Resin composition and its manufacturing method

Abstract

The problem to be solved is to provide a resin composition containing high-purity particulate material and a method for manufacturing the same. The composition comprises particulate material made of silica surface-treated with a silane compound and a resin material in which the particulate material is dispersed. The composition has a viscosity of 5 Pa·s or higher at a shear rate of 1 / sec, and contains less than 1.0 foreign matter per 100g with a major diameter of 20 μm or higher. The Na content in the extract obtained by placing 30 g of the sample in 30 mL of ion-exchange water and extracting at 121°C for 20 hours is less than 30 ppm. The BET specific surface area of ​​the ashed particulate material obtained by ashing at 800°C for 30 minutes in atmospheric conditions is 9–550 m² / g, and the total Na content based on the total mass of the ashed particulate material is less than 1000 ppm.

Description

[Technical Field]

[0001] This invention relates to resin compositions and their manufacturing methods. [Previous Technology]

[0002] In the past, inorganic materials such as silicon oxide have been superior to resin materials in terms of thermal stability, and resin compositions in which tiny particles formed from inorganic materials such as silicon oxide are dispersed in resin materials have been used in various applications.

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

[0004] For example, by controlling the excessive reactivity of the silane coupling agent to silicon oxide with a particle size of nanoscale, it is possible to produce a stable resin composition containing silicon oxide with a particle size of nanoscale without causing gelation (see Patent Document 2).

[0005] These resin compositions can be added to semiconductor sealants, adhesives, etc., or cured / shaped in a mixture with coatings or paints or suitable materials and are widely used in varnishes, prepregs, insulating films, etc., which can be used on electronic substrates.

[0006] In recent years, with the miniaturization and high performance of electronic devices such as personal computers and mobile phones, IC packaging miniaturization technology has advanced, leading to continuous progress in narrowing the pitch between bumps. In particular, the pitch between small bumps used in TSV interposers and other high-integration technologies in three dimensions is generally 55 μm, but it is foreseeable that the size will continue to shrink in the future, suggesting the possibility of the pitch length being reduced to 20 μm or 5 μm.

[0007] As can be seen from the above technical background, the bottom filler material used to fill the spaces between bumps also requires higher performance as the spacing decreases. For example, it is strongly required to reduce the size or amount of foreign matter that causes defects or to reduce the components (impurities) that corrode the bumps.

[0008] 『Patent Documents』 《Patent Document 1》: Japanese Patent Publication No. 2009-155138 《Patent Document 2》: Japanese Patent Publication No. H11-43319 [Summary of the Invention]

[0009] As explained above, with the miniaturization of semiconductor IC packaging, the presence of problem substances (microscopic foreign matter, bump corrosion components) that can cause defects has become a problem, and the need to reduce these is more intense than ever before.

[0010] However, resin compositions containing conventional particle materials with nanoscale particle sizes have high viscosity and therefore poor workability. In the subsequent processes after the resin composition is made, it is very difficult to reduce problematic substances.

[0011] The present invention was made in view of the above-mentioned facts, and aims to solve the problem of providing a resin composition containing particulate material with high purity and a method for manufacturing the same.

[0012] To solve the above-mentioned problems, the inventors have diligently conducted research and, as a result, completed the following invention. Specifically, the resin composition of the present invention comprises a particle material made of silica with a surface treated with a silane compound and a resin material in which the aforementioned particle material is dispersed. The viscosity at a shear rate of 1 / sec is 5 Pa·s or higher, and the number of foreign matter with a major diameter of 20 μm or higher is 2.0 pieces / 10g or less. When 50 g of the sample is placed in 50 mL of ion-exchange water and extracted at 121°C for 20 hours, the amount of Na in the extract is 30 ppm or less. The BET specific surface area of ​​the ashed particle material obtained by ashing at 800°C for 30 minutes in atmospheric conditions is 9–550 m² / g. The total Na content, based on the total mass of the ashed particle material, is 1000 ppm or less, and the Al content is 20–3000 ppm.

[0013] By containing Na and Al, the silicon oxide surface and the silane coupling agent become more easily chemically bonded, and the chemical bonding between the functional groups of the coupling agent and the resin is further increased. As a result, the viscosity of the resin containing silicon oxide decreases. As a resin material, it is preferable to use a resin material with a viscosity of 4.9 Pa·s or less at 25°C.

[0014] In particular, the mass of the aforementioned ashed particle material is preferably 10-80% by mass, based on the overall 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 is preferably 30 ppm or less, and the total amount of anions is preferably 30 ppm or less.

[0015] Preferably, among the aforementioned foreign matter, the content of those with a major diameter of 5 μm or more is 25.0 or less per 10g, and the aforementioned particle material has a peak originating from aliphatic molecules in the 2900-3000 cm-1 and a peak originating from aromatic rings in the 3000-3100 cm-1 spectrum measured by FT-IR.

[0016] Moreover, the method for manufacturing the resin composition of the present invention that solves the above-mentioned problems is a method for manufacturing the resin composition of the present invention, which includes: an ion removal step, in which an ion exchange resin is contacted with a raw material silica sol to form a refined silica sol; a resin composition preparation step, in which the dispersion medium of the aforementioned refined silica sol is removed and a resin material is mixed to prepare a resin composition; a removal step, in which, before the completion of the aforementioned resin composition preparation step, the aforementioned raw material silica sol and / or the aforementioned refined silica sol are filtered to remove foreign matter; and a surface treatment step, in which, before the completion of the aforementioned resin composition preparation step, the aforementioned raw material silica sol and / or the aforementioned refined silica sol are surface treated with a silane compound.

Implementation Method

[0018] The following describes in detail the resin composition and manufacturing method of the present invention based on embodiments.

[0019] The resin composition of this embodiment is suitable for use as a sealing material, underfill material, or other semiconductor-related filling material for semiconductor devices. In this specification, the numerical values ​​described can be modified to define a range using these values ​​as upper or lower limits; this range may or may not include these values. Furthermore, the numerical range "x to y" described in this specification includes both the lower limit x and the upper limit y. Moreover, new numerical ranges can be constructed by arbitrarily combining these upper and lower limits with the values ​​listed in the specification or examples. The new numerical range can also be defined as a range that does not include one or both of the upper and lower limits. For example, a range exceeding x or a range below y can be used. Furthermore, any value selected from any of the above numerical ranges can be defined as the upper or lower limit of the new numerical range.

[0020] (Resin composition)

[0021] The resin composition of this embodiment includes a particulate material and a resin material in which the particulate material is dispersed. Furthermore, the total Na content of the ashing particulate material described later is preferably 1000 ppm or less, and more preferably 900 ppm or less, 800 ppm or less, or 700 ppm or less, based on the overall mass.

[0022] Furthermore, the total Al content of the ashing particle material is 20 to 3000 ppm. Examples of lower limits for the 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.

[0023] The total Na and total Al content are measured after the ashing particle material is impregnated with hydrofluoric acid or the like to decompose the particle material, and then the whole material is placed into an inductively coupled plasma (ICP) emission spectrophotometer for measurement. Furthermore, in addition to the Na content, the K content is preferably within the above-mentioned range.

[0024] The resin composition of this embodiment has a lower limit of viscosity of 5 Pa·s or more, preferably 8 Pa·s or more, 10 Pa·s or more, or 15 Pa·s or more, and an upper limit of preferably 500 Pa·s or less, 300 Pa·s or less, or 200 Pa·s or less, at a shear rate of 1 / sec. Even with high viscosity, the resin composition of this embodiment contains few large-particle foreign matter. Generally, since viscosity increases with increasing the proportion of particulate material or increasing the molecular weight of the resin material, this is, in short, a resin composition characterized by a high concentration of silica particulate material or the use of a resin material with a large molecular weight and a low number of foreign matter.

[0025] In this embodiment, the amount of foreign matter with a major diameter of 20 μm or more is preferably 2.0 pieces / 10g or less, and preferably 1.0 piece / 10g or less. Furthermore, the amount of foreign matter with a major diameter of 10 μm or more is preferably 9.0 pieces / 10g or less, and preferably 5 pieces / 10g or less. Moreover, the amount of foreign matter with a major diameter of 5 μm or more is preferably 25.0 pieces / 10g or less, and preferably 20 pieces / 10g or less.

[0026] The amount of foreign matter can be measured as the number of particles remaining on a sieve when the resin composition is dispersed in a suitable dispersion medium or made into ashed particles as described above, and then passed through a sieve with a pore size of 20 μm. By using a amount of resin composition greater than 10 g during measurement, a more precise amount of foreign matter can be calculated.

[0027] Furthermore, after measuring 30 g of the resin composition into a pressure-resistant container as a sample, immersing it in 30 mL of ion-exchange water, and heating it in a sealed container at 121°C for 20 hours, the amount of Na in the PCT (pressure cooker test) extract is preferably 30 ppm or less, 25 ppm or less, 20 ppm or less, and the amount of anion is preferably 30 ppm or less, 25 ppm or less, 20 ppm or less, and 10 ppm or less. If the resin composition is a cured form of the former, then the measurement is performed there; if it is a cured form of the latter, then the sample is subdivided to a size of less than 1 mm before measurement. Furthermore, in addition to the amount of Na, the amount of K is also preferably within the above-mentioned range.

[0028] The particle material is made of silicon oxide. Here, "made of silicon oxide" means that, based on the overall mass of the particle material, the silicon oxide content is 50% or more, preferably 60%, 70%, 80%, 90%, 95%, 99%, or 100% (excluding unavoidable impurities).

[0029] The particle material is surface-treated using a silane compound. Examples of silane compounds include silane coupling agents and silicon nitrides. In particular, it is preferable to use a silane compound with functional groups that have high affinity for the contained resin composition.

[0030] Examples of silane coupling agents include those possessing functional groups such as epoxy, alkyl, phenyl, amino, methacrylyl, and phenylamino. Examples of silicon nitrides include hexamethyldisilazane. The surface of the particle material has carbon derived from the silane compound used for surface treatment, and the carbon content is preferably 30% or less, 20% or less, or 15% or less based on the mass of the particle material.

[0031] Furthermore, it is preferable that the silica particle material is 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 used. If B ÷ A is more than 1.2 times, it can be determined that the silica is bonded to the resin. The chemically bonded carbon content can be measured 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 these are not limited to.

[0032] Furthermore, FT-IR, Raman spectroscopy, and EGA-MS can also be used as evaluation methods for the chemically bonded organic compounds of silica after the removal of the physically adsorbed organic components described above. In FT-IR, it is preferable to detect a peak originating from aliphatic C-H at 2900–3000 cm⁻¹ and a peak originating from aromatic C-H at 3000–3100 cm⁻¹. Furthermore, the disappearance of the peak originating from silanol at 3740 cm⁻¹ indicates that the silanol has been completely reacted by the surface treatment agent.

[0033] The particle material is preferably made with a particle size of 2 nm or more and 300 nm or less. The lower limit of the desired particle size can be 10 nm, 9 nm, 7 nm, 5 nm, or 3 nm, and 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.

[0034] Here, the so-called particle size refers to the D50 value of the equivalent circle diameter (SEM diameter) of each particle material in a randomly selected field of view in an image obtained through SEM. D50 is the particle size that is 50% of the particle size when the volume of the smallest particle material is accumulated from the equivalent circle diameter.

[0035] The sphericity of the particle material is preferably above 0.70, 0.80, 0.85, or 0.90. Sphericity is calculated using SEM images, with the observed particle area and perimeter measured as follows: (Sphericity) = [4π × (Area) ÷ (Perimeter)²]. The closer to 1, the closer to a true sphere. Specifically, the average value of 100 particles is measured using image analysis software (Asahi Kasei Engineering Corporation: A-Image).

[0036] For the resin composition, the BET specific surface area of ​​the ashed particle material remaining after ashing treatment at 800°C for 30 minutes in atmospheric atmosphere, measured using nitrogen, is 9–550 m² / g. The lower limit of the BET specific surface area can be 9 m² / g, 14 m² / g, 18 m² / g, 27 m² / g, and 34 m² / g, and the upper limit can be 450 m² / g, 390 m² / g, 303 m² / g, and 273 m² / g. These upper and lower limits can be combined arbitrarily.

[0037] The mass of the ashed particle material is preferably 10-80% by mass, based on the total mass of the resin composition. The upper limit of the mass of the ashed particle material is preferably 70%, 60%, or 50% by mass, and the lower limit is preferably 15%, 20%, or 25% by mass. These upper and lower limits can be combined arbitrarily.

[0038] The true specific gravity of the ashing particle material is preferably above 2.1 g / cm³, 2.15 g / cm³, 2.17 g / cm³, 2.19 g / cm³, 2.21 g / cm³, or 2.25 g / cm³. The true specific gravity is measured and calculated using a hydrometer in a helium atmosphere.

[0039] Elemental analysis can be performed by inductively coupled plasmaluminescence analysis (ICP-OES) and / or ion chromatography.

[0040] After the ashing particle material is dissolved in hydrofluoric acid, the content of each element can be quantified by ICP-OES measurement.

[0041] The resin material may include polymers or other polymeric materials that melt upon heating, or precursors thereof, which are used to become polymeric materials. Examples of polymeric materials include polyimide resins, epoxy resins, urea resins, or their precursors. Preferably, the resin material itself has an upper limit of viscosity of 4.9 Pa·s, 4.0 Pa·s, 3.0 Pa·s, or 2.0 Pa·s at 25°C.

[0042] Furthermore, in addition to adding liquid polymer materials, particulate polymer materials can also be dispersed in refined silica sol. Afterwards, by removing the dispersion medium, a resin composition in which particulate materials made of silica are dispersed in the polymer material can be obtained. At this time, the appearance color when removing the dispersion medium is preferably transparent (transparent to white transparent).

[0043] (Method for manufacturing resin composition)

[0044] The method for manufacturing the resin composition according to this embodiment includes: an ion removal process, a resin composition preparation process, a removal process, a surface treatment process, and other processes selected as needed.

[0045] The ion removal process involves contacting the raw silica sol with both cation exchange resin and anion exchange resin 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 exchange resin and the anion exchange resin is not particularly limited.

[0046] Specific methods include: passing the raw material silica sol through a column filled with beads made of ion exchange resin, and separating the beads after dispersing them in the raw material silica sol. Regarding the degree of removal of cations and anions, it is preferable to reduce them to a level that achieves a favorable amount of cations and anions in the resin composition described above. Furthermore, in this specification, "silica sol" refers to a dispersion of silica particles in a dispersion medium.

[0047] The raw material, silica sol, can be an example of water glass. Water glass is formed by dissolving metallic silicon or silica in an aqueous solution containing an alkaline substance. As an alkaline substance, it is preferable to be free of metals, and examples include those containing ammonia or ammonium salts. Silica can be derived from natural sources, metallic silicon, silicon tetrachloride, etc., and is not particularly limited.

[0048] The resin composition preparation process is a process of obtaining a resin composition by replacing the dispersion medium of refined silica sol with resin material. As a method for replacing the dispersion medium, an example is a method of dissolving the resin material after replacing the dispersion medium with an aqueous organic solvent, and then removing the aqueous organic solvent. Furthermore, the process is performed by adding refined silica sol to the resin material solution to remove both the dispersion medium and the solvent.

[0049] The solvent for the resin material solution is an aqueous organic solvent. An aqueous organic solvent is a solvent that can dissolve resin materials, has a higher boiling point than the dispersion medium, and can be mixed with the dispersion medium.

[0050] As an aqueous organic solvent, examples include: propylene glycol monomethyl ether (propylene glycol-1-methyl ether, boiling point around 119℃; propylene glycol-2-methyl ether, boiling point around 130℃), butanol (boiling point 117.7℃), N-methyl-2-pyrrolidone (boiling point around 204℃), γ-butyrolactone (boiling point around 204℃), etc.

[0051] By removing the dispersion medium and solvent, a resin composition in which the silicon oxide particles contained in the refined silicon oxide sol are dispersed in the resin material can be obtained. The removal of the dispersion medium and solvent can be carried out by heating or reducing pressure.

[0052] The removal process is a process of filtering raw silica sol and / or refined silica sol to remove foreign matter before the completion of the resin composition preparation process. In particular, since the viscosity of the raw silica sol or refined silica sol before mixing the resin material is low, it is preferable to filter it before mixing the resin material.

[0053] Furthermore, if the substance to be removed is a magnetic material, magnetic force can be used to separate the substance to be removed.

[0054] The surface treatment process is a process of surface treating the raw material silica sol and / or refined silica sol with a silane compound before the completion of the resin composition preparation process. The type and amount of the silane compound can be directly described as above. The silane compound can be added or added in a solvent capable of dissolving the silane compound.

[0055] 『Example』

[0056] The resin composition and manufacturing method of the present invention will be described in detail with reference to the embodiments.

[0057] (Raw material: silica sol) . ST-OS (Average particle size: 9 nm, silica concentration: 20 wt%, manufactured by Nikko Chemical Industry) . SI-30 (Average particle size: 10 nm, silica concentration: 20 wt%, manufactured by Nichibukai Catalyst Chemical) . ST-O-40 (Average particle size: 22 nm, silica concentration: 40 wt%, manufactured by Nikko Chemical) . SI-45P (Average particle size: 45 nm, silica concentration: 40 wt%, manufactured by Nichibukai Catalyst Chemical) . ST-OL (Average particle size: 45 nm, silica concentration: 20 wt%, manufactured by Nikko Chemical) . SI-80P (Average particle size: 80 nm, silica concentration: 40 wt%, manufactured by Nichibukai Catalyst Chemical)

[0058] (Raw material silica sol: Experimental Example 1)

[0059] A 2 L reaction vessel was placed in a 50°C oil bath, and 222 g of ethanol, 590 g of water, and 295 g of 25 wt% ammonia were added. The mixture was stirred at 100 rpm using an air-driven stirrer while being heated to 50°C. Subsequently, while stirring the mixture, 190 g of tetraethoxysilane was continuously added over 10 minutes using a peristaltic pump, resulting in a silica slurry. The silica concentration was 5 wt%, the average particle size was 50 nm, and the sphericity was 0.67.

[0060] (Resin Materials) ZX-1059: Liquid bisphenol type epoxy resin, resin viscosity: 2.5 Pa·s, manufactured by NIPPON STEEL Chemical & Material Co., Ltd. YDF-8170C: Liquid bisphenol type epoxy resin, resin viscosity: 1.0 Pa·s, manufactured by NIPPON STEEL Chemical & Material Co., Ltd. JER630: Multifunctional epoxy resin, resin viscosity 0.8 Pa·s, manufactured by Mitsubishi Chemical.

[0061] (Silane Coupling Agent) KBM-303: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry; KBM-403: 3-epoxypropoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry; KBM-4803: 3-epoxypropoxyoctyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry; KBE-403: 3-epoxypropoxypropyltriethoxysilane, manufactured by Shin-Etsu Chemical Industry.

[0062] (Example 1)

[0063] 100 parts by weight of raw material silica sol (ST-OS, manufactured by Nichiman Chemical, 20% by weight of silica content, dispersed in water, volume average particle size 9 nm) was fully contacted with a strong acid cation exchange resin (HPR1024 H, manufactured by ORGANO CORPORATION) and then fully contacted with a strong base ion exchange resin (IRA400J CL) to obtain refined silica sol. (Ion removal process).

[0064] At this point, the amount of Na contained in the silicon oxide is 300 ppm, the amount of Na contained in the aqueous solution is <5 ppm, and the total amount of anions is <5 ppm.

[0065] Next, a surface treatment process (surface treatment step) 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 (KBM-403 (3-epoxypropoxypropyltrimethoxysilane), manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as a silane compound. The chemically bonded carbon content of this surface-modified silica sol was 6%. In FT-IR, a peak originating from aliphatic C-H was detected at 2900-3000 cm-1, and the peak originating from silanol at 3740 cm-1 disappeared.

[0066] Subsequently, it is mixed with 60 parts by mass of epoxy resin (ZX-1059, manufactured by NIPPON STEEL Chemical & Material Co., Ltd.) as the resin material, and passed through a filter cartridge with a filtration accuracy of 1 μm (removal process). The dispersion medium and aqueous solvent are removed by heating and depressurization through an evaporator to obtain the resin composition of this embodiment (resin composition preparation process). The amount of chemically bonded carbon in the silica particle material contained in this resin composition is 20%. In FT-IR, a peak originating from aliphatic C-H at 2900-3000 cm-1 and a peak originating from aromatic ring C-H at 3000-3100 cm-1 were detected, while the peak originating from silanol at 3740 cm-1 disappeared.

[0067] . Examples 2 to 6 were prepared with reference to the sample preparation method of Example 1, as described in Table 1.

[0068] (Comparative Example 1)

[0069] Except for omitting the removal step (1 μm filtration) of Example 1, the same procedure was performed to obtain the resin composition of this comparative example.

[0070] (Comparative Example 2)

[0071] Except for omitting the removal step in Example 6, the same procedure was performed to obtain the resin composition of this comparative example.

[0072] (Comparative Example 3)

[0073] Except for changing the operation of adding 300 parts by mass of PGM in Example 1 to adding 50 parts by mass of PGM, the same procedure was performed. However, since the viscosity of the mixture was quite high, it was not possible to filter to 1 μm.

[0074] (Comparative Example 4)

[0075] Except for changing the operation of adding 300 parts by mass of PGM in Example 6 to adding 50 parts by mass of PGM, the same procedure was performed. However, since the viscosity of the mixture was quite high, it was not possible to filter to 1 μm.

[0076] (Comparative Example 5)

[0077] Except for omitting the operation of contacting the strong acid cation exchange resin and the strong base ion exchange resin with the raw material silica sol in Example 2, the same procedure was performed to obtain the resin composition of this comparative example.

[0078] (Comparative Example 6)

[0079] Except for omitting the operation of contacting the strong acid cation exchange resin and the strong base ion exchange resin with the raw material silica sol in Example 6, the same procedure was performed to obtain the resin composition of this comparative example.

[0080] (Comparative Example 7)

[0081] Except for the silica sol obtained in Test Example 1, the same procedure as in Example 5 was carried out. However, since the resin dispersion became highly viscous and gelled into a white solid when the solvent was distilled off, it was impossible to evaluate the various physical properties of the resin dispersion.

[0082] (Comparative Example 8)

[0083] Except for omitting the operation of contacting the strongly basic ion exchange resin with the raw material silica sol in Example 4, the same procedure was performed to obtain the resin composition of this comparative example.

[0084] (Comparative Example 9)

[0085] Except for omitting the surface treatment operation with silane coupling agent in Example 2, the same procedure was performed to obtain the resin composition of this comparative example.

[0086] (Evaluation)

[0087] The resin compositions of each embodiment and comparative example were subjected to ashing treatment. The ashing treatment was performed by heating at 800°C for 30 minutes in an atmospheric atmosphere, and the residue was used as ashed particle material for BET specific surface area analysis using nitrogen. The results are shown in Table 2.

[0088] For the deionized aqueous solutions of each embodiment and comparative example, ion-exchanged water was added to adjust the silica sol concentration to 10 wt%, and the solution was added to a centrifugal ultrafiltration filter unit (molecular weight separation: 10000). The silica components were separated from the aqueous solution by applying 4000 G to a centrifuge (manufactured by Kubota Manufacturing Co., Ltd., high-speed cooling centrifuge, MODEL 6000) for 30 minutes. The amount of Na and anions in the recovered aqueous solution was measured by ion chromatography, and the results are shown in Table 1.

[0089] The viscosity of the resin compositions of each embodiment and comparative example was measured using an E-type viscometer at a shear rate of 1 / s. This is disclosed in Table 2.

[0090] 10 g of the resin composition of each embodiment and comparative example was mixed with 30 g of PGM, and the mixture was irradiated with ultrasound to fully dissolve the resin. Then, when the mixture was passed through a sieve with a specified aperture, the number of foreign objects captured on the sieve was measured. This is shown in Table 2.

[0091] The amount of Na and anion in the PCT extract obtained by the method described in the embodiments of the resin compositions of each example and comparative example were measured by ion chromatography, and the results are shown in Table 2.

[0092] . The amount of Na was measured using an inductively coupled plasma (ICP) emission spectrophotometer for the ashing particle material, and the results are shown in Table 2.

[0093] .The chemical bonding carbon content analysis and FT-IR measurement method of surface-modified silica are as follows. 10 g of surface-modified silica sol or 10 g of silica-containing resin composition mixed with 10 g of butyl acetate and 30 g of toluene as a poor solvent was irradiated with ultrasound for at least 5 minutes. Then, a centrifuge (made by Kubota Manufacturing Co., Ltd., high-speed cooling centrifuge, MODEL 6000) was used with 20,000 G for 30 minutes to precipitate the silica component. The supernatant was discarded, and an additional 30 g of butyl acetate was added. After irradiation with ultrasound for at least 5 minutes, a centrifuge was used with 20,000 G for 30 minutes to precipitate the silica component. The supernatant was then discarded, and the precipitated silicon oxide was dried using a hot air dryer. Residual solvent was distilled off, and the resulting dry powder was measured using a carbon content analyzer (HORIBA, EMIA-321V) and diffuse reflectance FT-IR spectroscopy. In the FT-IR, the presence or absence of peaks originating from aliphatic C-H at 2900–3000 cm⁻¹, the presence or absence of peaks originating from aromatic C-H at 3000–3100 cm⁻¹, and the presence or absence of a peak originating from SiOH at 3740 cm⁻¹ were confirmed.

[0094] 『Table 1』 Comparative Example 9 100 220 0.82 2.16 have have <5 <5 300 0 0 45 45 Fluid-passable White Turbid Gel Comparative Example 8 100 54 0.91 2.14 have none <5 200 300 1.5 2 370 40 Fluid-passable White discharge Comparative Example 7 400 70 0.67 1.95 have have <5 <5 300 1.5 1 80 20 Fluid-passable White Turbid Gel Comparative Example 6 6 97 34 0.88 2.15 none none 300 350 300 1 0.8 230 twenty two 11 Fluid-passable White discharge Comparative Example 5 100 220 0.83 2.14 none none 300 200 300 5 6 270 60 Fluid-passable White discharge Comparative Example 4 6 97 33 0.82 2.13 have have <5 <5 50 1 0.7 210 twenty two 11 block Comparative Example 3 100 300 0.83 2.13 have have <5 <5 50 5 6 200 60 block Comparative Example 2 6 97 33 0.88 2.13 have have <5 <5 300 1 0.7 210 twenty two 11 Unused White transparent Comparative Example 1 100 297 0.83 2.14 have have <5 <5 300 5 6 200 60 Unused transparent Example 6 6 97 30 0.91 2.13 have have <5 <5 300 1 0.7 230 twenty two 11 Fluid-passable White transparent Example 5 100 60 0.92 2.17 have have <5 <5 300 1.5 2 330 60 Fluid-passable White transparent Example 4 100 54 0.91 2.14 have have <5 <5 300 1.5 2 370 40 Fluid-passable White transparent Example 3 100 120 0.87 2.14 have have <5 <5 300 1.5 1.5 3 250 70 Fluid-passable transparent Example 2 100 220 0.82 2.16 have have <5 <5 300 5 5 220 45 45 Fluid-passable transparent Example 1 100 295 0.81 2.15 have have <5 <5 300 5 6 200 60 Fluid-passable transparent unit Quality Quality Quality Quality Quality Quality Quality Quality - Quality - - - - - ppm ppm Quality Quality Quality Quality Quality % μg / m2 Quality Quality Quality Quality - project ST-OS SI-30 ST-O-40 SI-45P ST-OL SI-80P Experimental Example 1 Specific surface area after drying and curing sphericity True specific gravity after drying and curing HPR1024 H HPR1200 H HPR1006NNC H IRA400J Cl IRA410J Cl Amount of Na+ Anion total dosage PGM KBM-303 KBM-403 KBM-4803 KBE-403 Carbon content after solvent cleaning Carbon content after solvent cleaning ZX-1059 YDF-8170C jER630 1 μm filter Appearance after solvent removal Micro-silicon oxide particle slurry Cation exchange resin Anion exchange resin Aqueous solution after ion removal Aqueous solvent Silane coupling agent Epoxy resin sieve

[0095] 『Table 2』 Comparative Example 9 25 400 150 220 Comparative Example 8 100 28 3 0 0 4 have have none <5 70 50 700 80 50 Comparative Example 7 25 1 1 60 Comparative Example 6 180 9 1 0 1 1.3 have have none 300 150 55 6400 120 30 Comparative Example 5 60 twenty two 4 0 0 16 have have none 220 90 25 9300 100 210 Comparative Example 4 Comparative Example 3 Comparative Example 2 129 31 40 16 3 1.1 have have none 20 9 55 880 100 30 Comparative Example 1 twenty three 78 30 15 3 17 have have none <5 <5 25 400 1200 300 Example 6 120 38 9 0 0 1.2 have have none 20 9 55 930 120 30 Example 5 53 60 3 0 0 4 have have none <5 8 50 640 1200 60 Example 4 80 62 2 0 0 4 have have none 20 <5 50 700 80 50 Example 3 40 79 1 0 0 12 have have none <5 <5 36 620 1100 120 Example 2 30 91 2 0 0 16 have have none 15 <5 25 400 150 220 Example 1 18 95 0 0 0 20 have have none <5 <5 25 290 1000 310 unit Pa. s %T 10g 10g 10g % 2900~3000 cm -1 The peak 3000~3100 cm -1 The peak 3740 cm -1 The peak ppm ppm wt% ppm ppm m 2 / g project Viscosity @ 1 / sec 860 nm transmittance Foreign objects larger than 5 μm Foreign objects larger than 10 μm Foreign objects larger than 20 μm Carbon content after solvent cleaning IR after solvent cleaning Na + quantity Anion total dosage Ash content ICP / Na content ICP / Al quantity BET specific surface area Various physical properties of resin dispersions PCT extract water of resin dispersion Various physical properties after ashing treatment

[0096] As can be seen from the table, the results of Example 2 and Comparative Example 5, and Example 6 and Comparative Example 6 show that by performing the ion removal process, the amount of Na in the obtained resin composition and the amount of Na and anions in the PCT extract can be reduced.

[0097] Furthermore, based on the results of Example 1 and Comparative Example 1, and Example 6 and Comparative Example 2, by performing the removal process, it became possible to reduce the number of foreign objects with particle sizes of 20 μm or more, 10 μm or more, and 5 μm or more. Furthermore, based on the results of Comparative Examples 3 and 4, it is evident that adding solvents such as PGM to facilitate the removal process is indeed effective.

[0098] Based on the results of Example 5 and Comparative Example 7, it was confirmed that by having a certain amount of Na and Al content in the silicon oxide particles, the reactivity of silicon oxide with the silane coupling agent and resin is promoted. As the blending of silicon oxide and resin improves, the viscosity of the resin dispersion is reduced.

[0099] The results of Example 4 and Comparative Example 8 show that by performing the anion removal process, the total amount of anions in the PCT extract of the obtained resin composition can be reduced. The results of Example 2 and Comparative Example 9 show that by performing the surface treatment process, the silane coupling agent acts as a bridge to chemically bond the resin and silicon oxide. After solvent removal, the silicon oxide does not agglomerate, thus imparting transparency, fluidity, and dispersibility. [Simplified Explanation of the Diagram]

[0017] None

Claims

1. A resin composition comprising a particle material formed from silicon oxide with a surface treated with a silane compound and a resin material in which the particle material is dispersed, wherein the resin composition has a viscosity of 5 Pa·s or higher at a shear rate of 1 / sec, and an amount of foreign matter with a major diameter of 20 μm or higher of 1.0 particles / 10g or less, wherein the amount of Na in the PCT extract obtained by extracting 30 g of the resin composition in 30 mL of ion-exchange water at 121°C for 20 hours is 30 ppm or less, and the BET specific surface area of ​​the ashed particle material obtained by ashing at 800°C for 30 minutes in atmospheric atmosphere is 9 to 550 m² / g, and the total Na content based on the total mass of the ashed particle material is 20 to 1000 ppm, and the Al content is 20 to 3000 ppm.

2. The resin composition as described in claim 1, wherein the mass of the aforementioned ashing particle material is 10 to 80% by mass based on the total mass, and the content of the aforementioned foreign matter having a major diameter of 10 μm or more is 9.0 particles / 10g or less, and the total anion concentration in the aforementioned PCT extract is 30 ppm or less.

3. The resin composition as described in claim 1 or 2, wherein the content of the aforementioned foreign matter having a major diameter of 5 μm or more is 25.0 particles / 10g or less, and the aforementioned particle material, when measured by FT-IR, has a peak originating from aliphatic molecules in the range of 2900–3000 cm⁻¹ and a peak originating from aromatic rings in the range of 3000–3100 cm⁻¹.

4. A method for manufacturing a resin composition, comprising: an ion removal step, wherein a cation exchange resin and an anion exchange resin are contacted with a raw material silica sol to form a refined silica sol; a resin composition preparation step, wherein the dispersion medium of the refined silica sol is removed and a resin material is mixed to prepare the resin composition; a removal step, wherein, before the completion of the resin composition preparation step, the raw material silica sol and / or the refined silica sol are filtered to remove foreign matter; and a surface treatment step, wherein, before the completion of the resin composition preparation step, the raw material silica sol and / or the refined silica sol are surface treated with a silane compound.

5. The method for manufacturing the resin composition as described in claim 4, comprising a dissolution step in which a raw material material made of metallic silicon and / or silicon oxide is contacted or dissolved in an alkaline aqueous solution to generate the aforementioned raw material silicon oxide sol.

6. The method for manufacturing an epoxy resin composition as described in claim 4 or 5, wherein the aforementioned removal step is a step of removing the aforementioned foreign matter until the foreign matter with a particle size of 20 μm or more becomes 1.0 particle / 10g.

7. The method for manufacturing a resin composition as described in claim 4 or 5, wherein the aforementioned removal step is a step of removing the aforementioned foreign matter until the foreign matter with a particle size of 10 μm or larger becomes 9.0 particles / 10g or less.

8. A method for manufacturing a resin composition as described in claim 4 or 5, wherein the aforementioned removal step is a step of removing the aforementioned foreign matter until the foreign matter with a particle size of 5 μm or larger becomes 25.0 particles / 10g or less.

9. The method for manufacturing a resin composition as described in claim 6, wherein the aforementioned removal step is a step of removing the aforementioned foreign matter until the number of foreign matter with a particle size of 10 μm or larger is 9.0 or less per 10g and the number of foreign matter with a particle size of 5 μm or larger is 25.0 or less per 10g.