JP6141482B1 - Nanobubble-containing inorganic oxide fine particle dispersion, abrasive containing the same, and production method thereof - Google Patents
Nanobubble-containing inorganic oxide fine particle dispersion, abrasive containing the same, and production method thereof Download PDFInfo
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- 239000010419 fine particle Substances 0.000 title claims abstract description 155
- 239000002101 nanobubble Substances 0.000 title claims abstract description 114
- 239000006185 dispersion Substances 0.000 title claims abstract description 103
- 229910052809 inorganic oxide Inorganic materials 0.000 title claims abstract description 102
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000005498 polishing Methods 0.000 claims description 35
- 239000007864 aqueous solution Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 29
- 238000001914 filtration Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 83
- 239000000377 silicon dioxide Substances 0.000 description 41
- 239000007788 liquid Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 14
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 11
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 11
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 239000011362 coarse particle Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 238000007517 polishing process Methods 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000009172 bursting Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000003703 image analysis method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- WSMQKESQZFQMFW-UHFFFAOYSA-N 5-methyl-pyrazole-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=NN1 WSMQKESQZFQMFW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Landscapes
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
【課題】研磨剤として用いる工程において濃縮安定性に優れるナノバブル含有無機酸化物微粒子分散液の製造方法の提供。【解決手段】平均粒子径が１〜５００ｎｍの微粒子を含む無機酸化物微粒子分散液と、平均気泡径が５０〜５００ｎｍのナノバブルを含むナノバブル水溶液とを含む溶液を、５〜８０℃に保持しつつ、混合する工程を備える、ナノバブル含有無機酸化物微粒子分散液の製造方法。【選択図】図１Provided is a method for producing a nanobubble-containing inorganic oxide fine particle dispersion having excellent concentration stability in a step of using as an abrasive. A solution containing an inorganic oxide fine particle dispersion containing fine particles having an average particle size of 1 to 500 nm and an aqueous nanobubble solution containing nanobubbles having an average bubble size of 50 to 500 nm is maintained at 5 to 80 ° C. The manufacturing method of a nanobubble containing inorganic oxide fine particle dispersion provided with the process to mix. [Selection] Figure 1
Description
本発明は、無機酸化物微粒子分散液がナノバブル（微小気泡）を含有してなるナノバブル含有無機酸化物微粒子分散液の製造方法と、その製造方法により得られるナノバブル含有無機酸化物微粒子分散液に関するものである。また、本発明は、該ナノバブル含有無機酸化物微粒子分散液を含む研磨剤（研磨用スラリー）の製造方法と、その製造方法により得られるナノバブル含有無機酸化物微粒子分散液を含む研磨剤（研磨用スラリー）に関する。 The present invention relates to a method for producing a nanobubble-containing inorganic oxide fine particle dispersion in which the inorganic oxide fine particle dispersion contains nanobubbles (microbubbles), and a nanobubble-containing inorganic oxide fine particle dispersion obtained by the production method. It is. The present invention also provides a method for producing an abrasive (polishing slurry) containing the nanobubble-containing inorganic oxide fine particle dispersion, and an abrasive containing an nanobubble-containing inorganic oxide fine particle dispersion obtained by the production method (for polishing). Slurry).
半導体基板、配線基板などの半導体デバイスなどにおいては、表面状態が半導体特性に影響するため、これらの部品の表面や端面を極めて高精度に研磨することが要求される。
従来、このような部材の研磨方法として、比較的粗い１次研磨処理を行った後、精密な２次研磨処理を行うことにより、平滑な表面あるいはスクラッチなどの傷が少ない極めて高精度の表面を得る方法が行われている。
このような仕上げ研磨としての２次研磨に用いる研磨剤として、従来、例えば次のような方法等が提案されている。
In semiconductor devices such as a semiconductor substrate and a wiring substrate, the surface state affects the semiconductor characteristics, and therefore, it is required to polish the surfaces and end faces of these components with extremely high accuracy.
Conventionally, as a polishing method for such a member, after performing a relatively rough primary polishing process, and then performing a precise secondary polishing process, a smooth surface or a highly accurate surface with few scratches such as scratches can be obtained. The way to get done.
Conventionally, for example, the following method has been proposed as an abrasive used for such secondary polishing as final polishing.
特許文献１には、シリカ微粒子が分散媒に分散してなるシリカゾルであって、該シリカ微粒子の粒子径分布における最頻値粒子径が５〜１００ｎｍの範囲にあり、更に１）最頻値粒子径を超えるシリカ微粒子の割合が、全シリカ微粒子に対して０．１〜３０体積％の範囲であり、２）最頻値粒子径以下の粒子径分布における粒子径変動係数が、８〜７０％の範囲であるという条件を満たすことを特徴とする研磨用シリカゾルが提案されている。そして、このような研磨用シリカゾルによれば、研磨用途に適用して、線状痕やスクラッチ等の発生が抑制され、優れた研磨速度を持続して示すと記載されている。 Patent Document 1 discloses a silica sol in which silica fine particles are dispersed in a dispersion medium, wherein the mode particle diameter in the particle size distribution of the silica fine particles is in the range of 5 to 100 nm, and 1) mode particles. The ratio of the silica fine particles exceeding the diameter is in the range of 0.1 to 30% by volume with respect to the total silica fine particles, and 2) the particle size variation coefficient in the particle size distribution below the mode particle size is 8 to 70%. There has been proposed a polishing silica sol characterized by satisfying the condition that it is in the range of. And, according to such a silica sol for polishing, it is described that it is applied to a polishing application, and generation of linear traces, scratches and the like is suppressed, and an excellent polishing rate is continuously exhibited.
一般にシリカ微粒子等の無機酸化物微粒子が分散媒に分散してなる無機酸化物微粒子分散液は、特に支障が無い限り、固形分濃度が高いものの方が運搬の作業や各種工程での取扱いに適している。また、該無機酸化物微粒子分散液を研磨用途に適用した場合、研磨処理は、開放系で行われることが多く、研磨液調製時には、周りの環境変化（温度、湿度等）やタンク内の撹拌による研磨液の液面変動、飛散液等により、乾燥物や一部濃縮によるミクロゲル等の異物が発生することが多いために、一般的には、必要とする工程若しくは最終工程で精密ろ過が行われている。また、研磨に時間を要する研磨基板（例えば、タンタル酸リチウム、タンタル酸ニオブ、サファイア等）については、必要に応じて研磨液を再度循環して使用されることが行われ、周りの環境変化や研磨液の消費に伴う循環タンクの液面変化、循環液の戻りラインからの研磨液の落下に伴う液面変動等により、循環タンク壁面でのスケール生成や研磨液の濃縮によるミクロゲルの発生、凝集物の生成等をもたらすことが多い。この様な異物は、精密ろ過により、硬くて大きな異物は、ある程度除去出来るが、特に柔軟なで細かいミクロゲルを完全に除去することは、困難とされている。このようなミクロゲル異物を含む無機酸化物微粒子分散液による研磨処理は、被研磨面でのスクラッチ（線状痕）の発生や研磨作業の作業性低下を招くことが知られている。
なお、無機酸化物微粒子分散液の濃縮により、被研磨面でのスクラッチ（線状痕）の発生や研磨作業の作業性低下を招く原因は、例えば、シリカ微粒子分散液の場合、シリカ微粒子分散液に含まれるミクロゲル（低分子シリカの凝集体等）が、濃縮により、ミクロゲルどうしで更に凝集すること、あるいはミクロゲルとシリカ微粒子との凝集が生じることにより、スクラッチ発生や作業性低下の原因となり得る大きさの凝集物が生成することが影響するものと考えられている。
また、シリカ微粒子分散液に限らず、無機酸化物微粒子分散液は、その調製工程及び研磨工程においても、周りの環境変化（温度、湿度等）やタンク内の撹拌による研磨液の液面変動、飛散液等により、非沈降性の微粒子あるいはミクロゲルが生成することが多い。無機酸化物微粒子分散液を研磨用途に適用する場合、前記非沈降性の微粒子あるいはミクロゲルは、更に凝集して粗大粒子となり、無機酸化物微粒子分散液を研磨用途に使用する前に行う濾過処理において、濾過性の低下を招き易いことが知られていた。
In general, inorganic oxide fine particle dispersions in which inorganic oxide fine particles such as silica fine particles are dispersed in a dispersion medium are suitable for transporting operations and handling in various processes unless there is a particular problem. ing. In addition, when the inorganic oxide fine particle dispersion is applied to a polishing application, the polishing treatment is often performed in an open system, and when the polishing liquid is prepared, the surrounding environment changes (temperature, humidity, etc.) and stirring in the tank In many cases, foreign matters such as dry matter and microgel due to partial concentration are generated due to fluctuations in the surface of the polishing liquid due to the liquid and splashed liquid. It has been broken. In addition, for polishing substrates that require time for polishing (for example, lithium tantalate, niobium tantalate, sapphire, etc.), the polishing liquid is circulated again and used as necessary, Due to changes in the level of the circulating tank due to the consumption of the polishing liquid, and fluctuations in the liquid level due to the falling of the polishing liquid from the return line of the circulating liquid, generation of microgel due to scale generation and concentration of the polishing liquid, and agglomeration It often leads to the production of things. Such foreign matters are hard and large foreign matters can be removed to some extent by microfiltration, but it is particularly difficult to completely remove fine microgels that are particularly flexible. It is known that such a polishing process using an inorganic oxide fine particle dispersion containing a microgel foreign material causes generation of scratches (linear marks) on the surface to be polished and a reduction in workability of the polishing operation.
The cause of the generation of scratches (linear traces) on the surface to be polished and the reduction in the workability of the polishing work due to the concentration of the inorganic oxide fine particle dispersion is, for example, in the case of a silica fine particle dispersion, The microgels (such as low-molecular silica aggregates) contained in can be further agglomerated between microgels due to concentration, or agglomeration between microgels and silica fine particles can cause scratches and reduced workability. It is considered that the formation of agglomerates is affected.
In addition to the silica fine particle dispersion, the inorganic oxide fine particle dispersion is also used in the preparation process and the polishing process, in the surrounding environment (temperature, humidity, etc.) and fluctuations in the liquid level of the polishing liquid due to stirring in the tank, In many cases, non-sedimentable fine particles or microgels are generated by the scattering liquid or the like. In the case where the inorganic oxide fine particle dispersion is applied for polishing, the non-sedimentable fine particles or microgel are further aggregated into coarse particles, and the filtration treatment is performed before the inorganic oxide fine particle dispersion is used for polishing. It has been known that the filterability tends to be lowered.
本発明は上記のような課題を解決するために鋭意検討し、シリカゾル等の無機酸化物微粒子分散液、ナノバブルを特定条件にて加え、ナノバブルがその機能が発揮できる特定条件で混合することで、上記の課題を解決することできる無機酸化物微粒子分散液あるいはそれを含む研磨剤が得られることを見出した。
すなわち、本発明は、研磨剤として用いる工程において濃縮安定性に優れるナノバブル含有無機酸化物微粒子分散液、それを含む研磨剤およびそれらの製造方法を提供することを目的とする。
本発明は、ナノバブルの破裂効果により、シリカ微粒子分散液などの無機酸化物微粒子分散液中に存在するミクロゲルを解砕・分散することにより、ミクロゲルを減少させ、延いては粗大粒子の発生を抑止することにより、濃縮安定性と濾過性向上を達成したものである。
The present invention has been intensively studied to solve the above-mentioned problems, by adding inorganic oxide fine particle dispersion liquid such as silica sol, nanobubbles under specific conditions, and mixing under specific conditions where the nanobubbles can exhibit their functions, It has been found that an inorganic oxide fine particle dispersion capable of solving the above problems or an abrasive containing the same can be obtained.
That is, an object of the present invention is to provide a nanobubble-containing inorganic oxide fine particle dispersion excellent in concentration stability in a process used as an abrasive, an abrasive containing the same, and a method for producing the same.
The present invention reduces the microgel by suppressing the generation of coarse particles by crushing and dispersing the microgel present in the inorganic oxide fine particle dispersion such as silica fine particle dispersion due to the bursting effect of the nanobubbles. By doing so, concentration stability and filterability improvement are achieved.
本発明者は上記課題を解決するため鋭意検討し、本発明を完成させた。
本発明は以下の（１）〜（７）である。
（１）平均粒子径が１〜５００ｎｍの微粒子を含む無機酸化物微粒子分散液と、平均気泡径が５０〜５００ｎｍのナノバブルを含むナノバブル水溶液とを含む溶液を、５〜８０℃に保持しつつ、混合する工程を備える、ナノバブル含有無機酸化物微粒子分散液の製造方法。
（２）前記ナノバブルがＮ2、Ｈ2およびＯ2からなる群から選ばれる少なくとも１つである、上記（１）に記載のナノバブル含有無機酸化物微粒子分散液の製造方法。
（３）前記ナノバブル水溶液が、１０5個／ｍＬ以上のナノバブルを含む、上記（１）または（２）に記載のナノバブル含有無機酸化物微粒子分散液の製造方法。
（４）前記無機酸化物微粒子分散液の内部で前記ナノバブルを発生させることで、前記無機酸化物微粒子分散液と前記ナノバブル水溶液とを含む前記溶液を得る、上記（１）〜（３）のいずれかに記載のナノバブル含有無機酸化物微粒子分散液の製造方法。
（５）上記（１）〜（４）のいずれかに記載の製造方法によってナノバブル含有無機酸化物微粒子分散液を得た後、これを用いて研磨剤を得る、研磨剤の製造方法。
（６）上記（１）〜（４）のいずれかに記載の製造方法によって製造されたナノバブル含有無機酸化物微粒子分散液。
（７）上記（６）に記載のナノバブル含有無機酸化物微粒子分散液を含む研磨材。
The inventor has intensively studied to solve the above-mentioned problems, and has completed the present invention.
The present invention includes the following (1) to (7).
(1) While maintaining a solution containing an inorganic oxide fine particle dispersion containing fine particles having an average particle size of 1 to 500 nm and a nanobubble aqueous solution containing nanobubbles having an average bubble size of 50 to 500 nm at 5 to 80 ° C., The manufacturing method of a nanobubble containing inorganic oxide fine particle dispersion provided with the process to mix.
(2) The method for producing a nanobubble-containing inorganic oxide fine particle dispersion liquid according to (1), wherein the nanobubble is at least one selected from the group consisting of N 2 , H 2 and O 2 .
(3) The method for producing a nanobubble-containing inorganic oxide fine particle dispersion as described in (1) or (2) above, wherein the nanobubble aqueous solution contains 10 5 / mL or more nanobubbles.
(4) Any of (1) to (3) above, wherein the nanobubbles are generated inside the inorganic oxide fine particle dispersion to obtain the solution containing the inorganic oxide fine particle dispersion and the nanobubble aqueous solution. A method for producing a nanobubble-containing inorganic oxide fine particle dispersion according to claim 1.
(5) A method for producing an abrasive, wherein a nanobubble-containing inorganic oxide fine particle dispersion is obtained by the production method according to any one of (1) to (4), and then an abrasive is obtained using the nanobubble-containing inorganic oxide fine particle dispersion.
(6) A nanobubble-containing inorganic oxide fine particle dispersion produced by the production method according to any one of (1) to (4) above.
(7) An abrasive containing the nanobubble-containing inorganic oxide fine particle dispersion described in (6) above.
本発明によれば、研磨剤として用いる工程において、濃縮等による固形分の上昇が生じても、濃縮安定性と濾過性に優れ、作業性低下が抑制されるナノバブル含有無機酸化物微粒子分散液、それを含む研磨剤およびそれらの製造方法を提供することができる。 According to the present invention, the nanobubble-containing inorganic oxide fine particle dispersion that is excellent in concentration stability and filterability and suppresses a decrease in workability even if solid content increases due to concentration or the like in the step of using as an abrasive, The abrasive | polishing agent containing it and those manufacturing methods can be provided.
本発明について説明する。
本発明は、平均粒子径が１〜５００ｎｍの微粒子を含む無機酸化物微粒子分散液と、平均気泡径が５０〜５００ｎｍのナノバブルを含むナノバブル水溶液とを含む溶液を、５〜８０℃に保持しつつ、混合する工程を備える、ナノバブル含有無機酸化物微粒子分散液の製造方法である。
このようなナノバブル含有無機酸化物微粒子分散液の製造方法を、以下では「本発明の製造方法」ともいう。
The present invention will be described.
The present invention maintains a solution containing an inorganic oxide fine particle dispersion containing fine particles having an average particle size of 1 to 500 nm and an aqueous nanobubble solution containing nanobubbles having an average bubble size of 50 to 500 nm at 5 to 80 ° C. A method for producing a nanobubble-containing inorganic oxide fine particle dispersion comprising a mixing step.
Hereinafter, such a method for producing a nanobubble-containing inorganic oxide fine particle dispersion is also referred to as “the production method of the present invention”.
本発明の製造方法では、初めに、無機酸化物微粒子分散液と、ナノバブル水溶液とを用意する。 In the production method of the present invention, first, an inorganic oxide fine particle dispersion and a nanobubble aqueous solution are prepared.
無機酸化物微粒子分散液は、平均粒子径が１〜５００ｎｍの無機酸化物微粒子（単に微粒子と記す場合もある）が溶媒に分散してなるものである。
なお、本発明において無機酸化物微粒子の平均粒子径は、画像解析法による測定結果から算定された値を意味する。
The inorganic oxide fine particle dispersion is obtained by dispersing inorganic oxide fine particles having an average particle diameter of 1 to 500 nm (sometimes simply referred to as fine particles) in a solvent.
In the present invention, the average particle size of the inorganic oxide fine particles means a value calculated from a measurement result by an image analysis method.
ここで無機酸化物微粒子は、例えばＳｉ、Ａｌ、Ｂ、Ｍｇ、Ｃａ、Ｂａ、Ｍｏ、Ｚｒ、Ｇａ、Ｂｅ、Ｓｒ、Ｙ、Ｌａ、Ｃｅ、Ｓｎ、Ｆｅ、Ｚｎ、ＭｎおよびＴｉからなる群から選ばれる少なくとも１つの元素を含む酸化物を主成分とするものであることが好ましい。また、無機酸化物微粒子は、このような酸化物から実質的になるものであることがより好ましい。なお、該無機酸化物微粒子は、無機複合酸化物微粒子であっても構わない。
ここで、「主成分」とは含有率が５０質量％以上である（すなわち、無機酸化物微粒子が含む、Ｓｉ、Ａｌ、Ｂ、Ｍｇ、Ｃａ、Ｂａ、Ｍｏ、Ｚｒ、Ｇａ、Ｂｅ、Ｓｒ、Ｙ、Ｌａ、Ｃｅ、Ｓｎ、Ｆｅ、Ｚｎ、ＭｎおよびＴｉの酸化物の合計含有率が５０質量％以上である）ことが好ましく、６０質量％以上であることがより好ましく、８０質量％以上であることがより好ましく、９０質量％以上であることがより好ましく、９５質量％以上であることがさらに好ましい。また、「実質的に」とは、原料や製造工程から混入する不純物は含まれ得ることを意味する。以下において「主成分」および「実質的に」の文言は、特に説明がない限り、このような意味で用いることとする。
無機酸化物微粒子がＣｅを含む場合（例えばセリア微粒子など）には、酸素欠陥が生じやすいので、これを回避するために、ナノバブルとしてＮ2あるいはＨ2等の非酸化性ガスを用いることがより好ましい。
また、無機酸化物微粒子がヘテロ元素の存在により、侵入型固溶体を形成し酸素欠損が増加している場合にも、ナノバブルとして非酸化性ガスを用いることが好ましい。この様な例としては、無機酸化物微粒子がＣｅを含み、更にＳｉ、Ｃ、Ｎ、Ｌａ、Ｚｒなどのヘテロ元素を含む場合を挙げることができる。
Here, the inorganic oxide fine particles are, for example, from the group consisting of Si, Al, B, Mg, Ca, Ba, Mo, Zr, Ga, Be, Sr, Y, La, Ce, Sn, Fe, Zn, Mn, and Ti. It is preferable that the main component is an oxide containing at least one selected element. The inorganic oxide fine particles are more preferably substantially composed of such an oxide. The inorganic oxide fine particles may be inorganic composite oxide fine particles.
Here, the “main component” has a content of 50% by mass or more (that is, Si, Al, B, Mg, Ca, Ba, Mo, Zr, Ga, Be, Sr, inorganic oxide fine particles are included). Y, La, Ce, Sn, Fe, Zn, Mn, and the total content of oxides of Ti and Ti are preferably 50% by mass or more, more preferably 60% by mass or more, and 80% by mass or more. More preferably, it is more preferably 90% by mass or more, and further preferably 95% by mass or more. Further, “substantially” means that impurities mixed in from the raw materials and the manufacturing process can be included. In the following, the terms “main component” and “substantially” are used in this sense unless otherwise specified.
When the inorganic oxide fine particles contain Ce (for example, ceria fine particles), oxygen defects are likely to occur. Therefore, in order to avoid this, it is more preferable to use a non-oxidizing gas such as N 2 or H 2 as nanobubbles. preferable.
In addition, it is preferable to use a non-oxidizing gas as nanobubbles even when the inorganic oxide fine particles form an interstitial solid solution due to the presence of heteroelements and oxygen vacancies increase. As such an example, there can be mentioned a case where the inorganic oxide fine particles contain Ce and further contain a hetero element such as Si, C, N, La and Zr.
無機酸化物微粒子の平均粒子径は５００ｎｍ以下であり、３００ｎｍ以下であることが好ましく、２００ｎｍ以下であることがより好ましく、１００ｎｍ以下であることがより好ましい。また、平均粒子径は１ｎｍ以上であり、５ｎｍ以上であることが好ましい。 The average particle size of the inorganic oxide fine particles is 500 nm or less, preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less. The average particle size is 1 nm or more, and preferably 5 nm or more.
このような無機酸化物微粒子が分散している溶媒は特に限定されないが、水（イオン交換水、純水を含む）であることが好ましい。 The solvent in which such inorganic oxide fine particles are dispersed is not particularly limited, but is preferably water (including ion-exchanged water and pure water).
ナノバブル水溶液は平均気泡径が５０〜５００ｎｍのナノバブルを含む。
ナノバブルとは、気泡径が５００ｎｍ以下である微細気泡である。この気泡径は４００ｎｍ以下であることが好ましく、３５０ｎｍ以下であることがさらに好ましい。また、この気泡径は５０ｎｍ以上であり、７０ｎｍ以上であることがさらに好ましい。
The nanobubble aqueous solution contains nanobubbles having an average bubble diameter of 50 to 500 nm.
Nano bubbles are fine bubbles having a bubble diameter of 500 nm or less. The bubble diameter is preferably 400 nm or less, and more preferably 350 nm or less. The bubble diameter is 50 nm or more, and more preferably 70 nm or more.
ナノバブルの平均気泡径及び気泡個数は、液中の気泡のブラウン運動移動速度をナノ粒子トラッキング解析法を用いて測定する。 The average bubble diameter and the number of bubbles of nanobubbles are measured by using the nanoparticle tracking analysis method for the Brownian movement speed of bubbles in the liquid.
ナノバブルに含まれる気体の種類については、ナノバブルの破裂によりミクロゲルを解砕する効果が発揮できるものであれば、特に限定されるものではないが、通常は、Ｎ2、Ｈ2およびＯ2からなる群から選ばれる少なくとも１つから実質的になることが好ましい。前記無機酸化物微粒子がシリカ微粒子の場合、ナノバブルがＮ2および／またはＯ2からなることが好ましい。前記無機酸化物微粒子がセリアなどＣｅを含む酸化物微粒子又は複合酸化物微粒子である場合、ナノバブルは非酸化性ガスであることが好ましい。 The type of gas contained in the nanobubble is not particularly limited as long as the effect of crushing the microgel by bursting of the nanobubble can be exerted, but usually composed of N 2 , H 2 and O 2. It is preferable to consist essentially of at least one selected from the group. When the inorganic oxide fine particles are silica fine particles, the nanobubbles are preferably composed of N 2 and / or O 2 . When the inorganic oxide fine particles are oxide fine particles or complex oxide fine particles containing Ce such as ceria, the nanobubbles are preferably a non-oxidizing gas.
ナノバブル水溶液が、１．０×１０5個／ｍＬ以上のナノバブルを含むことが好ましく、１．１×１０5個／ｍＬ以上のナノバブルを含むことがより好ましく、１．０×１０8個／ｍＬ以上のナノバブルを含むことがより好ましく、１．１×１０8個／ｍＬ以上のナノバブルを含むことがさらに好ましい。このナノバブルの個数は、１０００×１０8個／ｍＬ以下であることが好ましく、５００×１０8個／ｍＬ以下であることがより好ましく、１００×１０8個／ｍＬ以下であることがさらに好ましい。 The nanobubble aqueous solution preferably contains 1.0 × 10 5 / mL or more nanobubbles, more preferably 1.1 × 10 5 / mL or more nanobubbles, and 1.0 × 10 8 / mL. It is more preferable to include the above nanobubbles, and it is further preferable to include 1.1 × 10 8 / mL or more nanobubbles. The number of nanobubbles is preferably 1000 × 10 8 pieces / mL or less, more preferably 500 × 10 8 pieces / mL or less, and further preferably 100 × 10 8 pieces / mL or less.
マイクロバブルの発生方法は、特に制限されず、従来公知の方法を用いることができる。例えば、旋回流式、スタティックミキサー式、エジェクター式、ベンチュリー式、加圧溶解式、細孔式、回転式、超音波式、蒸気凝縮式、電気分解式などが挙げられる。 The generation method of microbubbles is not particularly limited, and a conventionally known method can be used. For example, a swirling flow type, a static mixer type, an ejector type, a venturi type, a pressure dissolution type, a pore type, a rotary type, an ultrasonic type, a vapor condensation type, an electrolysis type and the like can be mentioned.
次に、本発明の製造方法では、上記のような無機酸化物微粒子分散液と、ナノバブル水溶液とを含む溶液を得る。
この溶液は一方を他方へ加えることで得ることができるが、無機酸化物微粒子分散液の内部でナノバブルを発生させることでも得ることができる。
無機酸化物微粒子分散液の内部でナノバブルを発生させる方法は特に限定されず、前述の従来公知の方法を利用することができる。
Next, in the manufacturing method of this invention, the solution containing the above inorganic oxide fine particle dispersion liquid and nanobubble aqueous solution is obtained.
This solution can be obtained by adding one to the other, but can also be obtained by generating nanobubbles inside the inorganic oxide fine particle dispersion.
The method for generating nanobubbles inside the inorganic oxide fine particle dispersion is not particularly limited, and the above-described conventionally known methods can be used.
無機酸化物微粒子分散液と、ナノバブル水溶液とを含む溶液を得ながら、または、得た後、無機酸化物微粒子分散液とナノバブル水溶液とを含む溶液を５〜８０℃に保持しつつ、（好ましくは０．５時間以上）混合する。そうすると、研磨剤として用いる工程において濃縮安定性に優れるナノバブル含有無機酸化物微粒子分散液を得ることができる。 While obtaining a solution containing the inorganic oxide fine particle dispersion and the nanobubble aqueous solution, or after obtaining the solution containing the inorganic oxide fine particle dispersion and the nanobubble aqueous solution while maintaining the solution at 5 to 80 ° C. (preferably Mix for 0.5 hour or more). If it does so, the nanobubble containing inorganic oxide fine particle dispersion liquid which is excellent in concentration stability in the process used as an abrasive | polishing agent can be obtained.
無機酸化物微粒子分散液とナノバブル水溶液とを含む溶液を保持する温度は５〜８０℃であるが、５０℃以下であることが好ましく、３０℃以下であることがさらに好ましい。 Although the temperature which hold | maintains the solution containing inorganic oxide fine particle dispersion and nanobubble aqueous solution is 5-80 degreeC, it is preferable that it is 50 degrees C or less, and it is more preferable that it is 30 degrees C or less.
無機酸化物微粒子分散液にナノバブル水溶液を添加し、混合する。混合手段は格別に限定されるものではなく、撹拌による混合などがこのましい。混合する時間に格別の制限はないが、例えば、０．５時間以上混合することが好ましい。 An aqueous nanobubble solution is added to the inorganic oxide fine particle dispersion and mixed. The mixing means is not particularly limited, and mixing by stirring is preferable. Although there is no special restriction | limiting in the time to mix, For example, it is preferable to mix for 0.5 hour or more.
このようにして得られたナノバブル含有無機酸化物微粒子分散液は、半導体基板、配線基板などの半導体デバイスなどを製造する過程の１つである仕上げ研磨（２次研磨）に用いる研磨剤として好ましく用いることができる。
ナノバブル含有無機酸化物微粒子分散液をそのまま研磨剤として用いることもできるが、添加剤として、例えば、従来公知の研磨促進剤、界面活性剤、複素環化合物、ｐＨ調整剤およびｐＨ緩衝剤からなる群より選ばれる１種以上を含んでいてもよい。なお、ナノバブル含有無機酸化物微粒子分散液から研磨用スラリーを調製する際などに、ナノバブル含有無機酸化物微粒子分散液を希釈する必要がある場合は、ナノバブルを含有する水を添加して希釈することが望ましい。
The nanobubble-containing inorganic oxide fine particle dispersion obtained in this way is preferably used as an abrasive used for final polishing (secondary polishing), which is one of the processes for manufacturing semiconductor devices such as semiconductor substrates and wiring substrates. be able to.
The nanobubble-containing inorganic oxide fine particle dispersion can be used as a polishing agent as it is, but as an additive, for example, a group consisting of conventionally known polishing accelerators, surfactants, heterocyclic compounds, pH adjusting agents and pH buffering agents. One or more selected from more may be included. If it is necessary to dilute the nanobubble-containing inorganic oxide fine particle dispersion when preparing a polishing slurry from the nanobubble-containing inorganic oxide fine particle dispersion, add water containing nanobubbles to dilute. Is desirable.
また、研磨剤を用いて半導体デバイス等を研磨する場合、ミクロゲルが少ないと研磨剤の濾過を短時間に完了することができれば生産効率の向上につながるので好ましい。本発明のナノバブル含有無機酸化物微粒子分散液を研磨剤として用いる場合、濾過速度が非常に早いばかりでなく、濃縮安定性に優れる。
このように濾過速度が早く、濃縮安定性が良くなる理由は、ナノバブルが消滅する際に発生する衝撃波でミクロゲルが分散されるためと、本発明者は推測している。ミクロゲルが分散されることで消滅すれば、粗大粒子がより減少することになるため、被研磨面の面精度が向上（スクラッチ等の減少）に繋がると考えられる。さらに、研磨速度の向上も認められる。
Further, when polishing a semiconductor device or the like using an abrasive, it is preferable if the amount of microgel is small, since it is possible to improve the production efficiency if filtration of the abrasive can be completed in a short time. When the nanobubble-containing inorganic oxide fine particle dispersion of the present invention is used as an abrasive, not only the filtration rate is very fast, but also the concentration stability is excellent.
The inventor presumes that the reason why the filtration speed is fast and the concentration stability is improved is that the microgel is dispersed by the shock wave generated when the nanobubbles disappear. If the microgel disappears by being dispersed, coarse particles are further reduced, and it is considered that the surface accuracy of the polished surface is improved (reduction of scratches and the like). Furthermore, an improvement in the polishing rate is also observed.
本発明は、上記のような本発明の製造方法によって製造されたナノバブル含有無機酸化物微粒子分散液およびそれを含む研磨剤である。 The present invention is a nanobubble-containing inorganic oxide fine particle dispersion produced by the production method of the present invention as described above and an abrasive containing the same.
なお、このようなナノバブル含有無機酸化物微粒子分散液およびそれを含む研磨剤は、特定の無機酸化物微粒子分散液と、特定のナノバブル水溶液とを含む溶液を、特定温度に保持しつつ、（好ましくは特定時間）混合する工程を備える製造方法によって得られる物である。
特定の温度を保持しながら（好ましくは特定時間）混合することで、ナノバブルが適切に分散させると、上記のような極めて有効な効果を発揮することを特徴とする。
このような「適切にナノバブルが分散している状態や構造」を直接特定することは不可能である。また、それを規定する特性も存在しない。
したがって、製造方法によって規定される上記の本発明のナノバブル含有無機酸化物微粒子分散液およびそれを含む研磨剤は、その範囲が不明確ではない。
In addition, such a nanobubble-containing inorganic oxide fine particle dispersion and an abrasive containing the same are preferably maintained while holding a solution containing a specific inorganic oxide fine particle dispersion and a specific nanobubble aqueous solution at a specific temperature (preferably Is a product obtained by a production method comprising a step of mixing for a specific time.
When the nanobubbles are appropriately dispersed by mixing while maintaining a specific temperature (preferably for a specific time), the above-described extremely effective effect is exhibited.
It is impossible to directly specify such “state and structure in which nanobubbles are appropriately dispersed”. Also, there are no characteristics that define it.
Therefore, the range of the nanobubble-containing inorganic oxide fine particle dispersion of the present invention and the abrasive containing the same specified by the production method is not clear.
実施例及び比較例で用いた分析方法又は測定方法について以下に記す。 The analysis method or measurement method used in Examples and Comparative Examples is described below.
[無機酸化物微粒子の平均粒子径]
無機酸化物微粒子の平均粒子径は、画像解析法により測定した。具体的には、透過型電子顕微鏡（株式会社日立製作所製、Ｈ−８００）により、試料無機酸化物微粒子分散液を倍率２５万倍で写真撮影して得られる写真投影図における、任意の５００個の粒子について、その粒子径を測定し、その平均値を無機酸化物微粒子の平均粒子径とした。
[Average particle size of inorganic oxide particles]
The average particle diameter of the inorganic oxide fine particles was measured by an image analysis method. Specifically, arbitrary 500 pieces in a photographic projection view obtained by photographing a sample inorganic oxide fine particle dispersion at a magnification of 250,000 times with a transmission electron microscope (H-800, manufactured by Hitachi, Ltd.) The particle diameter of each particle was measured, and the average value was defined as the average particle diameter of the inorganic oxide fine particles.
[ナノバブルの平均気泡径と気泡個数]
ナノバブルの平均気泡径は、液中の気泡のブラウン運動移動速度をナノ粒子4トラッキング解析法を用いて測定した。具体的には、測定試料（ナノバブル含有無機酸化物微粒子分散液）約２０ｍＬを吸引させながら測定機器（Ｍａｌｖｅｒｎ社製「ナノサイト ＮＳ３００」）に注入し、ナノ粒子トラッキング解析法にて測定した。
[Average bubble size and number of bubbles]
The average bubble diameter of the nanobubbles was measured using the nanoparticle 4 tracking analysis method for the Brownian movement speed of the bubbles in the liquid. Specifically, about 20 mL of a measurement sample (nanobubble-containing inorganic oxide fine particle dispersion) was injected while being sucked into a measuring instrument (“Nanosite NS300” manufactured by Malvern) and measured by a nanoparticle tracking analysis method.
[濃縮安定性の測定方法]
実施例又は比較例で得られた無機酸化物微粒子分散液を１Ｌのナスフラスコに入れ、ロータリーエバボレーターに設置し、バス温度６０℃に設定した後、真空度−７４０ｍｍＨｇにて濃縮を行った。ナスフラスコ内壁面にゲル状物が見られた時点で濃縮を止め無機酸化物ゾルを回収し、固形分濃度を測定した。
[Method of measuring concentration stability]
The inorganic oxide fine particle dispersion obtained in Examples or Comparative Examples was placed in a 1 L eggplant flask, placed in a rotary evaporator, set at a bath temperature of 60 ° C., and then concentrated at a vacuum degree of −740 mmHg. When a gel-like substance was found on the inner wall surface of the eggplant flask, the concentration was stopped and the inorganic oxide sol was recovered, and the solid content concentration was measured.
[粗大粒子の個数測定方法]
測定試料を、ろ過助剤を含むフィルターでろ過処理する前（又は後）のコロイダルシリカスラリーを６ｍＬのシリンジで下記測定機器に注入し、粗大粒子量を測定した。
測定機器と測定条件は次のとおり。
測定機器：ＰＳＳ社製「アキュサイザー７８０ＡＰＳ」
インジェクション・ループ・ボリューム（Injection Loop Volume）：１ｍＬ
フローレート（Flow Rate）：６０ｍＬ／分
データ・コレクション・タイム（Data Collection Time）：６０ ｓｅｃ
チャンネル数（Number Channels）：１２８
[Method for measuring the number of coarse particles]
The colloidal silica slurry before (or after) filtering the measurement sample with a filter containing a filter aid was injected into the following measuring device with a 6 mL syringe, and the amount of coarse particles was measured.
Measuring equipment and measuring conditions are as follows.
Measuring equipment: “Accuriser 780APS” manufactured by PSS
Injection loop volume: 1mL
Flow Rate: 60 mL / min Data Collection Time: 60 sec
Number Channels: 128
＜参考例１＞
平均粒子径３ｎｍのシリカ微粒子が水に分散してなるシリカ微粒子分散液（固形分濃度５質量％）の５００ｇを用意し、温度を２０℃に保持し、ここへ平均気泡径が２００ｎｍの１．１×１０8個／ｍｌのＮ2含有のナノバブル水溶液５００ｇを添加した。そして、同温度を保持しつつ１Ｈｒ撹拌し、ナノバブル含有無機酸化物微粒子分散液を得た。得られたナノバブル含有無機酸化物微粒子分散液を、前記濃縮安定性の測定方法に従って濃縮し、濃縮安定性を評価した。処理条件等および各測定結果を第１表に示す。
また、得られたナノバブル含有無機酸化物微粒子分散液を、濾過フィルター（フィルター径：０．５μｍ）に濾過圧１ｍＰａで濾過させたときの濾過速度は３５ｇ／分であった。フィルターを通過したナノバブル含有無機酸化物微粒子分散液についてＰＳＳ社製アキュサイザー７８０ＡＰＳを用いて、粒子径０．５１μｍ以上の粗大粒子の個数を測定したところ、２０万個／ｍｌであった。
<Reference Example 1>
500 g of a silica fine particle dispersion (solid content concentration 5 mass%) in which silica fine particles having an average particle diameter of 3 nm are dispersed in water is prepared, and the temperature is maintained at 20 ° C. 500 g of an aqueous solution of nanobubbles containing 1 × 10 8 / ml N 2 was added. Then, the mixture was stirred for 1 hour while maintaining the same temperature to obtain a nanobubble-containing inorganic oxide fine particle dispersion. The obtained nanobubble-containing inorganic oxide fine particle dispersion was concentrated according to the concentration stability measurement method, and the concentration stability was evaluated. Table 1 shows the processing conditions and the measurement results.
The filtration rate when the obtained nanobubble-containing inorganic oxide fine particle dispersion was filtered through a filtration filter (filter diameter: 0.5 μm) at a filtration pressure of 1 mPa was 35 g / min. The number of coarse particles having a particle diameter of 0.51 μm or more was measured using an Accusizer 780APS manufactured by PSS for the nanobubble-containing inorganic oxide fine particle dispersion that passed through the filter, and found to be 200,000 particles / ml.
＜参考例２＞
平均粒子径８０ｎｍのシリカ微粒子が水に分散してなるシリカ微粒子分散液（固形分濃度４０質量％）の５００ｇを用意し、温度を２０℃に保持し、ここへ平均気泡径が１８０ｎｍの１．１×１０8個／ｍｌのＮ2含有のナノバブル水溶液５００ｇを添加した。そして、同温度を保持しつつ２Ｈｒ撹拌した後、得られた無機酸化物微粒子分散液を、前記濃縮安定性の測定方法に従って濃縮し、濃縮安定性を評価した。処理条件等および各測定結果を第１表に示す。
<Reference Example 2>
500 g of a silica fine particle dispersion (solid content concentration: 40% by mass) in which silica fine particles having an average particle diameter of 80 nm are dispersed in water is prepared, and the temperature is maintained at 20 ° C. 500 g of an aqueous solution of nanobubbles containing 1 × 10 8 / ml N 2 was added. Then, after stirring for 2 hours while maintaining the same temperature, the obtained inorganic oxide fine particle dispersion was concentrated according to the concentration stability measurement method, and the concentration stability was evaluated. Table 1 shows the processing conditions and the measurement results.
＜参考例３＞
平均粒子径１２ｎｍのシリカ微粒子が水に分散してなるシリカ微粒子分散液（固形分濃度３０質量％）の５００ｇを用意し、温度を２０℃に保持し、ここへ平均気泡径が１５０ｎｍの２．２×１０8個／ｍｌのＮ2含有のナノバブル水溶液５００ｇを添加した。そして、同温度を保持しつつ２Ｈｒ撹拌した後、得られた無機酸化物微粒子分散液を、前記濃縮安定性の測定方法に従って濃縮し、濃縮安定性を評価した。処理条件等および各測定結果を第１表に示す。
<Reference Example 3>
500 g of a silica fine particle dispersion (solid content concentration of 30% by mass) in which silica fine particles having an average particle diameter of 12 nm are dispersed in water is prepared and maintained at a temperature of 20 ° C. 500 g of an aqueous nanobubble solution containing 2 × 10 8 / ml N 2 was added. Then, after stirring for 2 hours while maintaining the same temperature, the obtained inorganic oxide fine particle dispersion was concentrated according to the concentration stability measurement method, and the concentration stability was evaluated. Table 1 shows the processing conditions and the measurement results.
＜参考例４＞
平均粒子径５ｎｍのシリカ微粒子が水に分散してなるシリカ微粒子分散液（固形分濃度２０質量％）の５００ｇを用意し、温度を２０℃に保持し、ここへ平均気泡径が２９３ｎｍの２．０×１０8個／ｍｌのＮ2含有のナノバブル水溶液５００ｇを添加した。そして、同温度を保持しつつ２Ｈｒ撹拌した後、得られた溶液について、参考例１と同様に濃縮した。処理条件等および結果を第１表に示す。
<Reference Example 4>
500 g of a silica fine particle dispersion (solid content concentration 20% by mass) in which silica fine particles having an average particle diameter of 5 nm are dispersed in water is prepared, the temperature is kept at 20 ° C., and 2.2 with an average bubble diameter of 293 nm. 500 g of an aqueous solution of nanobubbles containing N 2 at 0 × 10 8 pieces / ml was added. Then, after stirring for 2 hours while maintaining the same temperature, the obtained solution was concentrated in the same manner as in Reference Example 1 . Table 1 shows the processing conditions and the results.
＜参考例５＞
平均粒子径２５０ｎｍのシリカ微粒子が水に分散してなるシリカ微粒子分散液（固形分濃度４８質量％）の５００ｇを用意し、温度を５℃に保持し、ここへ平均気泡径が８０ｎｍの５．０×１０8個／ｍｌのＮ2含有のナノバブル水溶液５００ｇを添加した。そして、同温度を保持しつつ１．５Ｈｒ撹拌した後、得られた溶液について、参考例１と同様に濃縮した。処理条件等および結果を第１表に示す。
<Reference Example 5>
500 g of a silica fine particle dispersion (solid content concentration 48 mass%) in which silica fine particles having an average particle diameter of 250 nm are dispersed in water is prepared, and the temperature is maintained at 5 ° C. 500 g of an aqueous solution of nanobubbles containing N 2 at 0 × 10 8 pieces / ml was added. Then, after stirring for 1.5 hours while maintaining the same temperature, the obtained solution was concentrated in the same manner as in Reference Example 1 . Table 1 shows the processing conditions and the results.
＜参考例６＞
平均粒子径が２０ｎｍのシリカ微粒子が水に分散してなるシリカ微粒子分散液（固形分濃度：５質量％）のｐＨを９に維持し、温度を８０℃に保ちながら、硝酸セリウム水溶液（セリア換算濃度：５質量％）を５時間かけて添加した。なお、シリカ微粒子分散液と硝酸セリウム水溶液は、ＳｉＯ2／ＣｅＯ2質量比＝５０／５０となるように投入し、シリカ・セリア複合酸化物微粒子分散液（ＳｉＯ2／ＣｅＯ2質量比＝５０／５０）を調製した。
その後、限外膜にて水洗後、濃縮した。このようなＳｉＯ2・ＣｅＯ2からなる無機酸化物微粒子分散液（固形分濃度：２０質量％、平均粒子径２５ｎｍ）を５００ｇ用意した。そして、この水溶液内に、平均気泡径が３００ｎｍの１．０×１０8個／ｍｌのＯ2含有のナノバブルを発生させた。ナノバブルを発生させた後の溶液は１０００ｇとなった。
そして、溶液の温度を２０℃に保持しつつ２４Ｈｒ撹拌した後、得られた溶液について、参考例１と同様に濃縮した。処理条件等および結果を第１表に示す。
<Reference Example 6>
While maintaining the pH of silica fine particle dispersion (solid content concentration: 5% by mass), in which silica fine particles with an average particle size of 20 nm are dispersed in water, at 9 and maintaining the temperature at 80 ° C., an aqueous cerium nitrate solution (converted to ceria) Concentration: 5% by mass) was added over 5 hours. The silica fine particle dispersion and the cerium nitrate aqueous solution were added so that the SiO 2 / CeO 2 mass ratio = 50/50, and the silica / ceria composite oxide fine particle dispersion (SiO 2 / CeO 2 mass ratio = 50/50). 50) was prepared.
Then, it was concentrated with water after washing with an ultrafiltration membrane. 500 g of such inorganic oxide fine particle dispersion liquid (solid content concentration: 20 mass%, average particle diameter 25 nm) made of SiO 2 .CeO 2 was prepared. Then, 1.0 × 10 8 / ml O 2 -containing nanobubbles having an average bubble diameter of 300 nm were generated in this aqueous solution. The solution after generating nanobubbles was 1000 g.
Then, after stirring for 24 hours while maintaining the temperature of the solution at 20 ° C., the obtained solution was concentrated in the same manner as in Reference Example 1 . Table 1 shows the processing conditions and the results.
＜参考例７＞
平均粒子径が１７ｎｍのシリカ微粒子が水に分散してなるシリカ微粒子分散液（固形分濃度：５質量％）のｐＨを９に維持し、温度８０℃を保ちながら、炭酸ジルコニウムアンモニウム水溶液（ジルコニア換算濃度：５質量％）を５時間かけて添加した。なお、シリカ微粒子分散液と炭酸ジルコニウムアンモニウム水溶液は、ＳｉＯ2／ＺｒＯ2質量比＝７５／２５となるように投入し、シリカ・ジルコニア複合微粒子分散液（ＳｉＯ2／ＺｒＯ2質量比＝７５／２５）を調製した。
その後、限外膜にて水洗後、濃縮した。このようなＳｉＯ2・ＺｒＯ2からなる無機酸化物微粒子分散液（固形分濃度：２０質量％、平均粒子径２０ｎｍ）を５００ｇ用意し、温度を１０℃に保持し、ここへ平均気泡径が７０ｎｍの２．０×１０8個／ｍｌのＮ2含有のナノバブル水溶液５００ｇを添加した。そして、同温度を保持しつつ２Ｈｒ撹拌した後、得られた溶液について、参考例１と同様に濃縮した。処理条件等および結果を第１表に示す。
<Reference Example 7>
Maintaining the pH of a silica fine particle dispersion (solid content concentration: 5% by mass) in which silica fine particles having an average particle diameter of 17 nm are dispersed in water at 9 and maintaining the temperature at 80 ° C., an aqueous solution of zirconium ammonium carbonate (converted to zirconia) Concentration: 5% by mass) was added over 5 hours. Incidentally, the silica particle dispersion liquid and the ammonium zirconium carbonate solution is, SiO 2 / ZrO 2 mass ratio = 75/25 and charged so that the silica-zirconia composite fine particles dispersion (SiO 2 / ZrO 2 mass ratio = 75/25 ) Was prepared.
Then, it was concentrated with water after washing with an ultrafiltration membrane. 500 g of such an inorganic oxide fine particle dispersion liquid (solid content concentration: 20 mass%, average particle diameter 20 nm) made of SiO 2 .ZrO 2 is prepared, the temperature is maintained at 10 ° C., and the average bubble diameter is 70 nm. Of nanobubble aqueous solution containing 2.0 × 10 8 particles / ml of N 2 was added. Then, after stirring for 2 hours while maintaining the same temperature, the obtained solution was concentrated in the same manner as in Reference Example 1 . Table 1 shows the processing conditions and the results.
＜実施例１＞
平均粒子径が２０ｎｍのセリア微粒子が水に分散してなるセリア微粒子分散液（固形分濃度２０質量％）の５００ｇを用意し、温度を３０℃に保持し、ここへ平均気泡径が２９０ｎｍの１５×１０8個／ｍｌのＮ2含有のナノバブル水溶液５００ｇを添加した。そして、温度３０℃を保持しつつ６０時間撹拌した後、得られた溶液について、参考例１と同様に濃縮した。処理条件等および結果を第１表に示す。
<Example 1>
500 g of a ceria fine particle dispersion (solid content concentration 20% by mass) in which ceria fine particles having an average particle diameter of 20 nm are dispersed in water is prepared, the temperature is maintained at 30 ° C., and 15% of the average bubble diameter is 290 nm. 500 g of a nanobubble aqueous solution containing × 10 8 / ml N 2 was added. Then, after stirring for 60 hours while maintaining a temperature of 30 ° C., the obtained solution was concentrated in the same manner as in Reference Example 1 . Table 1 shows the processing conditions and the results.
＜比較例１＞
平均粒子径１２ｎｍのシリカ微粒子が水に分散してなるシリカ微粒子分散液（固形分濃度３０質量％）の５００ｇを用意し、温度を２０℃に保持し、ここへ平均気泡径が１５０ｎｍの２．２×１０8個／ｍｌのＮ2含有のナノバブル水溶液５００ｇを添加した。そして、同温度を保持しつつ０．１Ｈｒ撹拌した後、得られた溶液について、参考例１と同様に濃縮した。処理条件等および結果を第１表に示す。
また、得られたナノバブル含有無機酸化物微粒子分散液を、参考例１の場合と同様に濾過フィルター（フィルター径：０．５μｍ）に濾過圧１ｍＰａで濾過させたときの濾過速度は１０ｇ／分であった。フィルターを通過したナノバブル含有無機酸化物微粒子分散液についてＰＳＳ社製アキュサイザー７８０ＡＰＳを用いて、粒子径０．５１μｍ以上の粗大粒子の個数を測定したところ、６０万個／ｍｌであった。
<Comparative Example 1>
500 g of a silica fine particle dispersion (solid content concentration of 30% by mass) in which silica fine particles having an average particle diameter of 12 nm are dispersed in water is prepared and maintained at a temperature of 20 ° C. 500 g of an aqueous nanobubble solution containing 2 × 10 8 / ml N 2 was added. Then, after stirring for 0.1 Hr while maintaining the same temperature, the obtained solution was concentrated in the same manner as in Reference Example 1 . Table 1 shows the processing conditions and the results.
Further, the filtration rate when the obtained nanobubble-containing inorganic oxide fine particle dispersion was filtered through a filtration filter (filter diameter: 0.5 μm) at a filtration pressure of 1 mPa as in Reference Example 1 was 10 g / min. there were. The number of coarse particles having a particle diameter of 0.51 μm or more was measured using an Accusizer 780APS manufactured by PSS for the nanobubble-containing inorganic oxide fine particle dispersion that passed through the filter, and the result was 600,000 particles / ml.
＜比較例２＞
平均粒子径１２ｎｍのシリカ微粒子が水に分散してなるシリカ微粒子分散液（固形分濃度３０質量％）の５００ｇを用意し、温度を２０℃に保持し、ここへ平均気泡径１０００ｎｍの２×１０４個/ｍｌのＮ２含有ナノバブル水溶液５００ｇを添加した。そして、同温度を保持しつつ２Ｈｒ撹拌した後、得られた溶液について、参考例１と同様に濃縮した。処理条件等および結果を第１表に示す。
<Comparative example 2>
500 g of a silica fine particle dispersion (solid content concentration of 30% by mass) in which silica fine particles with an average particle diameter of 12 nm are dispersed in water is prepared, and the temperature is kept at 20 ° C., where 2 × 10 with an average bubble diameter of 1000 nm. 4 g / ml N 2 -containing nanobubble aqueous solution 500 g was added. Then, after stirring for 2 hours while maintaining the same temperature, the obtained solution was concentrated in the same manner as in Reference Example 1 . Table 1 shows the processing conditions and the results.
＜比較例３＞
平均粒子径８０ｎｍのシリカ微粒子が水に分散してなるシリカ微粒子分散液（固形分濃度４０質量％）の５００ｇを用意し、温度を２０℃に保持した。そしてナノバブル水溶液を添加せずに、参考例１と同様に濃縮した。処理条件等および結果を第１表に示す。
<Comparative Example 3>
500 g of a silica fine particle dispersion (solid content concentration: 40% by mass) obtained by dispersing silica fine particles having an average particle diameter of 80 nm in water was prepared, and the temperature was maintained at 20 ° C. And it concentrated similarly to the reference example 1 without adding nanobubble aqueous solution. Table 1 shows the processing conditions and the results.
＜比較例４＞
平均粒子径２５ｎｍのシリカ・セリア微粒子（ＳｉＯ2／ＣｅＯ2質量比＝５０／５０、固形分濃度２０質量％）が水に分散してなるシリカ・セリア微粒子分散液の５００ｇを用意し、温度を２０℃に保持した。そしてナノバブル水溶液を添加せずに、参考例６と同様に濃縮した。処理条件等および結果を第１表に示す。
<Comparative example 4>
Prepare 500 g of silica / ceria fine particle dispersion in which silica / ceria fine particles (SiO 2 / CeO 2 mass ratio = 50/50, solid content concentration 20% by mass) having an average particle diameter of 25 nm are dispersed in water. Maintained at 20 ° C. And it concentrated similarly to the reference example 6 without adding nanobubble aqueous solution. Table 1 shows the processing conditions and the results.
＜比較例５＞
平均粒子径２０ｎｍのシリカ・ジルコニア微粒子（ＳｉＯ2／ＺｒＯ2質量比＝７５／２５、固形分濃度２０質量％）が水に分散してなるシリカ・セリア微粒子分散液の５００ｇを用意し、温度２０℃に保持した。そしてナノバブル水溶液を添加せずに、参考例７と同様に濃縮した。処理条件等および結果を第１表に示す。
<Comparative Example 5>
500 g of a silica / ceria fine particle dispersion in which silica / zirconia fine particles (SiO 2 / ZrO 2 mass ratio = 75/25, solid concentration 20 mass%) having an average particle diameter of 20 nm are dispersed in water is prepared, and the temperature is 20 Held at 0C. And it concentrated similarly to the reference example 7 , without adding nanobubble aqueous solution. Table 1 shows the processing conditions and the results.
＜比較例６＞
平均粒子径２０ｎｍのセリア微粒子が水に分散してなるセリア微粒子分散液（固形分濃度２０質量％）の５００ｇを用意し、温度を２０℃に保持した。そしてナノバブル水溶液を添加せずに、実施例１と同様に濃縮した。処理条件等および結果を第１表に示す。
<Comparative Example 6>
500 g of a ceria fine particle dispersion (solid content concentration 20% by mass) obtained by dispersing ceria fine particles having an average particle diameter of 20 nm in water was prepared, and the temperature was maintained at 20 ° C. And it concentrated like Example 1 without adding nanobubble aqueous solution. Table 1 shows the processing conditions and the results.
濃縮安定性は、同種の無機酸化物の場合、無機酸化物微粒子の粒子径（平均粒子径）と相関があるため、平均粒子径と濃縮安定性の関係をグラフ（図１）に示した。
図１のグラフより、例えば、参考例３の場合、シリカ微粒子の平均粒子径が同等である比較例１又は比較例２に比べて、濃縮安定性に優れることがわかる。また、参考例２は、同じくシリカ微粒子の平均粒子径が同等である比較例３に比べて、濃縮安定性に優れることがわかる。
一方、無機酸化物微粒子分散液とナノバブル水溶液との撹拌時間が比較例１のように短かったり、撹拌時の溶液温度が比較例２のように高かったりすると、濃縮安定性が劣ることがわかった。また、比較例３にようにナノバブル水溶液を用いないと、濃縮安定性に劣ることがわかった。なお、本発明によるこれらの効果は、程度の差はあるものの、シリカ微粒子以外の無機酸化物微粒子分散液でも同様に発現することを参考例６と比較例４、参考例７と比較例５、実施例１と比較例６が示している。
In the case of the same kind of inorganic oxide, the concentration stability has a correlation with the particle size (average particle size) of the inorganic oxide fine particles, so the relationship between the average particle size and the concentration stability is shown in the graph (FIG. 1).
From the graph of FIG. 1, for example, in the case of Reference Example 3 , it can be seen that the concentration stability is superior to Comparative Example 1 or Comparative Example 2 in which the average particle diameter of the silica fine particles is the same. In addition, it can be seen that Reference Example 2 is superior in concentration stability as compared with Comparative Example 3 in which the average particle diameter of the silica fine particles is the same.
On the other hand, when the stirring time of the inorganic oxide fine particle dispersion and the nanobubble aqueous solution was short as in Comparative Example 1 or the solution temperature during stirring was high as in Comparative Example 2, it was found that the concentration stability was poor. . Moreover, when nanobubble aqueous solution was not used like the comparative example 3, it turned out that it is inferior to concentration stability. In addition, although these effects by this invention differ to some extent, it is expressed similarly in inorganic oxide fine particle dispersion liquids other than silica fine particles, Reference Example 6 and Comparative Example 4, Reference Example 7 and Comparative Example 5, Example 1 and Comparative Example 6 are shown.
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| WO2018221304A1 (en) * | 2017-06-01 | 2018-12-06 | 日揮触媒化成株式会社 | Nanobubble-containing inorganic oxide fine particles, and polishing agent including same |
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| JP2017179016A (en) | 2017-10-05 |
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