TW202342626A - Silica sol concentration method using ultrafiltration - Google Patents
Silica sol concentration method using ultrafiltration Download PDFInfo
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- TW202342626A TW202342626A TW112107328A TW112107328A TW202342626A TW 202342626 A TW202342626 A TW 202342626A TW 112107328 A TW112107328 A TW 112107328A TW 112107328 A TW112107328 A TW 112107328A TW 202342626 A TW202342626 A TW 202342626A
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- Prior art keywords
- concentration
- silica
- sol
- oxide
- silica oxide
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000000108 ultra-filtration Methods 0.000 title abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 319
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 128
- 239000002245 particle Substances 0.000 claims abstract description 48
- 239000002612 dispersion medium Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims description 72
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 46
- 239000007788 liquid Substances 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 239000012141 concentrate Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000012528 membrane Substances 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 150000001450 anions Chemical class 0.000 description 11
- 150000001768 cations Chemical class 0.000 description 11
- 239000011362 coarse particle Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011856 silicon-based particle Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/16—Feed pretreatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/141—Preparation of hydrosols or aqueous dispersions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
- C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Silicon Compounds (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
本發明係關於利用超過濾法的氧化矽溶膠之濃縮方法。The present invention relates to a method for concentrating silica oxide using ultrafiltration.
膠體狀氧化矽粒子分散於水性媒體之溶膠(氧化矽溶膠)可藉由加熱自作為原料的矽酸鈉水溶液取除鈉離子的矽酸水溶液，或藉由加熱將烷氧基矽烷經水解所得之矽酸水溶液而製造。一般在製造後的氧化矽溶膠為氧化矽成分呈低濃度之液體，將此經濃縮而使其製品化。 作為濃縮氧化矽成分之方法，有藉由極限過濾或蒸發法而進行濃縮。藉由極限過濾而濃縮氧化矽溶膠中的氧化矽成分之方法為，藉由通過極限過濾膜使水往系統外除去，進而提高氧化矽溶膠中之氧化矽成分的濃度者。 作為藉由極限過濾的濃縮方法，例如已有揭示將鋯鹽水溶液在尿素存在下進行加熱得到透明性氧化鋯溶膠後，添加螯合化劑及鋯以外之金屬化合物，在80℃以下之溫度下藉由極限過濾膜進行濃縮之方法(參照專利文獻1)。 又，自含有氧化矽的地熱流體生成膠態氧化矽濃縮物時，自初期溫度冷卻至核形成溫度而開始氧化矽膠體成長，將具有氧化矽粒子之流體藉由極限過濾得到氧化矽之濃縮物的方法(參照專利文獻2)。 [先前技術文獻] [專利文獻] A sol in which colloidal silica particles are dispersed in an aqueous medium (silica oxide sol) can be obtained by heating a silicic acid aqueous solution in which sodium ions are removed from a sodium silicate aqueous solution as a raw material, or by hydrolyzing alkoxysilane by heating Manufactured from silicic acid aqueous solution. Generally, the silicon oxide sol after manufacture is a liquid with a low concentration of silicon oxide components, which is concentrated to become a product. As a method of concentrating the silicon oxide component, there is concentration by extreme filtration or evaporation. The method of concentrating the silica oxide component in the silica oxide sol through extreme filtration is to increase the concentration of the silica oxide component in the silica oxide sol by removing water from the system through the extreme filtration membrane. As a concentration method by extreme filtration, for example, it has been disclosed that a zirconium salt aqueous solution is heated in the presence of urea to obtain a transparent zirconium oxide sol, and then a chelating agent and a metal compound other than zirconium are added, and the solution is heated at a temperature of 80° C. or lower. A method of concentrating with a limit filtration membrane (see Patent Document 1). Furthermore, when a colloidal silicon oxide concentrate is produced from a geothermal fluid containing silicon oxide, the silicon oxide colloid starts to grow when the initial temperature is cooled to the nucleation temperature, and the fluid containing silicon oxide particles is subjected to extreme filtration to obtain a silicon oxide concentrate. method (see Patent Document 2). [Prior technical literature] [Patent Document]
[專利文獻1]國際公開第90/09350號 [專利文獻2]特表2018-524256號公報 [Patent Document 1] International Publication No. 90/09350 [Patent Document 2] Special Publication No. 2018-524256
[發明所解決的問題][Problem solved by the invention]
在氧化矽溶膠中之氧化矽粒子的濃縮中，可使用超過濾法，但在極限過濾膜將過濾液往系統外除去時，於極限過濾膜之內面會形成稱為濾餅層(cake layer)之高濃度氧化矽粒子的堆積物。於該濾餅層所含的氧化矽粗大粒子，在將氧化矽溶膠在極限過濾裝置內使其循環而提高氧化矽粒子之濃度時，會脫落於氧化矽溶膠中，混入於最終製品(經濃縮的氧化矽溶膠製品)，其結果，使用此等製品時有著產生障礙之顧慮。例如在將該氧化矽溶膠製品使用於研磨用途時，粗大粒子會在研磨面上產生傷痕，而對於矽晶圓或裝置上可能具有缺陷。在產生此等粗大粒子之情況時，亦考慮到之後藉由濾器的除去，而因會產生濾器阻塞而不具效率。 因此，期待可抑制來自極限過濾裝置之極限過濾膜內面所形成的濾餅層之氧化矽粗大粒子的混入，且亦可提高氧化矽溶膠之氧化矽濃度的方法。 In the concentration of silica particles in silica sol, ultrafiltration can be used. However, when the extreme filtration membrane removes the filtrate out of the system, a cake layer will be formed on the inner surface of the extreme filtration membrane. ) is a deposit of high-concentration silicon oxide particles. The coarse silica particles contained in the filter cake layer will fall off the silica sol and mix into the final product (concentrated Oxidized silica sol products), as a result, there is a concern that obstacles may occur when using these products. For example, when the oxidized silica sol product is used for polishing, the coarse particles will cause scratches on the polishing surface, which may cause defects on the silicon wafer or device. When such coarse particles are generated, subsequent removal by a filter is also considered, and the filter will be clogged and inefficient. Therefore, a method is expected that can suppress the mixing of coarse silica particles from the filter cake layer formed on the inner surface of the limit filtration membrane of the limit filtration device and also increase the silicon oxide concentration of the silica sol.
本發明為有鑑於上述所成者，提供一種氧化矽之濃縮方法，該方法為，欲提高氧化矽溶膠中之氧化矽成分濃度而藉由超過濾法進行濃縮時，可防止在經濃縮的氧化矽溶膠中凝集氧化矽粒子之形成。In view of the above, the present invention provides a method for concentrating silicon oxide. This method can prevent the concentration of silicon oxide components from being oxidized by ultrafiltration in order to increase the concentration of the silicon oxide component in the silica oxide sol. Formation of agglomerated silica oxide particles in silica sol.
本發明者們，將上述課題的解決作為目標而進行詳細檢討結果，發現將於氧化矽溶膠中所含的氧化矽粒子之濃度藉由極限過濾裝置使其上升的濃縮步驟中，滿足下述要件A及要件B作為條件下，藉由提高極限過濾膜附近的氧化矽溶膠之液體流速而作成氧化矽粒子難凝集之狀況，防止於經濃縮的氧化矽溶膠中形成凝集的氧化矽粒子之氧化矽溶膠的濃縮方法，而完成本發明。 [解決課題的手段] The inventors of the present invention conducted a detailed examination with the aim of solving the above-mentioned problems, and found that the following requirements are met in the concentration step of increasing the concentration of silicon oxide particles contained in the silicon oxide sol using a limit filtration device. Under conditions A and B, by increasing the liquid flow rate of the silica oxide sol near the limit filtration membrane, a situation in which the silica oxide particles are difficult to agglomerate is created, thereby preventing the formation of agglomerated silica oxide particles in the concentrated silica oxide sol. The present invention is completed by a method for concentrating sol. [Means to solve the problem]
即，作為本發明之第1觀點，其關於將作為分散質粒子的氧化矽粒子分散於分散媒之溶膠(氧化矽溶膠)的濃縮方法，其特徵為含有將該氧化矽溶膠中所含的氧化矽粒子之濃度藉由極限過濾裝置而使其上升的濃縮步驟，在該濃縮步驟中滿足下述要件A及要件B之氧化矽溶膠的濃縮方法。 要件A：氧化矽溶膠在注入於極限過濾裝置之前的液溫為0至45℃之範圍。 要件B：藉由以極限過濾裝置使氧化矽溶膠循環，於濃縮步驟後在該氧化矽溶膠中所含的氧化矽粒子之濃度比濃縮步驟前更上升者。 作為第2觀點，其關於前述要件B中，於以極限過濾裝置使氧化矽溶膠循環的濃縮步驟中，或於濃縮步驟後，含有於極限過濾裝置進一步注入氧化矽溶膠，進一步注入之氧化矽溶膠的濃度為，含於濃縮步驟前之氧化矽溶膠中的氧化矽粒子之濃度的0.1～30倍作為特徵之第1觀點所記載的氧化矽溶膠之濃縮方法。 作為第3觀點，其關於前述要件A中，將氧化矽溶膠在注入於極限過濾裝置之前的液溫調整為0至30℃之範圍者作為特徵之第1觀點或第2觀點所記載的氧化矽溶膠之濃縮方法。 作為第4觀點，其關於前述要件B中，藉由於極限過濾裝置進一步注入與濃縮步驟前之氧化矽溶膠相同濃度之氧化矽溶膠，或藉由以極限過濾裝置使比濃縮步驟前之氧化矽溶膠的濃度高之氧化矽溶膠進行循環，於濃縮步驟後在該氧化矽溶膠中所含的氧化矽粒子之濃度比濃縮步驟前更上升者作為特徵之第2觀點所記載的氧化矽溶膠之濃縮方法。 作為第5觀點，其關於前述要件B中，經濃縮的氧化矽溶膠於濃縮步驟後自極限過濾裝置直接通過配管，在氧化矽粒子之濃度降低成5質量%以內之條件下填充於濃縮氧化矽溶膠填充容器作為特徵之第1觀點至第4觀點中任一所記載的氧化矽溶膠之濃縮方法。 作為第6觀點，其關於前述要件B中，在濃縮步驟後之氧化矽粒子的濃度對於濃縮步驟前之氧化矽粒子的濃度之濃度比為2至30之範圍下進行濃縮步驟作為特徵之第1觀點至第5觀點中任一所記載的氧化矽溶膠之濃縮方法。 作為第7觀點，其關於注入於極限過濾裝置前之氧化矽溶膠含有以下氧化矽粒子，該氧化矽粒子為，加熱自矽酸鹼水溶液除去鹼金屬離子所得的矽酸水溶液而得者作為特徵之第1觀點至第6觀點中任一所記載的氧化矽溶膠之濃縮方法。 [發明之效果] That is, the first aspect of the present invention relates to a method for concentrating a sol (oxidized silica sol) in which silica oxide particles as dispersion particles are dispersed in a dispersion medium, and is characterized by comprising: A concentration step in which the concentration of silicon particles is increased by a limit filtration device. In this concentration step, the concentration method of oxidized silica sol satisfies the following requirements A and B. Requirement A: The liquid temperature of the oxidized silica sol before being injected into the ultimate filtration device is in the range of 0 to 45°C. Requirement B: By circulating the oxidized silica sol through a limit filtration device, the concentration of silica oxide particles contained in the oxidized silica sol after the concentration step is higher than before the concentration step. As a second aspect, regarding the aforementioned requirement B, in the concentration step of circulating the oxidized silica sol with the extreme filtration device, or after the concentration step, the oxidized silica sol is further injected into the extreme filtration device, and the oxidized silica sol is further injected. The concentration method of the oxidized silica sol described in the first aspect is characterized by a concentration of 0.1 to 30 times the concentration of the silica oxide particles contained in the silica oxide sol before the concentration step. As a third aspect, the silica oxide described in the first aspect or the second aspect is characterized by adjusting the liquid temperature of the silica oxide sol before being injected into the limit filtration device to a range of 0 to 30°C in the aforementioned requirement A. Concentration method of sol. As a fourth aspect, regarding the aforementioned requirement B, by further injecting an oxidized silica sol with the same concentration as the oxidized silica sol before the concentration step through a limit filtration device, or by using a limit filtration device to make the oxidized silica sol higher than the oxidized silica sol before the concentration step. The concentration method of silica oxide described in the second aspect is characterized by circulating high-concentration silica oxide sol, and the concentration of silica oxide particles contained in the silica oxide sol after the concentration step is higher than before the concentration step. . As a fifth aspect, regarding the aforementioned requirement B, the concentrated silica sol is directly passed through the piping from the extreme filtration device after the concentration step, and is filled with concentrated silica under the condition that the concentration of the silica particles is reduced to within 5 mass %. A method for concentrating silica oxide sol according to any one of the first to fourth aspects is characterized by filling a sol container. As a sixth aspect, in the above-mentioned requirement B, the first feature of the concentration step is that the concentration ratio of the concentration of the silicon oxide particles after the concentration step to the concentration of the silicon oxide particles before the concentration step is in the range of 2 to 30. A method for concentrating silica oxide as described in any one of the viewpoints to the fifth viewpoint. As a seventh aspect, it is characterized in that the silica sol injected before the extreme filtration device contains silica particles obtained by heating a silicic acid aqueous solution obtained by removing alkali metal ions from an alkali silicate aqueous solution. The method for concentrating silica sol according to any one of the first to sixth aspects. [Effects of the invention]
本發明之方法為，欲提高氧化矽溶膠中之氧化矽成分的濃度而將濃縮以超過濾法進行時，可防止於經濃縮的氧化矽溶膠中形成凝集之氧化矽粒子，且可達成濃縮氧化矽溶膠之效果。The method of the present invention is to prevent the formation of agglomerated silicon oxide particles in the concentrated silica sol when the concentration is carried out by ultrafiltration in order to increase the concentration of the silica oxide component in the silica oxide sol, and achieve concentrated oxidation. The effect of silica sol.
[實施發明的型態][Types of carrying out the invention]
本發明為有關將作為分散質粒子之氧化矽粒子分散於作為分散媒之水的溶膠(氧化矽溶膠)之濃縮方法，含有將該氧化矽溶膠中所含的氧化矽粒子之濃度藉由極限過濾裝置而使其上升的濃縮步驟，在該濃縮步驟中滿足下述要件A及要件B之氧化矽溶膠之濃縮方法。 要件A：氧化矽溶膠在注入於極限過濾裝置之前的液溫為0至45℃，以0至40℃為佳，更佳為0至35℃，最佳為0至30℃之範圍。 要件B：藉由以極限過濾裝置使氧化矽溶膠循環，於濃縮步驟後在該氧化矽溶膠中所含的氧化矽粒子之濃度比濃縮步驟前更上升者。 以下詳細說明本發明。 The present invention relates to a concentration method for dispersing silica oxide particles as dispersion particles in a sol (silica oxide sol) containing water as a dispersion medium. A method for concentrating oxidized silica sol that satisfies the following requirements A and B in the concentration step for raising the concentration. Requirement A: The liquid temperature of the silica oxide before being injected into the extreme filtration device is 0 to 45°C, preferably 0 to 40°C, more preferably 0 to 35°C, and most preferably in the range of 0 to 30°C. Requirement B: By circulating the oxidized silica sol through a limit filtration device, the concentration of silica oxide particles contained in the oxidized silica sol after the concentration step is higher than before the concentration step. The present invention will be described in detail below.
作為在本發明中所使用的極限過濾裝置，例如可使用具備以下結構者，該結構為將極限過濾膜(UF膜)成型成試管狀，循環要濃縮的該試管之內側的氧化矽溶膠，於試管外側排出水性媒體的氧化矽溶膠之氧化矽成分經濃縮之結構。上述水性媒體之主成分為水，但含於氧化矽溶膠中之陽離子、陰離子亦可同時排出。極限過濾膜以交叉流方式為佳，藉由對極限過濾膜面而形成的平行流動，一邊抑制氧化矽溶膠中之懸浮物質或膠體狀氧化矽粒子於極限過濾膜面上的堆積現象，一邊可使氧化矽溶膠中之氧化矽成分濃度上升。As an extreme filtration device used in the present invention, for example, one having a structure in which an extreme filtration membrane (UF membrane) is molded into a test tube shape, and the oxidized silica sol inside the test tube to be concentrated is circulated, can be used. The structure in which the silica oxide component of the silica oxide sol is concentrated in the aqueous medium discharged from the outside of the test tube. The main component of the above-mentioned aqueous media is water, but the cations and anions contained in the silica oxide sol can also be discharged at the same time. The extreme filtration membrane is preferably in a cross-flow mode. Through the parallel flow formed on the extreme filtration membrane surface, it can suppress the accumulation of suspended matter in the oxidized silica sol or colloidal silica particles on the extreme filtration membrane surface. The concentration of silicon oxide component in the silica oxide sol is increased.
作為極限過濾膜之材質，例如可舉出聚乙烯、聚氟乙烯、聚偏二氟乙烯(polyvinylidene fluoride)、聚丙烯、乙酸纖維素、聚丙烯腈、聚醯亞胺、聚碸、聚醚碸等。又，對於膜材料可單獨使用氧化鋁、氧化鋯、氧化鈦、不銹鋼、玻璃等，或可與上述材質同時使用。作為極限過濾膜模組，例如可使用套管收納方式，將極限過濾膜與該支持體及流路材料等構件一體化後作為膜元件而收納於套管中，藉由幫浦將氧化矽溶膠壓入於套管內而進行水性媒體之過濾，濃縮膠體狀之氧化矽成分，可得到經濃縮的氧化矽溶膠製品。Examples of materials for the extreme filtration membrane include polyethylene, polyvinyl fluoride, polyvinylidene fluoride, polypropylene, cellulose acetate, polyacrylonitrile, polyimide, polystyrene, and polyetherstyrene. wait. In addition, as the membrane material, alumina, zirconium oxide, titanium oxide, stainless steel, glass, etc. can be used alone, or they can be used together with the above materials. As the extreme filtration membrane module, for example, a casing storage method can be used. The extreme filtration membrane is integrated with the support, flow path material and other components and then stored in the casing as a membrane element. The oxidized silica sol is pumped through the pump. Press it into the casing to filter the aqueous media and concentrate the colloidal silica oxide component to obtain a concentrated silica oxide sol product.
上述極限過濾膜之截留分子量(molecular weight cutoff)，例如，膜之公稱孔徑在5nm～100nm程度，作為適用粒子徑，例如為5nm～500nm，作為截留分子量，例如可使用50k(5萬)、100k(10萬)、300k(30萬)、500k(50萬)者。例如截留分子量、膜之公稱孔徑及適用粒子徑之間僅為一例子，但符合以下關係，但並非僅限定於此等關係者。 例如，截留分子量為5萬之情況時，膜之公稱孔徑為5nm，而適用粒子徑為15～30nm。截留分子量為10萬之情況時，膜之公稱孔徑為10nm，適用粒子徑為30～90nm。截留分子量為30萬之情況時，膜之公稱孔徑為35nm，適用粒子徑為90～200nm。截留分子量為100萬之情況時，膜之公稱孔徑為100nm，適用粒子徑為300～600nm。 The molecular weight cutoff of the above-mentioned limit filtration membrane, for example, the nominal pore diameter of the membrane is about 5nm to 100nm. As the applicable particle diameter, for example, it is 5nm to 500nm. As the molecular weight cutoff, for example, 50k (50,000) or 100k can be used. (100,000), 300k (300,000), 500k (500,000). For example, the relationship between the molecular weight cutoff, the nominal pore size of the membrane, and the applicable particle size is just an example, but the following relationships are met, but are not limited to these relationships. For example, when the molecular weight cutoff is 50,000, the nominal pore size of the membrane is 5 nm, and the applicable particle size is 15 to 30 nm. When the molecular weight cutoff is 100,000, the nominal pore size of the membrane is 10nm, and the applicable particle size is 30 to 90nm. When the molecular weight cutoff is 300,000, the nominal pore size of the membrane is 35nm, and the applicable particle size is 90 to 200nm. When the molecular weight cutoff is 1 million, the nominal pore size of the membrane is 100nm, and the applicable particle size is 300 to 600nm.
對氧化矽溶膠之UF裝置的輸送液(本說明書中，亦稱為注入、注液或壓入。)，例如可在0.01～10MPa、0.05～5.0MPa、0.1～1.0MPa或0.3～1.0MPa之壓力下進行。For example, the transport liquid of the UF device of oxidized silica sol (also referred to as injecting, injection or pressing in this specification) can be between 0.01 to 10MPa, 0.05 to 5.0MPa, 0.1 to 1.0MPa or 0.3 to 1.0MPa. Performed under pressure.
又，欲得到所望氧化矽濃度之氧化矽溶膠的濃縮所需時間為0.1～50小時程度。In addition, the time required for concentrating the silica sol to obtain a desired silica concentration is about 0.1 to 50 hours.
要件A係將氧化矽溶膠在注入於極限過濾裝置之前的液溫設定在0至45℃之範圍作為條件者。氧化矽溶膠之液溫，例如為，0～45℃、0～40℃、0～35℃或0～30℃。藉由將氧化矽溶膠設定在0～45℃、0～40℃、0～35℃或0～30℃之低溫下使流體通過極限過濾裝置，進行氧化矽粒子之矽烷醇基的聚縮合，可避開氧化矽粒子彼此的凝集。Requirement A is based on the condition that the liquid temperature of the silica oxide sol before being injected into the ultimate filtration device is set in the range of 0 to 45°C. The liquid temperature of the oxidized silica sol is, for example, 0 to 45°C, 0 to 40°C, 0 to 35°C, or 0 to 30°C. By setting the silica oxide sol at a low temperature of 0 to 45°C, 0 to 40°C, 0 to 35°C, or 0 to 30°C, the fluid passes through the extreme filtration device to perform polycondensation of the silanol groups of the silica oxide particles. Avoid aggregation of silicon oxide particles with each other.
要件A係將氧化矽溶膠在注入於極限過濾裝置之前的液溫設定在0至45℃之範圍作為條件者，若該氧化矽溶膠之液溫高於此溫度時，可藉由冷卻而將液溫調整至此範圍者為佳。冷卻為於循環冷卻水之槽中，使極限過濾膜模組沈積，將氧化矽溶膠冷卻至所定溫度為止者為佳。本發明中，將濃縮過程之氧化矽溶膠以循環於極限過濾膜模組之方法進行的情況時，注入於極限過濾膜模組之前的溫度為0～45℃、0～40℃、0～35℃、0～30℃、0～25℃或0～15℃，自極限過濾膜模組再度經由對上述溫度範圍的溫度調整(例如冷卻)而注入於極限過濾膜模組者為佳。Requirement A requires that the liquid temperature of the silica oxide sol before being injected into the extreme filtration device is set in the range of 0 to 45°C. If the liquid temperature of the silica oxide sol is higher than this temperature, the liquid can be cooled by cooling. It is better to adjust the temperature to this range. Cooling is preferably done by depositing the extreme filtration membrane module in a circulating cooling water tank and cooling the oxidized silica sol to a predetermined temperature. In the present invention, when the oxidized silica sol in the concentration process is circulated through the extreme filtration membrane module, the temperature before being injected into the extreme filtration membrane module is 0 to 45°C, 0 to 40°C, and 0 to 35°C. ℃, 0 ~ 30 ℃, 0 ~ 25 ℃ or 0 ~ 15 ℃, preferably from the extreme filtration membrane module and then injected into the extreme filtration membrane module through temperature adjustment (such as cooling) in the above temperature range.
要件B係將藉由以極限過濾裝置使氧化矽溶膠循環，於濃縮步驟後在該氧化矽溶膠中所含的氧化矽粒子之濃度比濃縮步驟前更上升作為條件者。Requirement B is a condition that the concentration of silica oxide particles contained in the silica oxide sol is increased after the concentration step by circulating the oxidized silica sol through a limit filtration device as compared with before the concentration step.
本說明書中所謂「循環」，例如表示將注入於極限過濾裝置而經由濃縮步驟之氧化矽溶膠一次回收後，再次注入於極限過濾裝置，或例如藉由於極限過濾裝置形成循環路線，無需回收該氧化矽溶膠而可重複進行濃縮步驟之意思，進一步亦可表示包含此等組合。The so-called "circulation" in this specification means, for example, that the oxidized silica sol injected into the extreme filtration device and passed through the concentration step is recovered once and then injected into the extreme filtration device again, or that there is no need to recover the oxidized silica sol by forming a circulation route through the extreme filtration device. The meaning of silica sol and the concentration step can be repeated, and further can also mean that these combinations are included.
對於要件B，藉由以極限過濾裝置使氧化矽溶膠循環，可抑制濾餅層之脫落。即，藉由使低濃度之氧化矽濃度的氧化矽溶膠進行循環時，可防止濾餅層溶入而混合於低濃度部分。然後，藉由比濃縮前之氧化矽溶膠更高濃度之氧化矽溶膠的循環而進行者為佳。Regarding requirement B, by circulating the oxidized silica sol with a limit filtration device, the shedding of the filter cake layer can be suppressed. That is, by circulating the silica sol with a low concentration of silica, the filter cake layer can be prevented from being dissolved and mixed with the low-concentration portion. Then, it is preferable to circulate the oxidized silica sol with a higher concentration than the oxidized silica sol before concentration.
要件B中，於極限過濾膜模組內進行循環的濃縮步驟中或濃縮步驟後之氧化矽溶膠中可進一步注入氧化矽溶膠。進一步注入的氧化矽溶膠的濃度為，濃縮步驟前之含於氧化矽溶膠中的氧化矽粒子之濃度的0.1～30倍者為佳。藉由進一步注入氧化矽溶膠，可進一步防止濾餅層溶入並混合於低濃度部分。且亦可在該濃度範圍下進行循環。最終，在濃縮步驟終了時，雖比濃縮步驟前更進一步濃縮，但因氧化矽溶膠的進一步注入，可藉由與濃縮步驟前之氧化矽溶膠相同濃度之氧化矽溶膠進行者為佳，該氧化矽溶膠之循環可在比濃縮前之氧化矽溶膠更高之濃度下進行者為更佳。In requirement B, oxidized silica sol can be further injected into the oxidized silica sol during the concentration step of circulation in the extreme filtration membrane module or after the concentration step. The concentration of the further injected silica sol is preferably 0.1 to 30 times the concentration of the silica particles contained in the silica sol before the concentration step. By further injecting silica oxide, the filter cake layer can be further prevented from being dissolved into and mixed with the low concentration portion. And it can also be circulated within this concentration range. Finally, at the end of the concentration step, although the concentration is further concentrated than before the concentration step, the further injection of the oxidized silica sol is preferably carried out by using an oxidized silica sol with the same concentration as the oxidized silica sol before the concentration step. This oxidation It is better if the silica sol can be recycled at a higher concentration than the oxidized silica sol before concentration.
然後經濃縮的氧化矽溶膠在作為最終製品而自極限過濾裝置取出時，作為搬出溶劑使用低濃度的氧化矽溶膠或水而自裝置取出之情況時，因搬出溶劑會產生暫時性濃度降低，濾餅層會藉由搬出溶劑而於氧化矽溶膠製品中脫落，此成為粗大粒子之原因。因此，經濃縮的氧化矽溶膠在濃縮終了時，自極限過濾裝置通過直接配管，在濃縮終了時的氧化矽濃度降低在5質量%以內之條件下作為濃縮氧化矽溶膠製品而包裝(填充濃縮氧化矽溶膠於容器)者為佳。Then, when the concentrated silica sol is taken out from the extreme filtration device as the final product, when a low-concentration silica oxide or water is used as the removal solvent, a temporary concentration decrease occurs due to the removal of the solvent, and the filter The cake layer will fall off in the oxidized silica sol product by removing the solvent, which causes coarse particles. Therefore, the concentrated silica oxide sol is packaged as a concentrated oxidized silica sol product (filled with concentrated oxidized silica sol) under the condition that the concentration of silica oxide at the end of the concentration is reduced to within 5% by mass, through direct piping from the limit filtration device. Silica sol in the container) is better.
又，此等操作為，得到氧化矽溶膠最終製品時且濃縮終了時，自極限過濾裝置直接通過配管，在濃縮終了時的氧化矽濃度降低在5質量%以內之條件下，例如在0～5質量%之範圍內的條件下，較佳為未產生氧化矽濃度降低而可作為濃縮氧化矽溶膠製品而包裝(填充於濃縮氧化矽溶膠填充容器)者。In addition, these operations are to obtain the final product of the silica sol and when the concentration is completed, directly from the extreme filtration device through the piping, and under the conditions that the silica concentration at the end of the concentration is reduced to within 5 mass %, for example, between 0 and 5 Under conditions within the range of mass %, it is preferable that the concentration of silica oxide does not decrease and that it can be packaged as a concentrated silica oxide sol product (filled in a concentrated silica oxide sol filling container).
在本發明中，濃縮步驟後之氧化矽粒子的濃度相對於濃縮步驟前之氧化矽粒子的濃度，可在濃度比2至30之範圍下進行氧化矽溶膠之濃縮步驟者為佳。In the present invention, it is preferable that the concentration ratio of the silica sol after the concentration step is in the range of 2 to 30 relative to the concentration of the silica particles before the concentration step.
又，本發明之氧化矽溶膠的濃縮方法的特徵為，在濃縮步驟前後中之於氧化矽溶膠中所含的離子成分(陽離子或陰離子)濃度變化較少者。Furthermore, the method for concentrating silica oxide of the present invention is characterized by a small change in the concentration of ionic components (cations or anions) contained in the silica oxide before and after the concentration step.
本發明中，在極限過濾之過程中，陽離子(例如含有鉀離子之陽離子，典型者為鉀離子)與陰離子(例如含有硫酸離子之陰離子，典型者為硫酸離子)雖會與水同時排除於系統外，但離子成分對氧化矽溶膠中之氧化矽粒子表面賦予電荷，形成適度氧化矽粒子之反發力而可防止氧化矽粒子之凝集。另一方面，即使存在大量離子成分時，亦不會產生氧化矽粒子彼此的凝集。此等氧化矽溶膠中之陽離子與陰離子之濃度會藉由極限過濾而減少該變化故較佳。例如以抑制陽離子與陰離子之濃度變化至該濃縮步驟前之氧化矽溶膠中之濃度(質量%濃度)的10倍以內者為佳。 將此等離子成分之濃度設定在上述範圍內時，可抑制濾餅層之生成。 In the present invention, during the extreme filtration process, cations (such as cations containing potassium ions, typically potassium ions) and anions (such as anions containing sulfate ions, typically sulfate ions) will be eliminated from the system together with water. In addition, the ionic component imparts charge to the surface of the oxidized silicon particles in the oxidized silicon sol, forming a moderate reactive force of the oxidized silicon particles and preventing the aggregation of the oxidized silicon particles. On the other hand, even if a large amount of ion components are present, aggregation of silicon oxide particles does not occur. It is preferable that the concentration of cations and anions in these oxidized silica sol can be reduced by extreme filtration. For example, it is preferable to suppress the concentration change of cations and anions to within 10 times of the concentration (mass % concentration) in the oxidized silica sol before the concentration step. When the concentration of this plasma component is set within the above range, the formation of a filter cake layer can be suppressed.
若設定在此等範圍時，可在藉由在濃縮步驟之氧化矽溶膠的注入或循環之製程(要件B)中進行調整。即藉由於經循環的濃縮步驟中或濃縮步驟後之氧化矽溶膠中進一步注入氧化矽溶膠(進一步注入的氧化矽溶膠中所含之氧化矽粒子的濃度為，於濃縮步驟前之氧化矽溶膠中所含的氧化矽粒子之濃度的0.1～30倍之濃度。)，或者藉由調整氧化矽溶膠之循環時間而設定在上述範圍中。If it is set within these ranges, it can be adjusted in the process (requirement B) by injecting or circulating the oxidized silica sol in the concentration step. That is, by further injecting silica oxide sol into the silica oxide sol during or after the concentration step of the cycle (the concentration of silica oxide particles contained in the silica oxide sol further injected is, in the silica oxide sol before the concentration step The concentration is 0.1 to 30 times the concentration of the contained silicon oxide particles.), or is set within the above range by adjusting the circulation time of the silicon oxide sol.
作為上述陽離子，例如可舉出1價陽離子，由可抑制粗大粒子之觀點來看，以鉀離子或鈉離子為特佳。Examples of the cation include monovalent cations, and potassium ions or sodium ions are particularly preferred from the viewpoint of suppressing coarse particles.
作為上述陰離子，例如可舉出含有硫酸離子之陰離子，由可抑制粗大粒子之觀點來看，以硫酸離子為特佳。Examples of the anion include anions containing sulfate ions, and sulfate ions are particularly preferred from the viewpoint of suppressing coarse particles.
本發明中，作為在極限過濾裝置進行濃縮之氧化矽溶膠，雖亦可使用藉由烷氧化物法之氧化矽溶膠，較佳為使用含有自矽酸鹼水溶液除去鹼金屬離子而得的矽酸水溶液經加熱後得到之氧化矽粒子的氧化矽溶膠。 [實施例] In the present invention, as the oxidized silica sol concentrated in an extreme filtration device, an oxidized silica sol obtained by an alkoxide method may also be used. However, it is preferable to use silicic acid containing silica sol obtained by removing alkali metal ions from an aqueous silicate alkali solution. Oxidized silica sol is an oxidized silica particle obtained by heating an aqueous solution. [Example]
(活性矽酸之製造) 作為原料之水溶性鹼金屬矽酸鹽，準備JIS3號之鈉水玻璃。該水玻璃之水以外的主要成分為SiO 2：28.8重量%，Na 2O：9.47質量%。將上述水玻璃833kg以純水5167kg稀釋後，調製出矽酸鈉水溶液(a)6000kg。其次，將上述矽酸鈉水溶液(a)以每小時的空間速度4.5流通於填充有氫型強酸性陽離子交換樹脂琥珀石IR-120B之管柱，回收活性矽酸之水溶液5500kg。 (氧化矽溶膠稀薄液之製造) 於具備攪拌機與加熱裝置之SUS製耐壓反應槽中，裝入活性矽酸之水溶液(作為SiO 2為3.2質量%)、10質量%之氫氧化鉀水溶液及純水，將pH調整至11.1，將反應液溫升溫至110～130℃。反應液溫到達110～130℃後，將反應液溫保持在110～130℃下，連續供給活性矽酸之水溶液使反應液的pH達到11.2。接著將所得之反應液一邊保持在110～130℃，一邊繼續加熱2小時後，冷卻至室溫後得到氧化矽溶膠(稀薄液1)。 (Production of activated silicic acid) As a raw material of water-soluble alkali metal silicate, JIS No. 3 sodium water glass was prepared. The main components of this water glass other than water are SiO 2 : 28.8% by weight, and Na 2 O : 9.47% by mass. After diluting 833kg of the above water glass with 5167kg of pure water, 6000kg of sodium silicate aqueous solution (a) was prepared. Next, the above-mentioned sodium silicate aqueous solution (a) was circulated at a space velocity of 4.5 per hour through a column filled with hydrogen-type strongly acidic cation exchange resin amber stone IR-120B, and 5500 kg of the active silicic acid aqueous solution was recovered. (Production of thin silica sol solution) Into a SUS-made pressure-resistant reaction tank equipped with a stirrer and a heating device, an aqueous solution of activated silicic acid (3.2% by mass as SiO2 ), a 10% by mass potassium hydroxide aqueous solution, and Pure water, adjust the pH to 11.1, and raise the temperature of the reaction solution to 110~130°C. After the reaction liquid temperature reaches 110 to 130°C, the reaction liquid temperature is maintained at 110 to 130°C, and an aqueous solution of activated silicic acid is continuously supplied to make the pH of the reaction liquid reach 11.2. Then, the obtained reaction liquid was heated for 2 hours while maintaining it at 110 to 130°C, and then cooled to room temperature to obtain silica oxide sol (thin liquid 1).
(實施例1) (氧化矽溶膠稀薄液之濃縮) 將所得之氧化矽溶膠稀薄液1循環流過截留分子量10萬之聚碸製的管狀極限過濾膜(亦稱為UF試管。內徑：1/2英吋)，藉由壓力0.25MPa，流量6.9L/分鐘，液溫30℃，濃縮至氧化矽濃度40質量%程度。 (LPC(粗大粒子數)之測定方法) LPC之測定為，將試樣的氧化矽濃度以純水稀釋至15.0質量%，藉由PSS日本股份有限公司製造AccuSizer FX-nano(Nihon Entegris G.K.製，商品名AccuSizer A9000)測定LPC值。試樣之氧化矽濃度未達15.0質量%之情況時，直接測定，將測定值換算為15.0質量%。 氧化矽濃度之測定為，精秤試樣約1g，在140℃之加熱板上使其乾燥，在1000℃燒烤0.5小時，自燒烤殘餘部分算出氧化矽濃度。 (游離離子量之測定方法) 將稀釋成15.0質量%之SiO 2的試樣放入於密閉容器，經全冷凍並解凍後，以孔徑0.45um之色譜盤進行過濾。以純水稀釋至該濾液中之離子濃度成為標準曲線之濃度範圍，藉由離子色譜分析裝置定量陽離子量與陰離子量。 (Example 1) (Concentration of the dilute silica sol solution 1) The obtained dilute silica sol solution 1 was circulated through a tubular limit filtration membrane (also called a UF test tube) made of polystyrene with a molecular weight cutoff of 100,000. Inner diameter: 1 /2 inches), with a pressure of 0.25MPa, a flow rate of 6.9L/min, and a liquid temperature of 30°C, it is concentrated to a silicon oxide concentration of about 40% by mass. (Measurement method of LPC (coarse particle number)) LPC was measured by diluting the silica concentration of the sample to 15.0% by mass with pure water, and using AccuSizer FX-nano (manufactured by Nihon Entegris GK, manufactured by PSS Japan Co., Ltd., Trade name AccuSizer A9000) to measure LPC value. When the silicon oxide concentration of the sample does not reach 15.0 mass%, measure it directly and convert the measured value to 15.0 mass%. To measure the silicon oxide concentration, weigh about 1g of the sample accurately, dry it on a hot plate at 140°C, grill it at 1000°C for 0.5 hours, and calculate the silicon oxide concentration from the remaining part of the grill. (Measurement method of free ion amount) A sample diluted to 15.0 mass% SiO 2 is placed in a closed container, completely frozen and thawed, and then filtered through a chromatographic disk with a pore size of 0.45um. Dilute with pure water until the ion concentration in the filtrate becomes the concentration range of the standard curve, and quantify the amount of cations and anions using an ion chromatography analysis device.
(實施例2) 將與實施例1相同操作所得之氧化矽溶膠，循環流通於截留分子量10萬之聚碸製管狀極限過濾膜(內徑1/2英吋)，在壓力0.10MPa，流量8.8L/分鐘且30℃下，濃縮至氧化矽濃度40質量%程度。 (Example 2) The oxidized silica sol obtained by the same operation as in Example 1 was circulated through a polystyrene tubular extreme filtration membrane (inner diameter 1/2 inch) with a molecular weight cutoff of 100,000, at a pressure of 0.10MPa, a flow rate of 8.8L/min and a flow rate of 30 ℃, and concentrated to a silicon oxide concentration of about 40% by mass.
(實施例3) 將與實施例1相同操作所得之氧化矽溶膠，循環流通於截留分子量10萬之聚碸製管狀極限過濾膜(內徑1/2英吋)，在壓力0.05MPa，流量9.5L/分鐘且30℃下，濃縮至氧化矽濃度40質量%程度。 (Example 3) The oxidized silica sol obtained by the same operation as in Example 1 was circulated through a polystyrene tubular extreme filter membrane (inner diameter 1/2 inch) with a molecular weight cutoff of 100,000, at a pressure of 0.05MPa, a flow rate of 9.5L/min and a flow rate of 30 ℃, and concentrated to a silicon oxide concentration of about 40% by mass.
(實施例4) 將與實施例1相同操作所得之氧化矽溶膠，循環流通於截留分子量50萬之聚碸製管狀極限過濾膜(內徑1/2英吋)，在壓力0.25MPa，流量6.9L/分鐘且30℃下，濃縮至氧化矽濃度40質量%程度。 (Example 4) The oxidized silica sol obtained by the same operation as in Example 1 was circulated through a polystyrene tubular extreme filter membrane (inner diameter 1/2 inch) with a molecular weight cutoff of 500,000, at a pressure of 0.25MPa, a flow rate of 6.9L/min and a flow rate of 30 ℃, and concentrated to a silicon oxide concentration of about 40% by mass.
(實施例5) 將與實施例1相同操作所得之氧化矽溶膠，循環流通於截留分子量50萬之聚碸製管狀極限過濾膜(內徑1/2英吋)，在壓力0.10MPa，流量8.8L/分鐘且30℃下，濃縮至氧化矽濃度40質量%程度。 (Example 5) The oxidized silica sol obtained by the same operation as in Example 1 was circulated through a polystyrene tubular extreme filter membrane (inner diameter 1/2 inch) with a molecular weight cutoff of 500,000, at a pressure of 0.10MPa, a flow rate of 8.8L/min and a flow rate of 30 ℃, and concentrated to a silicon oxide concentration of about 40% by mass.
(實施例6) 將與實施例1相同操作所得之氧化矽溶膠，循環流通於截留分子量50萬之聚碸製管狀極限過濾膜(內徑1/2英吋)，在壓力0.05MPa，流量9.5L/分鐘且30℃下，濃縮至氧化矽濃度40質量%程度。 (Example 6) The oxidized silica sol obtained by the same operation as in Example 1 was circulated through a polystyrene tubular extreme filter membrane (inner diameter 1/2 inch) with a molecular weight cutoff of 500,000, at a pressure of 0.05MPa, a flow rate of 9.5L/min and a flow rate of 30 ℃, and concentrated to a silicon oxide concentration of about 40% by mass.
(實施例7) 將與實施例1相同操作所得之氧化矽溶膠，循環流通於截留分子量10萬之聚碸製管狀極限過濾膜(內徑1/2英吋)，在壓力0.05MPa，流量9.5L/分鐘且15℃下，濃縮至氧化矽濃度40質量%程度。 (Example 7) The oxidized silica sol obtained by the same operation as in Example 1 was circulated through a polystyrene tubular extreme filter membrane (inner diameter 1/2 inch) with a molecular weight cutoff of 100,000, at a pressure of 0.05MPa, a flow rate of 9.5L/min and 15 ℃, and concentrated to a silicon oxide concentration of about 40% by mass.
表1中記載，使用內徑1/2英吋的UF試管，進行氧化矽溶膠之濃縮，UF濃縮後之沖洗水的混入(自所謂推水配管的氧化矽溶膠之取出操作)之有無。未使用UF濃縮後之沖洗水者記載為(無)，使用UF濃縮後之沖洗水者記載為(有)。 稀薄液1為，UF濃縮前之氧化矽濃度3.2質量%的氧化矽溶膠，其為藉由實施例1～實施例8及比較例1～5所得之下述氧化矽濃縮液1～13的原料。 濃縮液1為，實施例1所得之藉由UF濃縮的氧化矽濃度36.0質量%之氧化矽溶膠(實施例1)。 濃縮液2為，實施例2所得之藉由UF濃縮的氧化矽濃度35.7質量%之氧化矽溶膠(實施例2)。 濃縮液3為，實施例3所得之藉由UF濃縮之氧化矽濃度35.2質量%的氧化矽溶膠(實施例3)。 濃縮液4為，實施例4所得之藉由UF濃縮之氧化矽濃度38.4質量%的氧化矽溶膠(實施例4)。 濃縮液5為，實施例5所得之藉由UF濃縮之氧化矽濃度35.1質量%的氧化矽溶膠(實施例5)。 濃縮液6為，實施例6所得之藉由UF濃縮之氧化矽濃度36.9質量%的氧化矽溶膠(實施例6)。 濃縮液7為，實施例7所得之藉由UF濃縮之氧化矽濃度38.6質量%的氧化矽溶膠(實施例7)。 表1中之(──)表示未實施者。 Table 1 describes the concentration of silica oxide using a UF test tube with an inner diameter of 1/2 inch, and the presence or absence of mixing of rinse water after UF concentration (removing the silica oxide from the so-called water push pipe). Those who do not use UF-concentrated flushing water are recorded as (none), and those who use UF-concentrated flushing water are recorded as (yes). Thin liquid 1 is a silica sol with a silicon oxide concentration of 3.2% by mass before UF concentration, which is the raw material for the following silicon oxide concentrated liquids 1 to 13 obtained by Examples 1 to 8 and Comparative Examples 1 to 5. . Concentrated liquid 1 is a silica oxide sol with a silica oxide concentration of 36.0% by mass obtained in Example 1 and concentrated by UF (Example 1). Concentrated solution 2 is a silica oxide sol with a silica oxide concentration of 35.7% by mass obtained in Example 2 and concentrated by UF (Example 2). Concentrated solution 3 is a silica oxide sol with a silica oxide concentration of 35.2% by mass obtained by UF concentration in Example 3 (Example 3). Concentrated solution 4 is a silica oxide sol with a silica oxide concentration of 38.4% by mass obtained by UF concentration in Example 4 (Example 4). Concentrated solution 5 is a silica oxide sol with a silicon oxide concentration of 35.1% by mass obtained by UF concentration in Example 5 (Example 5). Concentrated solution 6 is a silica oxide sol with a silica oxide concentration of 36.9% by mass obtained by UF concentration in Example 6 (Example 6). Concentrate 7 is a silica oxide sol with a silica oxide concentration of 38.6% by mass obtained by UF concentration in Example 7 (Example 7). (──) in Table 1 indicates those that have not been implemented.
表2表示經濃縮的氧化矽溶膠之物理性質。其表示SiO 2濃度(質量%)、陽離子量(質量%)、陰離子量(質量%)。表2中之LPC表示，粒子徑0.48μm以上的粗大粒子之數目。表2中之( )表示未測定者。 Table 2 shows the physical properties of the concentrated silica oxide sol. It represents the SiO 2 concentration (mass %), the amount of cations (mass %), and the amount of anions (mass %). LPC in Table 2 represents the number of coarse particles with a particle diameter of 0.48 μm or more. In Table 2 ( ) indicates those that have not been measured.
在相同截留分子量與相同壓力下對實施例3與實施例7進行對比時，確認到UF處理溫度為30℃的實施例3之濃縮液3與UF處理溫度為15℃的實施例7之濃縮液7相比較，LPC的數值有降低之情況。 在相同溫度與相同截留分子量對於各實施例1～實施例3、實施例4～實施例6進行對比時，確認到UF處理壓力的上升亦可使LPC值上升。 When comparing Example 3 and Example 7 under the same molecular weight cutoff and the same pressure, it was confirmed that the concentrated solution 3 of Example 3 with a UF treatment temperature of 30°C and the concentrated solution of Example 7 with a UF treatment temperature of 15°C 7 In comparison, the value of LPC has decreased. When comparing Examples 1 to 3 and 4 to 6 at the same temperature and the same molecular weight cutoff, it was confirmed that an increase in the UF treatment pressure also increased the LPC value.
(實施例8) 將與實施例1相同操作所得之氧化矽溶膠，使用安裝有截留分子量10萬的聚偏二氟乙烯製管狀極限過濾膜(內徑1英吋)之販售品極限過濾裝置，藉由壓力0.3MPa且流速420L/分鐘在30℃下濃縮至SiO 2濃度為40質量%程度。未有UF濃縮後之沖洗水混入(自所謂推水配管的氧化矽溶膠之取出操作)。 (Example 8) A commercial extreme filtration device equipped with a tubular extreme filtration membrane (inner diameter 1 inch) made of polyvinylidene fluoride with a molecular weight cutoff of 100,000 was used for the oxidized silica sol obtained in the same manner as in Example 1. , concentrated to a SiO 2 concentration of about 40 mass% at 30°C with a pressure of 0.3MPa and a flow rate of 420L/min. There is no mixing of the rinse water after UF concentration (from the operation of removing the oxidized silica sol from the so-called water push pipe).
(比較例1～比較例5) 將與實施例1相同操作所得之氧化矽溶膠，使用安裝有截留分子量10萬的聚偏二氟乙烯製管狀極限過濾膜(內徑1英吋)之販售品極限過濾裝置，藉由壓力0.3MPa且流速420L/分鐘，在50～70℃濃縮至SiO 2濃度為40質量%程度。合併記載有混入UF濃縮後之沖洗水(自所謂推水配管的氧化矽溶膠之取出操作)之情況，與未進行之情況。所謂混入UF濃縮後之沖洗水的情況，其表示於UF試管內流入純水而回收濃縮液之情況時，藉由該操作可使濃縮液之氧化矽濃度可局部性地降低很多者。 濃縮液8為，實施例8所得之藉由UF濃縮之氧化矽濃度39.0質量%的氧化矽溶膠(實施例8)。 濃縮液9為，比較例1所得之藉由UF濃縮之氧化矽濃度36.6質量%的氧化矽溶膠(比較例1)。 濃縮液10為，比較例2所得之藉由UF濃縮之氧化矽濃度43.4質量%的氧化矽溶膠(比較例2)。 濃縮液11為，比較例3所得之藉由UF濃縮之氧化矽濃度40.0質量%的氧化矽溶膠(比較例3)。 濃縮液12為，比較例4所得之藉由UF濃縮之氧化矽濃度40.6質量%的氧化矽溶膠(比較例4)。 濃縮液13為，比較例5所得之藉由UF濃縮之氧化矽濃度44.3質量%的氧化矽溶膠(比較例5)。 表3中之(──)表示未實施者。 (Comparative Examples 1 to 5) The silica oxide obtained in the same manner as in Example 1 was used, and a commercially available tubular limit filtration membrane (inner diameter: 1 inch) made of polyvinylidene fluoride with a molecular weight cutoff of 100,000 was used. The product's extreme filtration device uses a pressure of 0.3MPa and a flow rate of 420L/min to concentrate the SiO 2 concentration to about 40 mass% at 50 to 70°C. The cases in which the rinse water after UF concentration was mixed (the operation of removing the oxidized silica sol from the so-called push water pipe) are combined, and the cases in which it was not performed are included. The so-called mixing of rinse water after UF concentration means that when pure water flows into a UF test tube and the concentrated liquid is recovered, the silicon oxide concentration of the concentrated liquid can be greatly reduced locally by this operation. Concentrated solution 8 is a silica oxide sol with a silica oxide concentration of 39.0% by mass obtained by UF concentration in Example 8 (Example 8). Concentrated solution 9 is a silica oxide sol with a silica oxide concentration of 36.6% by mass obtained by UF concentration in Comparative Example 1 (Comparative Example 1). Concentrated solution 10 is a silica oxide sol obtained by UF concentration with a silica oxide concentration of 43.4% by mass obtained in Comparative Example 2 (Comparative Example 2). Concentrated solution 11 is a silica oxide sol with a silica oxide concentration of 40.0% by mass obtained by UF concentration in Comparative Example 3 (Comparative Example 3). The concentrated liquid 12 is a silica oxide sol with a silica oxide concentration of 40.6% by mass obtained by UF concentration in Comparative Example 4 (Comparative Example 4). Concentrated solution 13 is a silica oxide sol obtained by UF concentration with a silica oxide concentration of 44.3% by mass obtained in Comparative Example 5 (Comparative Example 5). (──) in Table 3 indicates that it has not been implemented.
表4表示經濃縮的氧化矽溶膠之物理性質。其表示SiO 2濃度(質量%)、陽離子量(質量%)、陰離子量(質量%)。表4中之LPC表示粒子徑0.48μm以上的粗大粒子之數目。 Table 4 shows the physical properties of the concentrated silica oxide sol. It represents the SiO 2 concentration (mass %), the amount of cations (mass %), and the amount of anions (mass %). LPC in Table 4 represents the number of coarse particles with a particle diameter of 0.48 μm or more.
在相同截留分子量、相同壓力與未有UF後之沖洗水的情況進行對比時，由實施例8與比較例1及比較例3的對比確認到隨著UF處理溫度之上升，LPC之數值亦上升。 在相同截留分子量、相同壓力與相同UF處理溫度下進行對比時，未進行UF後之沖洗水混入的情況與進行UF後之沖洗水混入的情況中，由實施例8與比較例5之對比、比較例1與比較例2之對比、比較例3與比較例4之對比可得知，由於UF後之沖洗水混入，LPC大幅上升。所謂混入UF後之沖洗水表示，於UF試管內流入純水而回收濃縮液之操作的意思，其為濃縮液之氧化矽濃度呈局部性地大為降低者。其可推測藉由該操作，UF膜內面之濾餅層在氧化矽濃縮液中脫落而使LPC上升者。 對表1與表2之結果、表3與表4之結果進行對比時，使UF試管之內徑變大，使壓力變高之表3與表4中，其處理液之流速比表1與表2之結果亦高，可推測為氧化矽粒子之體積層因難形成於UF膜上故LPC的數值為低。 由表1至表4的結果可得知，藉由將UF處理溫度設定在本發明之範圍，且進行UF後之沖洗水混入時(即，與藉由連續提高氧化矽粒子之濃度的操作在極限過濾裝置使氧化矽溶膠進行循環，或於極限過濾裝置中進一步注入氧化矽溶膠(進一步注入的氧化矽溶膠為，含於濃縮步驟前之氧化矽溶膠中的氧化矽粒子之濃度的0.1～30倍濃度)，於濃縮步驟後在該氧化矽溶膠中所含的氧化矽粒子之濃度比濃縮步驟前更上升者相關。)，可抑制在氧化矽溶膠的濃縮步驟中產生的LPC(粗大粒子)之混入。 [產業上可利用性] When comparing the conditions of the same molecular weight cutoff, the same pressure and the absence of rinse water after UF, it was confirmed from the comparison between Example 8 and Comparative Examples 1 and 3 that as the UF treatment temperature increases, the LPC value also increases. . When comparing under the same molecular weight cut-off, the same pressure and the same UF treatment temperature, between the case where the rinse water after UF is not mixed and the case where the rinse water after UF is mixed, from the comparison between Example 8 and Comparative Example 5, From the comparison between Comparative Example 1 and Comparative Example 2, and the comparison between Comparative Example 3 and Comparative Example 4, it can be seen that the LPC increases significantly due to the mixing of rinse water after UF. The so-called flushing water mixed with UF means the operation of flowing pure water into the UF test tube and recovering the concentrated liquid, which means that the silicon oxide concentration of the concentrated liquid is greatly reduced locally. It is presumed that through this operation, the filter cake layer on the inner surface of the UF membrane falls off in the concentrated silicon oxide solution, causing the LPC to rise. When comparing the results in Tables 1 and 2, and the results in Tables 3 and 4, in Tables 3 and 4 in which the inner diameter of the UF test tube is enlarged and the pressure is increased, the flow rate of the treatment liquid is higher than that in Table 1 and Table 4. The results in Table 2 are also high. It can be inferred that the volume layer of silicon oxide particles is difficult to form on the UF film, so the LPC value is low. It can be seen from the results in Tables 1 to 4 that by setting the UF treatment temperature within the range of the present invention and mixing the rinse water after UF (that is, by continuously increasing the concentration of silicon oxide particles), The limit filtration device circulates the silica oxide sol, or further injects the silica oxide sol into the limit filtration device (the silica oxide further injected is 0.1 to 30 times the concentration of the silica oxide particles contained in the silica oxide sol before the concentration step) times the concentration), the concentration of the silica oxide particles contained in the oxidized silica sol after the concentration step is higher than before the concentration step.), which can suppress LPC (coarse particles) generated in the concentration step of the oxidized silica sol. mixed in. [Industrial availability]
本發明之氧化矽溶膠的濃縮方法中，在進行藉由極限過濾而提高氧化矽溶膠中之氧化矽成分的濃度之濃縮時，可防止凝集於經濃縮的氧化矽溶膠中之氧化矽粒子的形成。因此，例如在製造使用於半導體用矽晶圓或裝置之研磨的氧化矽溶膠時，前述方法因可抑制LPC(粗大粒子)對該氧化矽溶膠中之混入而有用。In the concentration method of the silica oxide sol of the present invention, when concentration is performed to increase the concentration of the silica oxide component in the silica oxide sol by extreme filtration, the formation of silica oxide particles aggregated in the concentrated silica oxide sol can be prevented. . Therefore, for example, when producing silica oxide sol used for polishing silicon wafers or devices for semiconductors, the above method is useful because it can suppress mixing of LPC (coarse particles) into the silica oxide sol.
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