201100327 六、發明說明： 【發明所屬之技術領域】 本發明關於磺酸修飾水性陰離子矽溶膠及其製法。 具體而言，係關於利用磺酸修飾使用水性介質之膠態 矽石（矽溶膠）的表面’以賦予陰離子性之磺酸修飾水性陰 離子矽溶膠及其製法。 【先前技術】 使用水性介質之膠態矽石（矽溶膠）係在紙、纖維、鋼 〇 鐵等領域作爲物性改良劑使用，且作爲半導體晶圓之硏磨 劑使用。矽溶膠係在酸性條件下矽石粒子彼此凝集，而有 安定性惡化的問題，正謀求一種在廣大的pH範圍內安定性 優異之矽溶膠。 專利文獻1中記載一種在酸性條件下安定性高的改性 膠態矽石。具體而言，係記載將可水解之矽化合物予以水 解·縮合而得之膠態矽石，且將其以改性劑改性所得之改性 Q 膠態矽石，特別係使用具有陽離子性基之矽烷偶合劑作爲 改性劑（專利文獻1之申請專利範圍第1項、段落[〇〇 18]等）。 專利文獻2與上述相反地，係記載在矽石表面賦予陰 離子性之高安定性改性膠態矽石。具體而言，記載使膠態 矽石與鋁酸鈉等之鋁酸鹽反應，藉此對矽石表面賦予陰離 子性之陰離子矽溶膠（專利文獻2之申請專利範圍第1 項、發明效果等）。 將此等先前產品之改性膠態矽石尤其是在酸性條件下 用於半導體晶圓之硏磨劑等用途時’還有更加改善的餘地。 -4- 201100327 也就是說，專利文獻1的陽離子性矽溶膠在酸性領域 下具有正r電位且高安定性。然而，在陽離子性溶膠的情 況下，於液性從中性變化成鹼性的途中，r電位通過零等 電點，在從酸性〜鹼性的寬廣範圍中並非具有高安定性。 又，在專利文獻2中，爲使鋁酸鹽反應，陰離子性矽溶膠 除了矽以外尙含有鋁元素，於部分用途，尤其是不欲雜質 金屬元素之化學機械硏磨（CMP)用途中並不適合。再者，作 爲硏磨劑等使用時，爲了在將硏磨液供給至硏磨裝置前去 ❹ 除粗粒，因此必須過濾，而且在將硏磨液循環重複使用之 設計上，要求硏磨液的過濾性爲高。也就是說，於過濾之 際，必須防止改性膠態矽石凝集、凝膠化。又，改性膠態 矽石含金屬雜質的情況下，由於有對半導體晶圓造成刮傷 等之可能性，因此要求金屬雜質的含量盡可能爲低。此點 上，先前品之改性膠態矽石係無法完全滿足上述要求，有 進一步改良之餘地。 〇 [先行技術文獻] [專利文獻] [專利文獻1]特開2005- 1 6253 3號公報 [專利文獻2]WO2008/111383號小冊 【發明內容】 發明欲解決之課題 本發明之目的爲提供一種在酸性條件下之安定性高、 金屬雜質之含量低，而且過濾性良好之磺酸修飾水性陰離 201100327 子矽溶膠及其製法。 解決課題之手段 本發明者爲了達成上述目的而反覆鑽硏探討’結果發 現藉由以具有特定官能基之矽烷偶合劑處理膠態矽石（矽 溶膠）中之矽石表面後，將該官能基變換爲磺酸基之製造方 法能夠達成上述目的，而完成了本發明。 即，本發明係關於下述磺酸修飾水性陰離子矽溶膠。 1. —種磺酸修飾水性陰離子矽溶膠，其係在PH2以上的酸 〇 性中ζ電位爲-1 5mV以下。 2. 如上述1記載之磺酸修飾水性陰離子矽溶膠’其中1) 選自鈉及鉀之鹼金屬、2)選自鈣及鎂之鹼土類金屬以及 3)選自銘、鐵、欽、鎳、鉻、銅、辞、鈴、銀、锰及銘 之重金屬及輕金屬之含量係分別爲1重量ppm以下。 3. 如上述項1或2記載之磺酸修飾水性陰離子矽溶膠，其 在酸性條件下，於調製後2週以上可防止凝集或凝膠化。 ❹4· 一種磺酸修飾水性陰離子矽溶膠之製法，其係對膠態矽 石添加具有能夠化學性地變換爲磺酸基的官能基之矽烷 偶合劑後，將該官能基變換爲磺酸基。 5 ·如上述4記載之製法，其中該能夠化學性地變換爲磺酸 基之官能基爲锍基。 6.如上述項4或5記載之製法，該膠態矽石係將可水解之 矽化合物水解.縮合而得。 以下詳細說明本發明之磺酸修飾水性陰離子矽溶膠及 201100327 其製法。 本發明之磺酸修飾水性陰離子砂溶膠係藉由：對膠態 矽石添加具有能夠化學性地變換爲磺酸基的官能基之矽烷 偶合劑後，將該官能基變換爲磺酸基之製造方法（以下稱爲 「本發明之製法」）而得。 原料之膠態矽石只要爲表面具有矽醇基者則無限定’ 但若考慮半導體中不含具有擴散性之金屬雜質或氯等腐蝕 性離子，則較佳爲將可水解之矽化合物（例如，烷氧基矽烷 Ό 或其衍生物）作爲原料，藉水解·縮合而得之膠態矽石。此 矽化合物係可使用1種或混合使用2種以上。 在本發明，較佳爲下述一般式1所示之烷氧基矽烷或 其衍生物。201100327 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a sulfonic acid modified aqueous anionic cerium sol and a process for the preparation thereof. Specifically, it relates to a sulfonic acid-modified aqueous anionic cerium sol which imparts an anionic property by modifying the surface of a colloidal vermiculite (anthracene sol) using an aqueous medium with a sulfonic acid, and a process for producing the same. [Prior Art] Colloidal vermiculite (anthraquinone sol) using an aqueous medium is used as a physical property improver in the fields of paper, fiber, steel ferritic, and the like, and is used as a honing agent for a semiconductor wafer. The cerium sol is a problem in which the gangue particles are agglomerated under acidic conditions and the stability is deteriorated, and a cerium sol having excellent stability in a wide pH range is being sought. Patent Document 1 describes a modified colloidal vermiculite having high stability under acidic conditions. Specifically, it is a modified Q colloidal vermiculite obtained by hydrolyzing and condensing a hydrolyzable hydrazine compound and modifying it with a modifier, particularly using a cationic group. The decane coupling agent is used as a modifier (Patent Document No. 1, paragraph 1, paragraph [〇〇18], etc.). Patent Document 2, contrary to the above, describes a high-stability modified colloidal vermiculite which imparts anionic properties to the surface of vermiculite. Specifically, an anionic anthraquinone which imparts an anionic property to the surface of the vermiculite by reacting colloidal vermiculite with an aluminate such as sodium aluminate is described (Patent Document 2, Patent Application No. 1, Invention Effect, etc.) . There is still room for improvement in the use of modified colloidal vermiculite from such prior products, particularly in applications such as honing agents for semiconductor wafers under acidic conditions. -4- 201100327 That is, the cationic cerium sol of Patent Document 1 has a positive r potential and high stability in the acidic field. However, in the case of the cationic sol, the r potential passes through the zero isoelectric point while the liquidity changes from neutral to alkaline, and does not have high stability in a wide range from acidic to basic. Further, in Patent Document 2, in order to react an aluminate, the anionic cerium sol contains aluminum in addition to cerium, and is not suitable for some applications, particularly chemical mechanical honing (CMP) applications in which metal elements are not desired. . Further, when used as a honing agent or the like, in order to remove the coarse particles before the honing liquid is supplied to the honing device, it is necessary to filter, and in the design in which the honing liquid is repeatedly used, the honing liquid is required. The filterability is high. That is to say, at the time of filtration, it is necessary to prevent the modified colloidal vermiculite from aggregating and gelling. Further, in the case where the modified colloidal vermiculite contains a metal impurity, there is a possibility that the semiconductor wafer is scratched or the like, and therefore the content of the metal impurities is required to be as low as possible. At this point, the modified colloidal vermiculite of the previous product cannot fully meet the above requirements, and there is room for further improvement.先 [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] JP-A-2005- 1 6253 No. 3 [Patent Document 2] WO2008/111383 OBJECT SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The object of the present invention is to provide The invention discloses a sulfonic acid modified aqueous anion-free 201100327 sub-sol with high stability under acidic conditions, low content of metal impurities, and good filterability and a preparation method thereof. Means for Solving the Problems The inventors of the present invention have repeatedly studied in order to achieve the above object. As a result, it has been found that the surface of the vermiculite in the colloidal vermiculite (the cerium sol) is treated by a decane coupling agent having a specific functional group. The present invention has been accomplished by a method for producing a sulfonic acid group. That is, the present invention relates to the following sulfonic acid-modified aqueous anionic cerium sol. 1. A sulfonic acid modified aqueous anionic cerium sol having a zeta potential of -1 5 mV or less in an acid enthalpy of pH 2 or higher. 2. The sulfonic acid-modified aqueous anionic oxime sol of the above 1 wherein 1) is selected from the group consisting of alkali metals of sodium and potassium, 2) alkaline earth metals selected from calcium and magnesium, and 3) selected from the group consisting of ing, iron, chin, and nickel. The contents of heavy metals and light metals of chromium, copper, rhodium, bell, silver, manganese and Ming are respectively below 1 ppm by weight. 3. The sulfonic acid-modified aqueous anionic oxime according to the above item 1 or 2, which is capable of preventing aggregation or gelation under acidic conditions for 2 weeks or more after preparation. ❹4· A method for producing a sulfonic acid-modified aqueous anionic cerium sol which is a decane coupling agent having a functional group capable of chemically converting into a sulfonic acid group to a colloidal vermiculite, and then converting the functional group into a sulfonic acid group. 5. The method according to the above 4, wherein the functional group which can be chemically converted into a sulfonic acid group is a fluorenyl group. 6. The method according to the above item 4 or 5, wherein the colloidal vermiculite is obtained by hydrolyzing and condensing a hydrolyzable hydrazine compound. Hereinafter, the sulfonic acid-modified aqueous anionic cerium sol of the present invention and the method for producing the same will be described in detail below. The sulfonic acid-modified aqueous anionic sand sol of the present invention is produced by adding a decane coupling agent having a functional group which can be chemically converted into a sulfonic acid group to a colloidal vermiculite, and converting the functional group into a sulfonic acid group. The method (hereinafter referred to as "the method of the present invention") is obtained. The colloidal vermiculite of the raw material is not limited as long as it has a sterol group on the surface. However, if it is considered that the semiconductor does not contain diffusing metal impurities or corrosive ions such as chlorine, it is preferred to hydrolyze the hydrazine compound (for example). , alkoxydecane oxime or a derivative thereof as a raw material, obtained by hydrolysis and condensation of colloidal vermiculite. These oxime compounds may be used alone or in combination of two or more. In the present invention, alkoxydecane represented by the following general formula 1 or a derivative thereof is preferred.
Si(〇R)4 (1) 〔式中，R爲烷基，較佳爲碳數1~8之低級烷基、更 佳爲碳數1〜4之低級烷基。〕 〇 作爲上述R，可例如甲基、乙基'丙基、異丙基、丁 基、戊基、己基等，以R爲甲基之四甲氧基矽烷、R爲乙 基之四乙氧基矽烷、R爲異丙基之四異丙氧基矽烷爲較 佳°又’作爲烷氧基矽烷之衍生物，亦可例如將烷氧基矽 院部分水解而得之低縮合物。在本發明，於易於控制水解 速度方面、易於獲得單（single)Ilm之微小矽石粒子方面、 未反應物的残留較少方面，以使用四甲氧基矽烷爲較佳。 述矽化合物係在反應溶劑中水解.縮合而成爲膠態 201100327 矽石。作爲反應溶劑者可使用水或含水之有機溶劑。 作爲有機溶劑，可舉出甲醇、乙醇、異丙醇、η-丁醇、 三級丁醇、戊醇、乙二醇、丙二醇、1,4-丁二醇等之醇類、 丙酮、甲基乙基酮等之酮類等親水性有機溶劑。此等有機 溶劑之中，特佳爲使用甲醇、乙醇、異丙醇等之醇類，由 反應溶劑之後處理等觀點來看，更佳爲使用具有與原料矽 化合物的烷基（R)相同之烷基的醇類。此等有機溶劑可使用 1種或2種以上。 〇 有機溶劑的使用量係無特別限定，矽化合物每1莫耳 以5〜5 0莫耳左右爲較佳。小於5莫耳時，會有喪失與矽化 合物之相溶性的情形。大於5 0莫耳時，會有製造效率減低 的情形。 有機溶劑中所添加的水量係無特別限定，只要存在矽 化合物之水解所必要的量即可，矽化合物每1莫耳以2〜1 5 莫耳左右爲較佳。又，有機溶劑中所混合的水量對所形成 Q 之膠態矽石的粒徑有很大的影響。水的添加量若相對地增 加，則可相對地增大膠態矽石的粒徑。若相對地減少水的 添加量，則可相對地減小膠態矽石的粒徑。因此，藉由改 .變水與有機溶劑之混合比率，能夠任意調整所製得之膠態 矽石的粒徑。 於反應溶劑，較佳爲添加鹼性觸媒以將反應溶劑調整 爲鹼性。藉此將反應溶劑較佳爲調整成pH 8~1 1、更佳爲 p Η 8.5 ~ 1 0.5，而可快速地形成膠態矽石。作爲鹼性觸媒， 201100327 若考慮雜質，則以有機胺、氨水爲較佳，特別可例如較佳 爲佳伸乙二胺、二伸乙三胺、三伸乙四胺、氨水、尿素、 乙醇胺、四甲基氫氧化銨等。 在反應溶劑中將矽化合物水解·縮合只要將原料化合 物添加於有機溶劑，在0~100°C、較佳爲0〜50°c之溫度條 件下進行攪拌即可。藉由在含水之有機溶劑中將矽化合物 邊攪拌邊進行水解·縮合，可得球狀且粒徑一致之膠態砂 石。 〇 在本發明，對膠態矽石添加具有能夠化學性地變換爲 磺酸基的官能基之矽烷偶合劑後，將該官能基變換爲磺酸 基，藉此將膠態矽石予以磺酸修飾。此係因爲磺酸基之酸 性度高導致水解，因此難以獲得具有磺酸基之矽烷偶合劑。 具有可化學性地變換爲磺酸基之官能基的矽烷偶合 劑，可舉出例如，1)具有藉由水解可變換爲磺酸基的磺酸 酯基之矽烷偶合劑、2)具有可藉由氧化變換爲磺酸基的锍 Q 基及/或硫化物（sulfide)基之偶合劑。又，膠態矽石表面之 磺酸修飾是在溶液中進行，因此爲了提高修飾效率，以使 用後者之具有疏基及/或硫化物基的偶合劑爲較佳。 作爲具有锍基之矽烷偶合劑，可舉出例如，3 -锍基丙 基三甲氧基矽烷、2-锍基丙基三乙氧基矽烷、2-锍基乙基 三甲氧基矽烷、2-锍基乙基三乙氧基矽烷等。 作爲具有硫化物基之偶合劑，可舉出例如，雙（3-三乙 氧基矽烷基丙基）二硫化物。 201100327 於膠態矽石添加偶合劑時，若考慮偶合劑之溶解性， 則以在膠態矽石含親水性有機溶劑爲較佳。此點，在以鹼 性觸媒將烷氧基矽烷在醇·水溶劑中水解.縮合之st6ber 法，藉此製得膠態矽石時，由於反應液中含醇，因此不需 進一步添加親水性有機溶劑。此時，相對於膠態矽石中的 水，親水性有機溶劑更佳爲50質量％以上，因此視需要藉 由濃縮反應液來進行調整。 另一方面，於水分散之膠態矽石添加矽院偶合劑的情 〇 況下，添加約可溶解矽烷偶合劑之親水性溶劑。作爲親水 性有機溶劑，可舉出例如，異丙基醇、乙醇及甲醇等之醇， 其中，以使用與矽化合物之水解所生成的醇相同種類的醇 爲較佳。其係因爲，藉由使用與矽化合物之水解所生成的 醇相同種類的醇，能夠使溶劑之回收、再利用容易化。 上述偶合劑之添加量相對於矽石而言爲0.1〜10質量％ 左右。若添加量少，則在酸性下的r電位有時無法充分安 Q 定。若添加量多，則有隨時間經過而致使改性矽溶膠凝膠 化的可能性。 添加偶合劑時的溫度係無限定，但以常溫（約20°C )~ 沸點爲較佳。反應時間亦無限定，惟以10分~ 10小時爲較 佳、3 0分〜2小時爲更佳。添加時的pH亦無限定，惟以7 以上、1 1以下爲較佳。在1 1以上之強鹼’矽烷偶合劑係 不與矽石表面反應，有矽烷偶合劑彼此發生自縮合之虞， 故不佳。 -10- 201100327 將經修飾之锍基及硫化物基氧化的方法，可使用氧化 劑。可舉出例如，硝酸、過氧化氫、氧、臭氧、有機過氧 酸（過羧酸）、溴、次氯酸鹽、過錳酸鉀、鉻酸等。此等氧 化劑之中，在處理較爲容易且氧化收率亦爲良好方面，以 過氧化氫及有機過氧酸（過乙酸、過氧苯甲酸類）爲較佳。 又，若考慮在反應所副生成的物質，則最佳係使用過氧化 氫。 氧化劑的添加量以矽烷偶合劑的3倍莫耳~ 1 00倍莫耳 〇 爲較佳。雖無特別限制添加量之上限，但以5 0倍莫耳左右 爲更佳。又，關於膠態矽石及矽烷偶合劑，由於除了氧化（變 換）成磺酸基之官能基以外，在氧化反應中具有安定的構 造，因此無副生成物。 依據上述方法所得的磺酸修飾水性陰離子矽溶膠係含 水以外之溶劑，因此爲了提高該矽溶膠之長期保存安定 性，視需要能夠將主要爲反應溶劑之分散媒以水做置換。 Q 又，此水置換可在添加偶合劑後或添加氧化劑前進行。 將主要爲反應溶劑之分散媒以水做置換的方法係無特 別限定，可舉出例如，邊加熱該矽溶膠邊以定量逐滴添加 水的方法。又，亦可舉出將該矽溶膠利用沈澱·分離、離心 分離等分離主要爲反應溶劑之分散媒後，使其再分散於水 中的方法。 利用本發明之製法所得之磺酸修飾水性陰離子矽溶 膠，由於溶膠中的矽石表面係以磺酸基改性，因此即使是 201100327 酸性分散媒，也能抑制該矽溶膠之凝集或凝膠化，能夠長 期間安定分散。例如，於酸性條件下，在調製後2週以上 可防止凝集或凝膠化。又，由於以磺酸基改性，雖然理由 不確定，但與表面未經修飾（僅矽醇基）的膠態矽石相比， 矽溶膠的透明度較高。 而且，藉由本發明之製法而得的該矽溶膠係1)選自鈉 及鉀之鹼金屬、2)選自鈣及鎂之鹼土類金屬以及3)選自 銘、鐵、欽、鎳、鉻、銅、鈴、鉛、銀、猛及銘之重金屬 〇 及輕金屬的含量分別少至1重量ppm以下，進一步不含具 有腐蝕性之氯、溴等之鹵素元素，爲高純度。 又，該矽溶膠所含之改性矽石的粒徑爲lOOOnm以下、 較佳爲5〜500nm、更佳爲10~300nm。 本發明之該矽溶膠係在寬廣的pH値範圍中長期間的 分散安定性優良。矽溶膠之安定性可藉由測定矽溶膠之Γ 電位予以評價。Γ電位係指互相接觸的固體與液體進行相 Q 對運動時，在兩者的界面所產生之電位差，若r電位的絕 對値增加，則粒子間的排斥力強，粒子安定性變高，Γ電 位的絕對値越接近零，粒子越容易凝集。 本發明之矽溶膠特別在酸性範圍中具有高安定性。由 於使用具有陰離子性基之偶合劑作爲改性劑，因此於分散 媒爲pH2以上之酸性時，（電位爲負電位（_15mV以下）， 故縱使分散媒爲酸性亦具有高度分散安定性。如此地，由 於Γ電位的絕對値爲大，故具有高度分散安定性，隨之而 -12- 201100327 來，矽溶膠的動黏度亦小。 本發明之矽溶膠係可高濃度化。如特開200 5 -0602 1 9 「矽溶膠及其製法」、W02008/0 15943「矽溶膠及其製法」 所揭示’雖然嘗試添加鹼以在高pH下維持膠態矽石之安定 性、或添加少量有機酸的鹽，藉以使其高濃度化，但此等 先前物之矽石濃度界限爲40wt%左右。相對於此，以磺酸 基修飾的本發明之陰離子矽溶膠在酸性〜鹼性之寬廣範圍 內可爲50質量％以上之高濃度化。 〇 本發明之矽溶膠可使用於硏磨劑、紙之塗布劑等各種 用途，且在寬廣的pH範圍下能夠長期間安定分散，而且爲 鈉或鐵、鎳、鋁等之金屬雜質含量爲1重量ppm以下之高 純度。半導體製品之不良大半係因污染所致，而且因鐵、 鎳、鉻、銅、鋅等之重金屬及鈉、鈣等之鹼金屬倒置的污 染主要是因爲與液體接觸而附著污.染。若有金屬污染，則 有氧化膜之絕縁被破壞之虞，因此使其不接觸金屬雜質係 Ο 爲重要。因此，低抑了金屬雜質含量的本發明之磺酸修飾 水性陰離子矽溶膠可特別適合用來作爲半導體晶圓之CMP 硏磨用硏磨劑。 本發明之矽溶膠之過濾性良好。以分散劑或矽醇基之 陰離子化或陽離子化能夠使矽溶膠之動黏度減低，與過濾 性沒有直接關連。對此，藉由進行磺酸修飾，確實地成爲 過濾性優良的矽溶膠。尤其將本發明之矽溶膠用作爲CMP 硏磨劑（硏磨液）時，在將硏磨液供給至硏磨裝置前必須進 -13- 201100327 行過濾，同時在循環重複使用之設計上’矽溶膠的過濾性 高係具有優點。 以CMP將矽溶膠作爲硏磨劑使用時’於循環漿料中混 入了最初硏磨中所產生的硏磨墊之硏磨屑或將硏磨墊之狀 態安定化時之修整屑等大小異物，若直接利用則會對晶圓 造成刮傷，晶圓本身成爲無法使用之物。 又，即使不將漿料循環的系統中，也會有較大粒子導 致的微刮痕之問題，爲了避免此問題，認爲在CMP裝置前 〇 緊接著進行過濾（filtration)爲重要程序。 即使在矽溶膠之製程中，由於不僅是目的物之矽石粒 子，粒子凝集而成的凝集物也生成，因此在製品化的最後 程序中，過濾是必要的。 不限於CMP，因粗粒爲問題之矽溶膠用途，過濾步驟 爲工業上重要的程序，改善矽溶膠本身的過濾性，從亦可 延長用於過濾之過濾器本身的壽命而言，亦可稱得上有益 Q 之物性改善。 發明效果 本發明之磺酸修飾水性陰離子矽溶膠在PH2以上的酸 性中ζ電位爲-1 5mV以下。於是，縱使分散媒爲酸性亦可 具有高度分散安定性。如此，由於（電位的絕對値爲大， 故具有高度分散安定性’隨之而來，矽溶膠的動黏度亦爲 小。又，不僅可高濃度化且過濾性良好。特別係將可水解 之矽化合物水解.縮合而得到原料膠態矽石時，由於能夠 -14- 201100327 顯著地減低金屬雜質之含量，因此本發明之矽溶膠 於作爲半導體晶圓之CMP硏磨劑。 【實施方式】 實施發明之形態 以下例示實施例及比較例以具體地説明本發明 發明係不限於實施例。 實施例1 於純水787.9g、26%氨水水（鹼性觸媒）786.0g 〇 12924g的混合液中，將液溫保持於35°C並且歷55 四甲氧基矽烷1522.2g、甲醇413.0g之混合液，得 與甲醇作爲分散媒之矽溶膠。 將該矽溶膠在常壓下加熱濃縮至5 OOOnU。於該 中添加作爲矽烷偶合劑之3-锍基丙基三甲氧基矽烷 在沸點下回流進行熱熟成。然後，爲了將容量保持 邊追加純水邊將甲醇及氨水進行水置換，在pH成爲 Q 的時點暫時將矽溶膠之液溫降低至室溫。接著添加 氧化氫水5 3 . 5 g，再度加熱，持續反應8小時，冷卻 後’得到磺酸修飾水性陰離子矽溶膠。 實施例2 於純水2 2 1 2.7 g、2 6 %氨水水（鹼性觸媒）5 6 7.3 g 1 2 3 9 1 g的混合液中，邊將液溫保持於2 0°C邊歷2 5 四甲氧基矽烷1522.2g、甲醇413.0g之混合液’得 與甲醇作爲分散媒之矽溶膠。 亦可適 。但本 、甲醇 分滴下 到以水 濃縮液 6.0g > 定量， 8以下 3 5 %過 至室溫 、甲醇 分滴下 到以水 -15- 201100327 將該矽溶膠在常壓下加熱濃縮至2500ml。於該濃縮液 中添加作爲矽烷偶合劑之3-锍基丙基三甲氧基矽烷6.0g， 在沸點下回流進行熱熟成。然後，爲了將容量保持定量， 邊追加純水邊將甲醇及氨水進行水置換、在pH成爲8以下 的時點暫時將矽溶膠之液溫降低至室溫。接著添加35%過 氧化氫水28g，再度加熱，持續反應8小時，冷卻至室溫 後’得到磺酸修飾水性陰離子矽溶膠。 比較例1 ❹ 於純水2212.7g、26%氨水水（鹼性觸媒）5 67.3 g、甲醇 12391g的混合液中，邊將液溫保持於20°C邊歷25分滴下 四甲氧基矽烷1522.2g、甲醇413.0g之混合液，得到以水 與甲醇作爲分散媒之矽溶膠。 將該矽溶膠在常壓下加熱濃縮至25 00ml。爲了將該濃 縮液之容量保持定量，邊追加純水邊將甲醇及氨水進行水 置換，藉由使pH成爲8以下而得到膠態矽石。 〇 比較例2 於比較例1所得之膠態矽石1 8 00g中，在攪拌下邊保 持液溫25°(：邊添加以1〇8純水稀釋八12〇3含量18.8%的市 售鋁酸鈉水溶液2.6 5 g而成的水溶液。接著在沸點下回流2 小時，得到鹼性鋁改質膠態矽石。 在室溫下，於所得鹼性鋁改質膠態矽石中投入陽離子 父換樹脂（AmberiteIR-124H)30g，進行攪拌直到pH爲3.5 以下。然後，除去陽離子交換樹脂，得到酸性鋁改質膠態 -16- 201100327 矽石。 ^ _族飾水性陰離子砂溶膠及各比 將各實施例所得之磺酸修胃 較例所得之膠態矽石的物性示於下述表1° 金屬雜質含量係使用原子吸光測定裝置進行測定。 又，Γ電位係使用測定裝置ELS-Ζ(大塚電子公司製），以動 實施例1 實施例2 比較例1 比較例2 PH 5.6 6.6 7.3 2.9 矽石濃度(質量％) 12.0 20.0 19.5 19.5 —次粒徑(nm) 12 33 33 35 二次粒徑(腦） 30 71 68 69 金屬雜質(ppm) Na 0.2 <0.1 <0.1 10 K <0.1 <0.1 <0.1 0.11 Fe <0.01 <0.01 <0.01 0.02 A1 <0.1 <0.1 <0.1 123 Ca <0.1 <0.1 <0.1 <0.1 Mg <0.01 <0.01 <0.01 <0.01 Ti <0.01 <0.01 <0.01 <0.01 Ni <0.01 <0.01 <0.01 <0.01 Cr <0.01 <0.01 <0.01 <0.01 Cu <0.01 <0.01 <0.01 <0.01 Zn <0.01 <0.01 <0.01 <0.01 Pb <0.02 <0.02 ^ <0.02 <0.02 Ag <0.01 <0.01 <0.01 <0.01 Co <0.01 <0.01 <0.01 <0.01 Mn <0.01 <0.01 <0.01 <0.01 t電位(mV) pH3 -25.0 -46.6 7.0 -41.9 pH5 -29.9 -48.5 -7.6 -47.8 pH7 -28.8 -49.0 -30.2 -45.9 pH9 -36.1 -52.0 -44.3 -53.8 pHll -33.6 -53.2 -39.5 -46.6 透過量 _ 710 260 - 態光散射都普勒法測定。 [表1 ] -17- 201100327 試驗例1 (隨時間經過之變化觀察） 將實施例1、2所得之磺酸修飾水性陰離子矽溶膠及比 較例1所得之膠態矽石的pH調整爲3與4.5之2種，保持 在4 3 °C與6 0 °C的恆溫槽中’硏究1週後及2週後的隨時間 經過之變化。 動黏度係以Canon-Fenske黏度計測定。 一次粒徑是由比表面積藉由換算而算出。二次粒徑 (ELS値）是以十二烷基硫酸鈉水溶液或檸檬酸水溶液稀釋 法測定。 實施例1之測定結果示於下述表2。實施例2之測定 結果示於下述表3。比較例1之測定結果示於下述表4。又， 表中之「聚集比」係以二次粒徑除以一次粒徑所得之數値。 [表2]Si(〇R)4 (1) wherein R is an alkyl group, preferably a lower alkyl group having 1 to 8 carbon atoms, more preferably a lower alkyl group having 1 to 4 carbon atoms. 〇 〇 as the above R, may be, for example, methyl, ethyl 'propyl, isopropyl, butyl, pentyl, hexyl, etc., with R as the methyl tetramethoxynonane, and R as the ethyl tetraethoxy A tetradecyloxydecane having a decyl alkane and an isopropyl group is preferably a derivative of an alkoxydecane, and a low condensate obtained by partially hydrolyzing an alkoxy oxime. In the present invention, it is preferred to use tetramethoxynonane in terms of easy control of the hydrolysis rate, ease of obtaining a single fine-grained vermiculite particle of 1 mol, and less residual of the unreacted material. The ruthenium compound is hydrolyzed in a reaction solvent to condense to form a colloidal 201100327 vermiculite. As the reaction solvent, water or an aqueous organic solvent can be used. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, η-butanol, tertiary butanol, pentanol, ethylene glycol, propylene glycol, and 1,4-butanediol, and acetone and methyl groups. A hydrophilic organic solvent such as a ketone such as ethyl ketone. Among these organic solvents, it is particularly preferable to use an alcohol such as methanol, ethanol or isopropyl alcohol, and it is more preferable to use the same alkyl group (R) as the raw material ruthenium compound from the viewpoint of post-treatment of the reaction solvent. Alkyl alcohols. These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent to be used is not particularly limited, and the ruthenium compound is preferably about 5 to 50 moles per 1 mole. When it is less than 5 moles, there is a case where the compatibility with the ruthenium compound is lost. When it is more than 50 m, there is a case where the manufacturing efficiency is lowered. The amount of water to be added to the organic solvent is not particularly limited as long as it is necessary for the hydrolysis of the ruthenium compound, and the ruthenium compound is preferably about 2 to 15 moles per 1 mole. Further, the amount of water mixed in the organic solvent greatly affects the particle size of the colloidal vermiculite which forms Q. If the amount of water added is relatively increased, the particle size of the colloidal vermiculite can be relatively increased. If the amount of water added is relatively reduced, the particle size of the colloidal vermiculite can be relatively reduced. Therefore, the particle size of the obtained colloidal vermiculite can be arbitrarily adjusted by changing the mixing ratio of the water to the organic solvent. In the reaction solvent, it is preferred to add a basic catalyst to adjust the reaction solvent to be alkaline. Thereby, the reaction solvent is preferably adjusted to a pH of 8 to 1, preferably more preferably p Η 8.5 to 1 0.5, and colloidal vermiculite can be rapidly formed. As an alkaline catalyst, 201100327, in consideration of impurities, organic amines, ammonia water is preferred, and particularly, for example, preferably ethylenediamine, diethylenetriamine, triethylenetetramine, ammonia, urea, ethanolamine, Tetramethylammonium hydroxide and the like. The ruthenium compound is hydrolyzed and condensed in the reaction solvent, and the raw material compound may be added to the organic solvent to be stirred at a temperature of from 0 to 100 ° C, preferably from 0 to 50 ° C. By subjecting the hydrazine compound to hydrolysis and condensation while stirring in an aqueous organic solvent, a spherical colloidal sand having a uniform particle diameter can be obtained. In the present invention, after adding a decane coupling agent having a functional group which can be chemically converted into a sulfonic acid group to a colloidal vermiculite, the functional group is converted into a sulfonic acid group, whereby the colloidal vermiculite is subjected to a sulfonic acid. Modification. This is because the acidity of the sulfonic acid group is high, resulting in hydrolysis, so that it is difficult to obtain a decane coupling agent having a sulfonic acid group. Examples of the decane coupling agent having a functional group which can be chemically converted into a sulfonic acid group include, for example, 1) a decane coupling agent having a sulfonic acid ester group which can be converted into a sulfonic acid group by hydrolysis, and 2) A ruthenium-based and/or sulfide-based coupling agent that is converted to a sulfonic acid group by oxidation. Further, since the sulfonic acid modification on the surface of the colloidal vermiculite is carried out in a solution, in order to improve the modification efficiency, it is preferred to use a coupling agent having a sparing group and/or a sulfide group in the latter. Examples of the decane coupling agent having a mercapto group include 3-mercaptopropyltrimethoxydecane, 2-mercaptopropyltriethoxydecane, 2-mercaptoethyltrimethoxydecane, and 2- Mercaptoethyl triethoxy decane and the like. The coupling agent having a sulfide group may, for example, be bis(3-triethoxydecylpropyl) disulfide. 201100327 When a coupling agent is added to colloidal vermiculite, it is preferred to include a hydrophilic organic solvent in the colloidal vermiculite in consideration of the solubility of the coupling agent. In this point, in the case of a colloidal vermiculite obtained by hydrolyzing a condensed alkoxydecane in an alcohol/water solvent with an alkaline catalyst, thereby obtaining a colloidal vermiculite, since the reaction liquid contains alcohol, no further hydrophilicity is required. Organic solvents. In this case, the hydrophilic organic solvent is more preferably 50% by mass or more based on the water in the colloidal vermiculite, and therefore it is adjusted by concentrating the reaction liquid as needed. On the other hand, in the case where a colza coupler is added to the water-dispersed colloidal vermiculite, a hydrophilic solvent which dissolves the decane coupling agent is added. The hydrophilic organic solvent may, for example, be an alcohol such as isopropyl alcohol, ethanol or methanol. Among them, an alcohol of the same kind as the alcohol produced by hydrolysis of the hydrazine compound is preferably used. This is because the use of the same type of alcohol as the alcohol produced by the hydrolysis of the hydrazine compound can facilitate the recovery and reuse of the solvent. The amount of the coupling agent added is about 0.1 to 10% by mass based on the vermiculite. If the amount of addition is small, the r potential under acidic conditions may not be sufficiently stabilized. If the amount is too large, there is a possibility that the modified cerium sol gels over time. The temperature at the time of adding a coupling agent is not limited, but it is preferably a normal temperature (about 20 ° C) to a boiling point. The reaction time is also not limited, but it is preferably 10 minutes to 10 hours, more preferably 30 minutes to 2 hours. The pH at the time of addition is not limited, but it is preferably 7 or more and 1 or less. The strong base 'decane coupling agent of 11 or more does not react with the surface of the vermiculite, and the decane coupling agent is self-condensed with each other, which is not preferable. -10- 201100327 An oxidizing agent can be used for the oxidation of the modified sulfhydryl group and the sulfide group. For example, nitric acid, hydrogen peroxide, oxygen, ozone, organic peroxyacid (percarboxylic acid), bromine, hypochlorite, potassium permanganate, chromic acid or the like can be mentioned. Among these oxidizing agents, hydrogen peroxide and organic peroxyacids (peracetic acid, peroxybenzoic acid) are preferred in terms of easy handling and good oxidation yield. Further, in consideration of the substance produced by the reaction, it is preferable to use hydrogen peroxide. The amount of the oxidizing agent to be added is preferably from 3 times to 100 times moles of the decane coupling agent. Although the upper limit of the amount of addition is not particularly limited, it is preferably about 50 times Mo. Further, the colloidal vermiculite and the decane coupling agent have a stable structure in the oxidation reaction except for the functional group which is oxidized (transformed) into a sulfonic acid group, and thus have no by-products. Since the sulfonic acid-modified aqueous anionic oxime obtained by the above method is a solvent other than water, in order to improve the long-term storage stability of the cerium sol, a dispersion medium mainly containing a reaction solvent can be replaced with water as needed. Q Again, this water replacement can be carried out after the addition of the coupling agent or before the addition of the oxidizing agent. The method of replacing the dispersion medium mainly as a reaction solvent with water is not particularly limited, and for example, a method of quantitatively adding water while heating the sol-gel is mentioned. Further, a method in which the ruthenium sol is separated into a dispersion medium mainly composed of a reaction solvent by precipitation, separation, centrifugation or the like, and then redispersed in water is also mentioned. The sulfonic acid-modified aqueous anionic cerium sol obtained by the process of the present invention can inhibit the agglomeration or gelation of the cerium sol even if the surface of the vermiculite in the sol is modified with a sulfonic acid group, even if it is an acidic dispersion medium of 201100327. , can be stable and dispersed for a long period of time. For example, under acidic conditions, aggregation or gelation can be prevented for more than 2 weeks after preparation. Further, since the reason is not determined by the modification with a sulfonic acid group, the transparency of the cerium sol is higher than that of the colloidal vermiculite having an unmodified surface (only sterol group). Further, the oxime sol obtained by the process of the present invention is selected from the group consisting of alkali metals of sodium and potassium, 2) alkaline earth metals selected from calcium and magnesium, and 3) selected from the group consisting of ing, iron, chin, nickel, and chromium. The contents of heavy metal bismuth and light metal of copper, bell, lead, silver, and yam are as little as 1 ppm by weight or less, and further contain no halogen such as corrosive chlorine or bromine, and are of high purity. Further, the modified vermiculite contained in the cerium sol has a particle diameter of 100 nm or less, preferably 5 to 500 nm, more preferably 10 to 300 nm. The ruthenium sol of the present invention is excellent in dispersion stability during a long period of a wide pH range. The stability of the cerium sol can be evaluated by measuring the zeta potential of the cerium sol. The zeta potential refers to the potential difference generated at the interface between the solid and the liquid in contact with each other. If the absolute enthalpy of the r potential increases, the repulsive force between the particles is strong, and the stability of the particles becomes high. The closer the absolute 値 of the potential is to zero, the easier the particles will agglomerate. The cerium sol of the present invention has high stability especially in the acidic range. Since a coupling agent having an anionic group is used as a modifier, when the dispersion medium is acidic at pH 2 or higher (the potential is a negative potential (_15 mV or less), the dispersion medium is highly acidic and stable even when it is acidic. Since the absolute enthalpy of the zeta potential is large, it has a high degree of dispersion stability, and as a result, -12-201100327, the kinetic viscosity of the cerium sol is also small. The sol-gel system of the present invention can be highly concentrated. -0602 1 9 "The ruthenium sol and its preparation method", W02008/0 15943 "The ruthenium sol and its preparation method", although attempted to add a base to maintain the stability of colloidal vermiculite at high pH, or to add a small amount of organic acid The salt is made to have a high concentration, but the vermiculite concentration limit of the precursors is about 40% by weight. In contrast, the anionic cerium sol of the present invention modified with a sulfonic acid group can be in a wide range from acidic to alkaline. The concentration of the cerium sol of the present invention can be used for various purposes such as a honing agent and a coating agent for paper, and can be stably dispersed for a long period of time in a wide pH range, and is sodium or iron. The metal impurity content of aluminum or the like is high purity of 1 ppm by weight or less. The majority of the semiconductor products are caused by contamination, and the heavy metals such as iron, nickel, chromium, copper, zinc, and alkali metals such as sodium and calcium are inverted. The pollution is mainly caused by the contact with the liquid and the adhesion and staining. If there is metal contamination, the oxide film is completely destroyed, so it is important that it does not contact the metal impurity system. Therefore, the metal impurities are suppressed. The content of the sulfonic acid-modified aqueous anionic cerium sol of the present invention is particularly suitable for use as a honing agent for CMP honing of semiconductor wafers. The sol of the present invention has good filterability. Anionization with a dispersant or a sterol group. Alternatively, the cationization can reduce the kinetic viscosity of the cerium sol and is not directly related to the filterability. In this case, the sulfonic acid modification is used to surely become a cerium sol having excellent filterability. In particular, the cerium sol of the present invention is used as a CMP 硏. In the case of grinding agent (honing fluid), it is necessary to filter in the -13-201100327 line before supplying the honing liquid to the honing device, and at the same time in the design of recycling and reuse The high system has the advantage. When the ruthenium sol is used as a honing agent by CMP, the honing pad of the honing pad generated in the initial honing is mixed in the circulating slurry or the state of the honing pad is stabilized. If foreign matter such as chips is scratched, the wafer will be scratched, and the wafer itself will become unusable. Even in a system where the slurry is not circulated, there will be micro scratches due to larger particles. In order to avoid this problem, it is considered that it is an important procedure to carry out the filtration immediately before the CMP apparatus. Even in the process of the ruthenium sol, the agglomerates formed by the agglomeration of the particles due to not only the meteorite particles of the target substance It is also generated, so filtration is necessary in the final procedure of productization. Not limited to CMP, the use of coarse particles as a problem of sol, the filtration step is an industrially important procedure to improve the filterability of the cerium sol itself. In terms of extending the life of the filter itself for filtration, it can also be said to improve the physical properties of the Q. EFFECTS OF THE INVENTION The sulfonic acid-modified aqueous anionic cerium sol of the present invention has a zeta potential of -1 to 5 mV or less in an acidity of pH 2 or higher. Thus, the dispersion medium can be highly dispersed and stable even if it is acidic. In this way, (the absolute enthalpy of the potential is large, so the dispersion stability is high), and the kinetic viscosity of the cerium sol is also small. Moreover, it is not only highly concentrated but also has good filterability. When the hydrazine compound is hydrolyzed and condensed to obtain a raw colloidal vermiculite, the cerium sol of the present invention can be used as a CMP honing agent for a semiconductor wafer because the content of the metal impurities can be remarkably reduced by -14 to 201100327. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION The following examples and comparative examples are given to illustrate the invention in detail, and are not limited to the examples. Example 1 In a mixed solution of 787.9 g of pure water and 786.0 g of an aqueous ammonia (basic catalyst) of 6.012924 g The liquid temperature was maintained at 35 ° C and a mixture of 55 tetramethoxy decane 1522.2 g and methanol 413.0 g was obtained, and a sol was obtained as a dispersion medium with methanol. The cerium sol was heated and concentrated under normal pressure to 5 OOOnU. In this case, 3-mercaptopropyltrimethoxydecane as a decane coupling agent is added and refluxed at a boiling point for hot aging. Then, methanol and ammonia are water-disposed while maintaining the capacity while adding pure water. When the pH became Q, the liquid temperature of the cerium sol was temporarily lowered to room temperature. Then, 5 3 g of hydrogen peroxide water was added, and the mixture was heated again, and the reaction was continued for 8 hours. After cooling, the sulfonic acid-modified aqueous anionic cerium sol was obtained. Example 2 In a mixture of pure water 2 2 1 2.7 g, 2 6 % aqueous ammonia (basic catalyst) 5 6 7.3 g 1 2 3 9 1 g, while maintaining the liquid temperature at 20 ° C 2 5 a mixture of 1522.2 g of tetramethoxy decane and 413.0 g of methanol can be obtained as a sol of methanol as a dispersing medium. However, methanol and methanol are added dropwise to a water concentrate of 6.0 g > 3 5 % to room temperature, methanol was added dropwise to water -15-201100327 The cerium sol was heated and concentrated under normal pressure to 2500 ml. To the concentrate was added 3-mercaptopropyltrimethoxy as a decane coupling agent. 6.0 g of decane was refluxed at a boiling point to carry out thermal aging. Then, in order to keep the capacity constant, methanol and ammonia water were replaced with water while adding pure water, and the temperature of the sol sol was temporarily lowered when the pH became 8 or less. Room temperature, then add 35% hydrogen peroxide water 28g, heat again, continue After 8 hours, after cooling to room temperature, 'the sulfonic acid-modified aqueous anionic oxime sol was obtained. Comparative Example 1 ❹ In a mixture of 2212.7 g of pure water, 26% of ammonia water (basic catalyst) 5 67.3 g, and methanol of 12391 g, While maintaining the liquid temperature at 20 ° C, a mixture of 1522.2 g of tetramethoxy decane and 413.0 g of methanol was added dropwise thereto to obtain a cerium sol containing water and methanol as a dispersing medium. The cerium sol was heated under normal pressure. The concentrate was concentrated to 2500 ml. In order to keep the volume of the concentrate constant, water and methanol were replaced with pure water while adding pure water, and the colloidal vermiculite was obtained by setting the pH to 8 or less. 〇Comparative Example 2 In the colloidal vermiculite obtained in Comparative Example 1, 1 8 00 g, while maintaining the liquid temperature at 25 ° under stirring (: adding a commercially available aluminate having an 18.8% content of 18.8% diluted with 1 〇 8 pure water An aqueous solution of 2.6 5 g of a sodium aqueous solution, followed by reflux at a boiling point for 2 hours to obtain an alkaline aluminum modified colloidal vermiculite. At room temperature, a cationic parent is exchanged in the obtained basic aluminum modified colloidal vermiculite. 30 g of resin (Amberite IR-124H) was stirred until the pH was 3.5 or less. Then, the cation exchange resin was removed to obtain an acidic aluminum modified colloidal-16-201100327 vermiculite. ^ _ Decorative water-based anionic sand sol and each ratio The physical properties of the colloidal vermiculite obtained by the example of the sulfonic acid-strained sulphate obtained in the examples are shown in the following Table 1. The metal impurity content was measured by using an atomic absorption spectrometer. Further, the zeta potential was measured using a measuring device ELS-Ζ (大冢Example 1 Example 2 Comparative Example 2 PH 5.6 6.6 7.3 2.9 Vermiculite concentration (% by mass) 12.0 20.0 19.5 19.5 - Secondary particle diameter (nm) 12 33 33 35 Secondary particle diameter (brain) 30 71 68 69 Metal impurities (ppm) Na 0.2 <0.1 ≪ 0.1 10 K < 0.1 < 0.1 < 0.1 0.11 Fe < 0.01 < 0.01 < 0.01 0.02 A1 < 0.1 < 0.1 < 0.1 123 Ca < 0.1 < 0.1 < 0.1 < 0.1 Mg < 0.01 < 0.01 < 0.01 < 0.01 Ti < 0.01 < 0.01 < 0.01 < 0.01 Ni < 0.01 < 0.01 < 0.01 < 0.01 Cr < 0.01 < 0.01 < 0.01 <; 0.01 Cu < 0.01 < 0.01 < 0.01 < 0.01 Zn < 0.01 < 0.01 < 0.01 < 0.01 Pb < 0.02 < 0.02 ^ < 0.02 < 0.02 Ag < 0.01 < 0.01 <; 0.01 < 0.01 Co < 0.01 < 0.01 < 0.01 < 0.01 Mn < 0.01 < 0.01 < 0.01 < 0.01 t potential (mV) pH 3 -25.0 -46.6 7.0 -41.9 pH5 -29.9 -48.5 - 7.6 -47.8 pH7 -28.8 -49.0 -30.2 -45.9 pH9 -36.1 -52.0 -44.3 -53.8 pHll -33.6 -53.2 -39.5 -46.6 Permeation _ 710 260 - Determination by state light scattering by Doppler. [Table 1] -17- 201100327 Test Example 1 (observed as a function of time) The pH of the sulfonic acid-modified aqueous anionic oxime sol obtained in Examples 1 and 2 and the colloidal vermiculite obtained in Comparative Example 1 was adjusted to 3 and Two of 4.5 were kept in a constant temperature bath at 4 3 ° C and 60 ° C. The change over time was observed after 1 week and 2 weeks. The dynamic viscosity was measured by a Canon-Fenske viscometer. The primary particle diameter is calculated from the specific surface area by conversion. The secondary particle size (ELS値) is measured by a sodium dodecyl sulfate aqueous solution or a citric acid aqueous solution dilution method. The measurement results of Example 1 are shown in Table 2 below. The measurement results of Example 2 are shown in Table 3 below. The measurement results of Comparative Example 1 are shown in Table 4 below. Further, the "aggregation ratio" in the table is a number obtained by dividing the secondary particle diameter by the primary particle diameter. [Table 2]
將pH調整爲3 '在431下保存 將pH調整爲3、在60°C下保存 \ 1週後 2週後 1週後 2週後 pH 3.02 3.03 3.02 3.04 動黏度(mm2/S) 1.5 1.5 1.5 1.5 —次粒徑㈣ 11.3 11.0 11.2 11.1 二次粒徑(nm) 28.3 28.2 28.3 30.0 聚集比 2.51 2.56 2.54 2.71 將PH調整爲4.5 、在43°C下保存 將pH調整爲4.5 、在60。。下保存 1週後 2週後 1週後 2週後 PH 4.49 4.42 4.25 4.01 動黏度(mm2/S) 1.6 1.6 1.6 1.6 —次粒徑(麵） 11.0 11.2 11.1 11.4 二次粒徑(酿） 28.8 28.3 27.9 28.5 聚集比 2.62 2.54 2.52 2.50 -18- 201100327Adjust pH to 3 'Save under 431 Adjust pH to 3, store at 60 ° C \ 1 week after 2 weeks 1 week later 2 weeks after pH 3.02 3.03 3.02 3.04 Dynamic viscosity (mm2/S) 1.5 1.5 1.5 1.5 - Secondary particle size (4) 11.3 11.0 11.2 11.1 Secondary particle size (nm) 28.3 28.2 28.3 30.0 Aggregation ratio 2.51 2.56 2.54 2.71 Adjust the pH to 4.5 and store at 43 °C to adjust the pH to 4.5 at 60. . After 1 week, 2 weeks, 1 week, 2 weeks, 2 weeks later, PH 4.49 4.42 4.25 4.01 Dynamic viscosity (mm2/S) 1.6 1.6 1.6 1.6—Secondary particle size (surface) 11.0 11.2 11.1 11.4 Secondary particle size (brewed) 28.8 28.3 27.9 28.5 aggregation ratio 2.62 2.54 2.52 2.50 -18- 201100327
[表3] 將pH調整爲3 、在43°C下保存 將pH調整爲3 、在60。。下保存 1週後 2週後 1週後 2週後 pH 3.20 3.20 3.22 3.29 動黏度(mm2/S) 1.4 1.4 1.4 1.4 一次粒徑(nm) 33.6 34.4 33.6 34,4 二次粒徑(nm) 71.3 71.0 70.4 71.0 聚集比 2.12 2.07 2.10 2.06 將pH調整爲4.5 、在43°C下保存 將pH調整爲4.5 、在60°C下保存 1週後 2週後 1週後 2週後 pH 4.73 4.75 4.83 4.83 動黏度(mm2/S) 1.5 1.4 1.4 1.4 一次粒徑(nm ) 33.5 33.8 33.7 33,9 二次粒徑(nm) 71.1 71.2 71.7 70.8 聚集比 2.12 2.11 2.13 2.09 [表4] \ 將pH調整爲3、在43°C下保存 將pH調整爲3，在6(TC下保存 1週後 2週後 1週後 2週後 PH 3.36 3.36 在第7日凝膠化 動黏度(mm2/S) 1.6 2.8 一次粒徑(nm) 35.2 34.8 二次粒徑(nm) 130.5 306.2 聚集比 3.71 8.80 將pH調整爲4.5、在43°C下保存 將pH調整爲4.5、在6(TC下保存 1週後 2週後 1週後 2週後 PH 5.2 5.22 在第7日凝膠化 動黏度(rmn2/S) 3.5 3.6 —次粒徑(nm) 36.2 34.6 二次粒徑(nm) 247.2 371.1 聚集比 6.82 10.7 201100327 試驗例2(透過量（過濾性）評價） 硏究實施例2所得之磺酸修飾水性陰離子矽溶膠及比 較例1所得之膠態砂石的透過量（過濾性）。具體而言，使 用 Adventec東洋公司之開孔 3μπι的薄膜過濾器（型 番：Α300Α047Α)，以-0.07MPa的減壓度之條件進行吸引過 濾，測定1 0分鐘內上述矽溶膠或膠態矽石透過濾紙之透過 量，藉此評價過濾性。 考量測定數據之偏差，各測定6次，去除所測得之透 0 過量的最大値與最小値，以4次測定數據的平均値進行評 價。將10分鐘內透過濾紙之膠態矽石透過量的結果一倂示 於上述表1。由表1的結果可知：實施例2所得之磺酸修 飾水性陰離子矽溶膠相較於比較例1的膠態矽石，透過A (過濾性）大了約2.7倍。 【圖式簡單說明】 •fm*. 無。 Q 【主要元件符號說明】 無。 -20-[Table 3] The pH was adjusted to 3 and stored at 43 ° C. The pH was adjusted to 3 at 60. . After 1 week, 2 weeks, 1 week, 2 weeks, 2 weeks later, pH 3.20 3.20 3.22 3.29 Dynamic viscosity (mm2/S) 1.4 1.4 1.4 1.4 Primary particle size (nm) 33.6 34.4 33.6 34,4 Secondary particle size (nm) 71.3 71.0 70.4 71.0 Aggregation ratio 2.12 2.07 2.10 2.06 Adjust pH to 4.5, store at 43 °C, adjust pH to 4.5, store at 60 °C for 1 week, 2 weeks after 1 week, 2 weeks later, pH 4.73 4.75 4.83 4.83 Dynamic viscosity (mm2/S) 1.5 1.4 1.4 1.4 Primary particle size (nm) 33.5 33.8 33.7 33,9 Secondary particle size (nm) 71.1 71.2 71.7 70.8 Aggregation ratio 2.12 2.11 2.13 2.09 [Table 4] \ Adjust pH to 3 Store at 43 °C to adjust the pH to 3, 6 weeks after storage for 1 week, 2 weeks after 1 week, 2 weeks after the pH 3.36 3.36 gelation viscosity on the 7th day (mm2/S) 1.6 2.8 Primary particle size (nm) 35.2 34.8 Secondary particle size (nm) 130.5 306.2 Aggregation ratio 3.71 8.80 Adjust pH to 4.5, store at 43 °C, adjust pH to 4.5, and store at 6 (TC for 1 week, 2 weeks) After 2 weeks after 1 week, PH 5.2 5.22 Gelation dynamic viscosity (rmn2/S) on the 7th day 3.5 3.6 - Secondary particle size (nm) 36.2 34.6 Secondary particle size (nm) 247.2 371.1 Aggregation ratio 6.82 10.7 20110032 7 Test Example 2 (Evaluation of the amount of permeation (filterability)) The permeation amount (filterability) of the sulfonic acid-modified aqueous anionic cerium sol obtained in Example 2 and the colloidal grit obtained in Comparative Example 1 was examined. Specifically, Adventec Toyo Co., Ltd. opened a membrane filter of 3 μm (type: Α300Α047Α), and suctioned and filtered under the condition of a decompression degree of -0.07 MPa, and measured the permeation amount of the above-mentioned cerium sol or colloidal meteorite permeable filter paper in 10 minutes. In this way, the filterability was evaluated. The deviation of the measurement data was measured, and each measurement was performed 6 times, and the maximum enthalpy and minimum enthalpy of the measured osmotic excess were removed, and the average enthalpy of the four measurement data was evaluated. The filter paper was permeable within 10 minutes. The results of the colloidal vermiculite permeation amount are shown in the above Table 1. From the results of Table 1, it is understood that the sulfonic acid-modified aqueous anionic cerium sol obtained in Example 2 was compared with the colloidal vermiculite of Comparative Example 1, through A ( The filterability is about 2.7 times larger. [Simplified illustration] • fm*. Q [Main component symbol description] None. -20-