a resin material solution to the refined silica sol, thereby removing the dispersion medium and solvent.

[0054] The solvent for the resin material solution is an aqueous organic solvent. An aqueous organic solvent is a solvent that can dissolve the resin material, has a boiling point higher than the dispersion medium, and is miscible with the dispersion medium.

[0055] Examples of aqueous organic solvents include propylene glycol monomethyl ether (propylene glycol-1-methyl ether, boiling point approximately 119°C; propylene glycol-2-methyl ether, boiling point approximately 130°C), butanol (boiling point 117.7°C), N-methyl-2-pyrrolidone (boiling point approximately 204°C), and γ-butyrolactone (boiling point approximately 204°C).

[0056] By removing the dispersion medium and solvent, a resin composition containing particles of silica contained in refined silica sol can be obtained. The removal of the dispersion medium and solvent can be carried out by heating or reducing pressure.

[0057] The removal process is a step performed before the resin composition preparation process is completed, in which raw silica sol and / or refined silica sol are filtered to remove foreign matter. In particular, the raw silica sol and refined silica sol before mixing the resin materials have low viscosity, therefore filtration is preferably performed before mixing the resin materials.

[0058] In addition, when the substance to be removed is a magnetic material, magnetic force can be used to separate the substance.

[0059] The surface treatment step is a process of treating the raw silica sol and / or refined silica sol with a silane compound before the resin composition preparation step is completed. The type and amount of silane compound can be directly referred to in the above description. The silane compound can be added directly or dissolved in a solvent that can dissolve the silane compound.

[0060] Example

[0061] The resin composition and its manufacturing method of the present invention will be described in detail based on the embodiments.

[0062] (Raw material: silica sol)

[0063] ST-OS (average particle size: 9nm, silica concentration: 20wt%, manufactured by Nissan Chemical Industries)

[0064] SI-30 (average particle size: 10nm, silica concentration: 20wt%, manufactured by Nichibujin catalyst)

[0065] ST-O-40 (average particle size: 22nm, silica concentration: 40wt%, manufactured by Nissan Chemical).

[0066] SI-45P (average particle size: 45nm, silica concentration: 40wt%, manufactured by Nichibujote catalyst)

[0067] ST-OL (average particle size: 45nm, silica concentration: 20wt%, manufactured by Nissan Chemical).

[0068] SI-80P (average particle size: 80nm, silica concentration: 40wt%, manufactured by Nichibukai Catalyst Chemicals)

[0069] (Raw material: silica sol: Experimental Example 1)

[0070] A 2L reaction vessel was placed in a 50°C oil bath. 222g of ethanol, 590g of water, and 295g of 25wt% ammonia solution were added. The mixture was stirred at 100rpm using a pneumatic stirrer while being heated to 50°C. Then, while stirring the mixture, 190g of tetraethoxysilane was continuously added over 10 minutes using a tubular pump to obtain a silica slurry. The silica concentration was 5wt%, the average particle size was 50nm, and the sphericity was 0.67.

[0071] (Resin material)

[0072] ZX-1059: Liquid bisphenol-type epoxy resin, resin viscosity: 2.5 Pa s, Nippon Steel Chemical & Material Manufacturing

[0073] YDF-8170C: Liquid bisphenol-type epoxy resin, resin viscosity: 1.0 Pa s, Nippon Steel Chemical & Material Manufacturing

[0074] jER630: Multifunctional epoxy resin, resin viscosity 0.8 Pa s, Mitsubishi Chemical Co., Ltd.

[0075] (Silane coupling agent)

[0076] KBM-303: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry.

[0077] KBM-403: 3-Glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0078] KBM-4803: 3-Glycidoxyoctyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry.

[0079] KBE-403: 3-Glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0080] (Example 1)

[0081] A refined silica sol was obtained by fully contacting 100 parts by weight of raw silica sol (ST-OS, manufactured by Nissan Chemical, silica content 20% by weight: dispersed in water: volume average particle size 9 nm) with a strongly acidic cation exchange resin (HPR1024 H, manufactured by Organo) and then fully contacting it with a strongly basic ion exchange resin (IRA400J CL). (Ion removal process).

[0082] At this point, the amount of Na contained in the silica is 300 ppm, the amount of Na in the aqueous solution is <5 ppm, and the total amount of anions is <5 ppm.

[0083] Next, surface treatment was performed using 300 parts by mass of an aqueous solvent (propylene glycol monomethyl ether (hereinafter referred to as "PGM")) and a silane coupling agent as a silane compound (KBM-403 (3-glycidoxypropyltrimethoxysilane), manufactured by Shin-Etsu Chemical Industry Co., Ltd.). The chemically bound carbon content of this surface-modified silica sol was 6%, and it was detected in FT-IR at 2900-3000 cm⁻¹. -1 The peak from aliphatic CH, 3740 cm⁻¹-1 The peak from silanol disappeared.

[0084] Then, 60 parts by weight of epoxy resin (ZX-1059, manufactured by Nippon Steel Chemical & Material) as the resin material were mixed, and after passing through a cartridge filter with a filtration accuracy of 1 μm (removal step), the dispersion medium and aqueous solvent were removed by heating and depressurization in an evaporator to obtain the resin composition of this embodiment (resin composition preparation step). The chemically bound carbon content of the silica particles in this resin composition is 20%, and 2900-3000 cm⁻¹ was detected in FT-IR. -1 The peaks from aliphatic CH and 3000-3100 cm⁻¹ -1 The peak from the aromatic ring CH, 3740 cm⁻¹ -1 The peak from silanol disappeared.

[0085] Examples 2 through 6 were prepared according to the sample preparation method of Example 1, as described in Table 1.

[0086] (Comparative Example 1)

[0087] Except for omitting the removal process (1μm filtration) of Example 1, the same steps were performed to obtain the resin composition of this comparative example.

[0088] (Comparative Example 2)

[0089] Except for omitting the removal step in Example 6, the same steps were performed to obtain the resin composition of this comparative example.

[0090] (Comparative Example 3)

[0091] The same steps were performed except that the addition of 300 parts by mass of PGM in Example 1 was changed to the addition of 50 parts by mass of PGM, but the viscosity of the mixture was so high that it could not be filtered to 1 μm.

[0092] (Comparative Example 4)

[0093] The same steps were performed except that the addition of 300 parts by mass of PGM in Example 6 was changed to the addition of 50 parts by mass of PGM, but the viscosity of the mixture was so high that it could not be filtered to 1 μm.

[0094] (Comparative Example 5)

[0095] Except for omitting the step of contacting the strongly acidic cation exchange resin and the strongly basic ion exchange resin with the raw material silica sol in Example 2, and changing the silane coupling agent KBE-403 to KBM-403, the same steps were performed to obtain the resin composition of this comparative example.

[0096] (Comparative Example 6)

[0097] Except for omitting the step of contacting the strongly acidic cation exchange resin and the strongly basic ion exchange resin with the raw material silica sol in Example 6, the same steps were performed to obtain the resin composition of this comparative example.

[0098] (Comparative Example 7)

[0099] Except for using the silica sol obtained in Example 1, the same steps as in Example 5 were followed. However, when the solvent was distilled off, the high viscosity gelled into a white solid, so it was impossible to evaluate the various physical properties of the resin dispersion.

[0100] (Comparative Example 8)

[0101] Except for omitting the step of contacting the strongly basic ion exchange resin with the raw material silica sol in Example 4, the same steps were performed to obtain the resin composition of this comparative example.

[0102] (Comparative Example 9)

[0103] Except for omitting the surface treatment with silane coupling agent as in Example 2, the same steps were performed to obtain the resin composition of this comparative example.

[0104] (evaluate)

[0105] The resin compositions of each embodiment and comparative example were subjected to ashing treatment. The ashing treatment was carried out at 800°C for 30 minutes under atmospheric atmosphere. The residue was used as the ashed particle material, and the BET specific surface area was analyzed using nitrogen. The results are shown in Table 2.

[0106] For the aqueous solutions after ion removal in each embodiment and comparative example, ion-exchanged water was added to adjust the silica sol concentration to 10 wt%. A centrifugal ultrafiltration filter unit (molecular weight: 10000) was added, and the silica components and aqueous solution were separated using a centrifuge (a high-speed cooling centrifuge MODEL6000 manufactured by Kubota Corporation) at 4000G for 30 minutes. The amount of Na and anions in the recovered aqueous solution was determined by ion chromatography, and the results are shown in Table 1.

[0107] For the resin compositions of each embodiment and comparative example, the viscosity at a shear rate of 1 / s was measured using an E-type viscometer. The results are shown in Table 2.

[0108] 10g of the resin compositions from each example and comparative example were mixed with 30g of PGM, and the resins were fully dissolved by ultrasonic irradiation. Then, the number of foreign objects captured on the sieve when passed through a sieve with a specified aperture was recorded. The results are shown in Table 2.

[0109] For the resin compositions of each embodiment and comparative example, the PCT extract obtained by the method described in the embodiments was subjected to determination of the amount of Na and anions by ion chromatography, and the results are shown in Table 2.

[0110] The Na content of the ashing particle material was determined using an inductively coupled plasma (ICP) luminescence spectrophotometer, and the results are shown in Table 2.

[0111] The chemically bound carbon content analysis and FT-IR determination methods for surface-modified silica are as follows. 10g of surface-modified silica sol or 10g of a silica-containing resin composition was mixed with 10g of butyl acetate and 30g of toluene (both low-solvent components). After ultrasonic irradiation for at least 5 minutes, the silica components were precipitated using a centrifuge (Kubota Corporation MODEL6000 high-speed refrigerated centrifuge) at 20000G for 30 minutes. The supernatant was discarded, and 30g of butyl acetate was added. After ultrasonic irradiation for at least 5 minutes, the silica components were precipitated using a centrifuge at 20000G for 30 minutes. The supernatant was then discarded, and the precipitated silica was dried using a hot air dryer. Residual solvent was distilled off, and the resulting dry powder was analyzed using a carbon content analyzer (HORIBA EMIA-321V) and FT-IR diffusion reflectance spectroscopy. In the FT-IR, the carbon content of aliphatic CH4 (2900–3000 cm⁻¹) was confirmed. -1 The presence or absence of peaks, originating from the aromatic ring CH at 3000–3100 cm⁻¹ -1 The presence or absence of the peak, and the origin of SiOH at 3740 cm⁻¹ -1 The presence or absence of a peak.

[0112]

[0113]

[0114] As can be seen from the table, based on the results of Examples 2 and 5, and Examples 6 and 6 and 6, the amount of Na in the obtained resin composition, as well as the amount of Na and anion in the PCT extract, can be reduced by performing the ion removal process.

[0115] Furthermore, based on the results of Examples 1 and 1, and Examples 6 and 2, the number of foreign matter with particle sizes of 20 μm or larger, 10 μm or larger, and 5 μm or larger can be reduced by performing the removal process. Additionally, based on the results of Comparative Examples 3 and 4, adding solvents such as PGM is effective in facilitating the removal process.

[0116] Based on the results of Example 5 and Comparative Example 7, when the Na and Al contents of the silica particles are at a certain level, the reactivity of silica with the silane coupling agent and the resin is promoted, the affinity between silica and the resin is improved, and the viscosity of the resin dispersion is reduced.

[0117] From the results of Example 4 and Comparative Example 8, it is evident that by performing an anion removal process, the total amount of anions in the PCT extract of the obtained resin composition can be reduced. From the results of Example 2 and Comparative Example 9, it is evident that by performing a surface treatment process, the silane coupling agent chemically bonds as a bridge between the resin and silica, and the silica does not agglomerate after solvent removal, thus imparting transparency, fluidity, and dispersibility.

Claims

1. A resin composition comprising a particulate material and a resin material dispersing the particulate material, said particulate material being composed of silica whose surface has been surface-treated with a silane compound. The viscosity of the resin composition at a shear rate of 1 / sec is 5 Pa. The content of foreign matter with a length diameter of 20 μm or more and a major diameter of 20 μm or more is less than 1.0 per 10g. A 30g sample of the resin composition was added to 30mL of ion-exchange water and extracted at 121℃ for 20 hours. The Na content in the resulting solution was below 30ppm. The BET specific surface area of ​​the ashed particle material obtained by ashing at 800℃ for 30 minutes in the atmosphere is 9–550 m². 2 / g, Furthermore, the total Na content of the resin composition, based on the total mass of the ashing particle material, is 20 to 1000 ppm, and the Al content is 20 to 3000 ppm.

2. The resin composition according to claim 1, wherein, The mass of the ashing particle material is 10-80% of the total mass. Of the foreign matter, the content of foreign matter with a major diameter of 10 μm or more is less than 9.0 per 10g. The amount of Na in the PCT extract of the resin composition is less than 30 ppm, and the total amount of anions is less than 30 ppm.

3. The resin composition according to claim 1 or 2, wherein, Of the foreign matter, the content of foreign matter with a major diameter of 5 μm or more is less than 25.0 per 10g. The FT-IR spectrum of the particle material is in the range of 2900–3000 cm⁻¹. -1 There are peaks from aliphatic molecules, in the range of 3000–3100 cm⁻¹. -1 There are peaks from the aromatic ring.

4. A method for manufacturing a resin composition, comprising the method for manufacturing the resin composition according to any one of claims 1 to 3, wherein: The ion removal process involves contacting raw silica sol with cation exchange resin and anion exchange resin to produce refined silica sol. The resin composition preparation step involves removing the dispersion medium of the refined silica sol and mixing it with resin materials to prepare a resin composition. Before the resin composition preparation process is completed, a removal process is performed to remove foreign matter by filtering the raw material silica sol and / or the refined silica sol, and... A surface treatment process in which the raw material silica sol and / or the refined silica sol are surface-treated with a silane compound before the completion of the resin composition preparation process.

5. The method for manufacturing the resin composition according to claim 4, comprising a dissolution step of contacting and dissolving a raw material composed of metallic silicon and / or silicon dioxide in an alkaline aqueous solution to generate the raw material silicon dioxide sol.

6. The method for manufacturing the epoxy resin composition according to claim 4 or 5, wherein, The removal process is a process of removing foreign matter until the number of foreign matter particles larger than 20 μm is reduced to less than 1.0 particle / 10g.

7. The method for manufacturing the resin composition according to any one of claims 4 to 6, wherein, The removal process is a process of removing foreign matter until the number of foreign matter particles larger than 10 μm is reduced to less than 9.0 particles / 10g.

8. The method for manufacturing the resin composition according to any one of claims 4 to 7, wherein, The removal process is a process of removing foreign matter until the number of foreign matter particles larger than 5μm is reduced to less than 25.0 particles / 10g.

Images