1247723 ⑴ 玖、發明說明 【發明所屬之技術領域】 本發明係有關使用種粒子分散液之矽石溶膠之製造方 法及藉由該製造方法取得之矽石溶膠。 【先前技術】1247723 (1) Field of the Invention The present invention relates to a method for producing a vermiculite sol using a seed particle dispersion and a vermiculite sol obtained by the production method. [Prior Art]
先行技術中，被提出各種製造矽石溶膠之方法。其中 又以於種粒子分散液中使鹼金屬矽酸鹽進行脫鹼後，進行 添加所取得之酸性矽酸液的方法中，其取得矽石膠質粒子 之粒徑爲均勻者，具可調整所期待粒徑等優點，如：本申 請發明者於特開昭63 — 45 1 1 4號公報（專利文獻1 )中，調 製種粒子後，於以使水玻璃等鹼金屬矽酸鹽水溶液以離子 交換樹脂等進行脫鹼後，加入取得之酸性矽酸液，於種粒 子表面使酸性矽酸進行結合、層合，析出後，成長種粒子 後揭示製造矽石溶膠之方法。In the prior art, various methods for producing a vermiculite sol have been proposed. Further, in the method for removing the alkali metal citrate in the seed particle dispersion, and adding the obtained acid citric acid solution, the particle size of the gangue colloidal particles is uniform, and the adjustable In the case of the invention, the inventors of the present invention have prepared an alkali metal citrate aqueous solution such as water glass by ionizing the seed particles in JP-A-63-45 1 1 (Patent Document 1). After the alkali removal of the exchange resin or the like, the obtained acidic citric acid solution is added, and the acid tannic acid is bonded and laminated on the surface of the seed particles, and after precipitation, the seed particles are grown to reveal a method for producing the vermiculite sol.
惟，於此種粒子分散液進行添加酸性矽酸液之方法中 ，將出現（1 )酸性矽酸聚合度爲1〜4之極低聚合度，因 此，粒子成長時間極長，特別是取得含均勻大粒徑矽石粒 子之矽石溶膠時，務必重複進行粒子成長。又，（2 )伴 隨粒子成長降低粒子表面積，如··務必降低酸性矽酸液之 添加速度，因此，降低生產能力、生產性，另外，時間縮 短後，加速酸性矽酸液之添加速度，造成粒子凝聚’產生 新的微細粒子後，所取得矽石溶膠其粒徑分佈出現不均等 問題點產生。另外，（3 )酸性矽酸液降低安定性，其工 程管理條件非得極爲嚴格不可等問題點。 -5- (2) 1247723 【發明內容】 本發明係提供一種於種粒子分散液中添加含所定尺寸 之活性矽酸粒子之分散液後，可使種粒子迅速成長粒子之 製造矽石溶膠之方法者。 本發明之目的更提供藉由該製造方法取得矽石溶膠者 〇 本發明之矽石溶膠製造方法其特徵係於下記（a )之 種粒子分散液中將下記（b )之活性矽酸粒子分散液進行 加熱之同時以連續性或間歇性進行加入，附者活性矽酸粒 子於種粒子後，使粒子成長者。 (a )藉由雷射光以動態光散射法所測定之平均粒徑 (DLS) 5〜1000 nm之種粒子水性分散液者，pH 爲7〜12 種粒子分散液。 (b )藉由雷射光以動態光散射法所測定之平均粒徑 (Dlf )爲2〜50 nm (惟，平均粒徑（DLF )爲小於平均粒 徑（DLS )。），且，以NaOH滴定法所測定之平均粒徑（ DNaF)爲9〜6 nm者，更且，該平均粒徑（DLF)與該平均 粒徑（DNaF)相互之比（DLF) / (DNaF)爲1.8〜30之活 性矽酸粒子水性分散液者，pH爲5〜1 1之活性矽酸粒子 分散液。 此製造方法中，以60〜160 °C之溫度下進行上述之加 熱者宜。 又，該活性矽酸粒子以（a )酸進行中和矽酸鹼後， 以鹼使所生成之矽石氫化溶膠進行解膠後，取得活性矽酸 -6- 1247723 (3) 粒子，或（b )以酸中和矽酸鹼後，以鹼使所生成之矽石 氫化溶膠進行解膠之同時進行機械性微細化後取得活性矽 酸粒子者宜。 又，該活性矽酸粒子之平均粒徑（DLF )其該種粒子 平均粒徑（DLS )爲12 nm以下時，該平均粒徑（dls )爲7 / 1 0以下，該種粒子平均粒徑（DLS )爲超出1 2 nm時，該 平均粒徑（DLS)爲5/10以下者宜。 本發明矽石溶膠之特徵係藉由雷射光以動態光散射法 所測定之平均粒徑（DLZ)爲12〜200 nm者，且，以NaOH 滴定法所測定之平均粒徑（DNaZ)爲5〜30 nm者，更且， 該平均粒徑（Dlz)與該平均粒徑（DNaZ)相互之比（Dlz )/ (DNaZ)爲 2〜30 者。 本發明矽石溶膠之製造方法係使具所定範圍粒徑之良 .好反應性活性矽酸粒子附著於種粒子表面後使粒子成長者 ，因此，可迅速進行此粒子之成長。藉由此，縮短矽石溶 膠之製造時間，極具經濟效益。更可取得含均勻大粒徑之 矽石粒子的矽石溶膠。 【實施方式】 〔發明實施之最佳形態〕 以下，針對本發明進行具體說明。 〔種粒子分散液〕 做爲本發明種粒子分散液者可使用藉由雷射光以動態 光散射法所測定之平均粒徑（Dls )爲5 nm〜1 000 nm之種 (4) 1247723 粒子水性分散液，pH爲7〜12者。 做爲本發明所使用之種粒子分散液之種粒子者可使用 如：Si〇2、AhCh、Ti〇2、Zr〇2等無機氧化物或此等複合氧 化物之微粒子，而，其中又以SiCh爲理想使用者。此種 粒子通常以分散於水中之水性溶膠狀態下被使用之。 又，亦可使用其他先行公知之種粒子分散液，如··該 特開昭63 - 45 1 1 4號公報中所揭示之種子液亦爲理想使用 者。具體而言，可混合矽酸鹼水溶液及/或鹼水溶液與酸 性矽酸液混合後，調整混合液之Si〇2 / M:0 ( Μ :鹼金屬 )莫耳比爲2.8〜10之後，以60 °C以上之溫度下藉由進行 完熟後取得種子液（種粒子分散液）。 種粒子之粒徑可選擇考量最後取得矽石溶膠之矽石粒 徑最適者使用之。本發明矽石溶膠之製造方法中其粒子成 長速度快，因此，用於此之種粒子無法預先耗費時間調製 種粒子，可使用小粒徑種粒子做爲種粒子之機能。 此種粒子之平均粒徑藉由雷射光動態光散亂法進行測 定時，約爲5〜10000 nm，較佳者爲7〜100 nm。當平均粒 徑不足5 nm時，則種粒子不安定，添加活性矽酸粒子分散 液時呈凝膠化，出現凝聚。反之，平均粒徑超出1 000 nm 時，則通常耗費調製種粒子之時間，不符合本發明迅速使 種粒子進行粒子成長，提昇生產性之主旨。 種粒子分散液之濃度並未特別限定，一般以氧化物換 算爲0.1〜20重量％，較佳者爲0.5〜10重量％。當此値以 氧化物換算時不足0.1重量％時，則濃度太低，易於溶解 而減少粒子，或使粒子消失，無法發揮種粒子之功能。反 -8- (5) 1247723 之，種粒子分散液濃度以氧化物換算時，起出2 0重量％則 種粒子出現凝聚，則無法取得單分散均勻粒徑之溶膠。且 ，種粒子濃度過高而延遲活性矽酸粒子分散液之供給速度 ，務必預防凝聚。更且，種粒子數量太多，一個個粒子之 成長受抑制，妨礙粒子之迅速成長。 種粒子分散液之pH通常爲7〜12，更佳者爲8〜11。 當pH不足7則降低粒子表面之電位、粒子出現凝聚，反 之，pH起出1 2則種粒子溶解或所添加之活性矽酸粒子溶 解而造成延遲粒子之成長，粒徑分佈不均之問題。 必要時，種粒子分散液中可添加NaOH、KOH，等鹼 金屬水溶液、胺水溶液等者，種粒子分散液中之SiCh / M2〇（ Μ:鹼金屬）莫耳比爲2.8〜200，特別以2.8〜120爲 更佳。當SzO: / Μ2〇莫耳比不足2.8時，則出現溶解種粒 子現象，反之，Si〇2 /Μ2〇莫耳比起出200時，則種粒子 分散液中供入活性矽酸粒子分散液時將降低分散液之pH 出現粒子之凝聚。 〔活性矽酸粒子分散液〕 做爲本發明活性矽酸粒子分散液者其以雷射光動態光 散射法所測定平均粒徑（DLF )爲2〜50 nm (惟，平均粒 徑（D L F )小於平均粒徑（D L s )。）者，且，以N a Ο Η滴 定法所測定之平均粒徑（DNaF )爲0.9〜6 nm者，更且， 該平均粒徑（Dlf)與該平均粒徑（DNaF)相互之比（Dlf )/ ( DNaF )爲1 ·8〜30之活性矽酸粒子水性分散液者， pH以5〜1 1被使用之。 (6) 1247723 本發明所使用之活性矽酸粒子務必附與種粒子之迅速 成長粒子而期待爲所定範圍之粒子者。更於種粒子附著活 性砂酸粒子後，使粒子成長之，因此，活性砂酸粒子之平 均粒徑使用小於其種粒子者。針對此活性砂酸粒子之製造 方法並未特別限定，一般如：以矽石氫化凝膠做爲原料所 調製之活性矽酸粒子等例。又，本發明所使用之活性矽酸 粒子爲多孔性者，因此，做爲其平均粒徑之規定方法者， 不僅需要雷射光動態光散射法之測定値，亦需NaOH滴定 法之測定値。 以下，針對此進行詳述。 於種粒子分散液中添加不足2 nm活性矽酸粒子平均粒 徑（DLF )之活性矽酸粒子分散液時，種粒子之粒子成長 速度遲緩，且，此活性矽酸粒子分散液與酸性矽酸液相同 呈不安定時，不易做成高濃度者。於種粒子分散液中添加 低濃度之活性矽酸粒子分散液後，分散液中之種粒子濃度 亦下降，結果降低其生產效率。 另外，活性矽酸粒子之平均粒徑（DLF )超出50 nm時 ，則幾乎無法寄望種粒子粒子成長。因此，此平均粒徑（ 〇lf)以3〜40 nm者宜。 雷射光動態光散射法之粒徑可藉由如：粒徑分佈測定 裝置（Particle Sizing Systems公司製· NICOMP — 380) 所測定者，取得目測測定値。 又，爲取得更快速之粒子成長速度時，該活性矽酸粒 子之平均粒徑（DLF)之種粒子平均粒徑（DLS)爲12 nm 以下時，該平均粒徑（DLS )爲7 / 1〇以下者，該種粒子之 -10- (7) 1247723 平均粒徑（DLS )超出1 2 nm時，該平均粒徑（DLS )爲5 / 1〇以下者宜。 更且，該活性矽酸粒子以NaOH滴定法所測定之平均 粒徑（DNaF )爲0.9〜6 nm者，且，該平均粒徑（DLF )與 平均粒徑（DNaF)相互之比（DlF) / (DNaF)以〗·8〜30 者宜。 該平均粒徑（DNaF)不足0.9 nm時，則該種粒子之成 長速度與使用先前酸性矽酸液爲相同遲緩者，且，活性矽 酸粒子分散液之安定性亦不足，因此，無法使活性矽酸粒 子分散液做成高濃度者，亦無法提昇生產性。反之，該平 均粒徑（DNaF )超出6 nm時，則依其種粒子粒徑之不同， 於種粒子表面選擇性無法析出，生成新粒子，最後取得矽 石粒子粒徑分佈不均之傾向。 另外，使用雷射光動態光散射法所測定之活性矽酸粒 子平均粒徑與使用NaOH滴定法所測定之同粒子平均粒徑 之比（DLF ) / ( DNaF )爲不足1 .8時，則依其平均粒徑（ DLF )之不同尺寸，降低活性矽酸粒子之反應性，且，提 高粒子成長速度效果亦不足。反之，該平均粒徑之比（ DlF) / (DNaF)超出30則取得砂石粒子強度變弱，如： 做爲硏磨用粒子用於半導體基板等硏磨材料時，無法取得 充份之硏磨速度。However, in the method of adding an acidic citric acid solution to such a particle dispersion, (1) the degree of polymerization of the acid citrate having a degree of polymerization of 1 to 4 is extremely low, and therefore, the growth time of the particles is extremely long, particularly in obtaining When the vermiculite sol of the uniform large-size vermiculite particles is uniform, the particle growth must be repeated. Further, (2) the surface area of the particles is reduced by the growth of the particles, and the addition rate of the acidic citric acid solution must be lowered, so that the productivity and productivity are lowered, and after the time is shortened, the rate of addition of the acidic citric acid liquid is accelerated, resulting in an increase in the speed of the acidic citric acid solution. After the particles are aggregated to produce new fine particles, the problem of uneven distribution of the particle size distribution of the obtained vermiculite sol occurs. In addition, (3) acidic citric acid liquid reduces stability, and its engineering management conditions are extremely strict and cannot be equal. -5- (2) 1247723 SUMMARY OF THE INVENTION The present invention provides a method for producing a vermiculite sol by adding a dispersion containing active phthalic acid particles of a predetermined size to a seed particle dispersion to rapidly grow particles of the seed particles. By. The object of the present invention is to provide a method for producing a vermiculite sol according to the present invention, which is characterized in that the active citric acid particles of the following (b) are dispersed in the particle dispersion of the following (a); When the liquid is heated, it is continuously or intermittently added, and the active phthalic acid particles are added to the seed particles to grow the particles. (a) An aqueous dispersion of particles having an average particle diameter (DLS) of 5 to 1000 nm as measured by dynamic light scattering by laser light, and a pH of 7 to 12 kinds of particle dispersions. (b) The average particle diameter (Dlf) measured by dynamic light scattering by laser light is 2 to 50 nm (except that the average particle diameter (DLF) is smaller than the average particle diameter (DLS)), and NaOH is used. The average particle diameter (DNaF) measured by the titration method is 9 to 6 nm, and the ratio of the average particle diameter (DLF) to the average particle diameter (DNaF) (DLF) / (DNaF) is 1.8 to 30. The active citric acid particle dispersion having a pH of 5 to 1 1 is active in the aqueous dispersion of citric acid particles. In the production method, the above heating is preferably carried out at a temperature of 60 to 160 °C. Further, after the active citric acid particles neutralize the citric acid base with the (a) acid, the produced gangue hydrogenated sol is degummed with a base to obtain active citric acid-6-1247723(3) particles, or b) It is preferred to neutralize the citric acid base with an acid and then obtain the active citric acid particles by mechanically refining the produced vermiculite hydrogenated sol with a base. Further, when the average particle diameter (DLS) of the active citric acid particles is 12 nm or less, the average particle diameter (dls) is 7 / 10 or less, and the average particle diameter of the particles is When the (DLS) is more than 12 nm, the average particle diameter (DLS) is preferably 5/10 or less. The meteorite sol of the present invention is characterized in that the average particle diameter (DLZ) measured by dynamic light scattering by laser light is 12 to 200 nm, and the average particle diameter (DNaZ) measured by NaOH titration is 5 In the case of 〜30 nm, the ratio of the average particle diameter (Dlz) to the average particle diameter (DNaZ) (Dlz) / (DNaZ) is 2 to 30. The method for producing the vermiculite sol of the present invention is such that the particles having a predetermined range are good. The highly reactive active tannic acid particles adhere to the surface of the seed particles to grow the particles, so that the growth of the particles can be rapidly performed. By this, the manufacturing time of the vermiculite sol is shortened, which is extremely economical. Further, a vermiculite sol containing a uniform large particle size of vermiculite particles can be obtained. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be specifically described. [Particle particle dispersion] As the particle dispersion of the present invention, an average particle diameter (Dls) of 5 nm to 1 000 nm measured by dynamic light scattering by laser light can be used. (4) 1247723 Particle water-based Dispersion, pH is 7~12. As the seed particles of the seed dispersion used in the present invention, inorganic oxides such as Si〇2, AhCh, Ti〇2, and Zr〇2 or fine particles of such composite oxides can be used, and SiCh is the ideal user. Such particles are usually used in the state of an aqueous sol dispersed in water. Further, other known particle dispersions can be used, and the seed liquid disclosed in Japanese Laid-Open Patent Publication No. SHO63-45119A is also preferably used. Specifically, after mixing the aqueous citric acid solution and/or the aqueous alkali solution with the acidic citric acid solution, adjusting the Si〇2 / M:0 (Μ: alkali metal) molar ratio of the mixed solution to 2.8 to 10, The seed liquid (seed particle dispersion) was obtained by completion of the temperature at a temperature of 60 ° C or higher. The particle size of the particles can be selected to determine the optimum particle diameter of the vermiculite sol. In the method for producing a vermiculite sol of the present invention, since the particle growth rate is fast, it is not possible to prepare the seed particles in advance for the particles of the seed, and the small particle size particles can be used as the seed particle function. The average particle size of such particles is measured by a laser light dynamic dispersion method, which is about 5 to 10,000 nm, preferably 7 to 100 nm. When the average particle diameter is less than 5 nm, the seed particles are unstable, and when the active citric acid particle dispersion is added, gelation occurs and aggregation occurs. On the other hand, when the average particle diameter exceeds 1 000 nm, the time for modulating the seed particles is usually consumed, and the object of the invention is not in accordance with the present invention, and the particles are rapidly grown and the productivity is improved. The concentration of the particle dispersion is not particularly limited, and is usually 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the oxide. When the enthalpy is less than 0.1% by weight in terms of oxide, the concentration is too low, it is easy to dissolve, the particles are reduced, or the particles are eliminated, and the function of the seed particles cannot be exhibited. In the case of the anti--8-(5) 1247723, when the concentration of the particle dispersion liquid is 20% by weight in terms of oxide, the seed particles are agglomerated, and a monodisperse uniform particle size sol cannot be obtained. Further, if the concentration of the seed particles is too high and the supply speed of the active ceric acid particle dispersion is delayed, it is necessary to prevent aggregation. Moreover, the number of seed particles is too large, and the growth of individual particles is suppressed, hindering the rapid growth of particles. The pH of the particle dispersion is usually from 7 to 12, more preferably from 8 to 11. When the pH is less than 7, the potential on the surface of the particles is lowered, and the particles are agglomerated. On the other hand, when the pH is 1 2, the seed particles are dissolved or the added active tannic acid particles are dissolved to cause retardation of the growth of the particles, and the particle size distribution is uneven. When necessary, an alkali metal aqueous solution, an aqueous amine solution, or the like may be added to the seed particle dispersion, and the SiCh / M2 〇 (alkali: alkali metal) molar ratio in the seed particle dispersion is 2.8 to 200, particularly 2.8~120 is better. When the SzO: / Μ2〇 molar ratio is less than 2.8, the phenomenon of dissolved seed particles occurs. On the contrary, when the Si〇2 /Μ2〇 molar ratio is 200, the active phthalic acid particle dispersion is supplied into the seed dispersion. When the pH of the dispersion is lowered, the agglomeration of particles occurs. [Reactive citrate particle dispersion] The active citric acid particle dispersion of the present invention has a mean particle diameter (DLF) of 2 to 50 nm as measured by laser light dynamic scattering (only, the average particle diameter (DLF) is smaller than The average particle diameter (DL s ), and the average particle diameter (DNaF ) measured by the N a Ο Η titration method is 0.9 to 6 nm, and further, the average particle diameter (Dlf) and the average particle diameter The ratio of the diameter (DNaF) to each other (Dlf) / (DNaF) is an aqueous dispersion of active citric acid particles of 1 · 8 to 30, and the pH is used in the range of 5 to 11. (6) 1247723 The active citric acid particles used in the present invention are preferably attached to the rapidly growing particles of the seed particles and are expected to be particles of a predetermined range. Further, after the active particles of the seed are adhered to the seed particles, the particles are grown. Therefore, the average particle diameter of the active acid particles is smaller than that of the particles. The method for producing the active oleic acid particles is not particularly limited, and examples thereof include, for example, active citric acid particles prepared by using vermiculite hydrogenated gel as a raw material. Further, since the active citric acid particles used in the present invention are porous, the method of determining the average particle diameter requires not only the measurement of the laser light dynamic scattering method but also the measurement by NaOH titration. Hereinafter, this will be described in detail. When the active citric acid particle dispersion liquid having an average particle diameter (DLF) of less than 2 nm active citric acid particles is added to the seed particle dispersion, the growth rate of the particles of the seed particles is slow, and the active citric acid particle dispersion and the acidic citric acid are dispersed. The same liquid is unsafe, and it is not easy to make a high concentration. When a low concentration active citric acid particle dispersion is added to the seed dispersion, the concentration of the seed particles in the dispersion is also lowered, and as a result, the production efficiency is lowered. Further, when the average particle diameter (DLF) of the active citric acid particles exceeds 50 nm, it is almost impossible to expect the growth of the seed particles. Therefore, the average particle diameter (〇lf) is preferably 3 to 40 nm. The particle diameter of the laser light dynamic scattering method can be measured by, for example, a particle size distribution measuring apparatus (manufactured by Particle Sizing Systems, Inc., NICOMP-380). Further, in order to obtain a faster particle growth rate, when the average particle diameter (DLS) of the average particle diameter (DLF) of the active citric acid particles is 12 nm or less, the average particle diameter (DLS) is 7 / 1 . In the case where the average particle diameter (DLS) of the 10-(7) 1247723 of the particle exceeds 12 nm, the average particle diameter (DLS) is preferably 5 / 1 〇 or less. Further, the average particle diameter (DNaF) of the active citric acid particles measured by the NaOH titration method is 0.9 to 6 nm, and the ratio of the average particle diameter (DLF) to the average particle diameter (DNaF) (DlF) / (DNaF) to 〗 〖8~30. When the average particle diameter (DNaF) is less than 0.9 nm, the growth rate of the particles is the same as that of the prior acid citrate solution, and the stability of the active citric acid particle dispersion is insufficient. Therefore, the activity cannot be made active. When the tannic acid particle dispersion is made into a high concentration, productivity cannot be improved. On the other hand, when the average particle diameter (DNaF) exceeds 6 nm, depending on the particle size of the seed particles, the surface selectivity of the seed particles cannot be precipitated, and new particles are formed, and finally the particle size distribution of the vermiculite particles tends to be uneven. Further, when the ratio of the average particle diameter of the active citric acid particles measured by the laser light dynamic scattering method to the average particle diameter of the same particles measured by the NaOH titration method (DLF) / (DNaF ) is less than 1.8, The different sizes of the average particle diameter (DLF) reduce the reactivity of the active citric acid particles, and the effect of increasing the particle growth rate is also insufficient. On the other hand, when the ratio of the average particle diameter (DlF) / (DNaF) exceeds 30, the strength of the sandstone particles is weakened. For example, when the particles for honing are used for a honing material such as a semiconductor substrate, it is not possible to obtain sufficient entanglement. Grinding speed.
NaOH滴定法之粒徑係以Sears法測定所計算之活性砂 酸比表面積（S ANa )後，於下式（1 )計算後可求取之： D]\ia = 6000 / ( 2.2xSAn3) ...... (1) 式（1)中，定數2.2爲矽石之真比重者。NaOH滴定 -11 - 1247723 (8) 法所測定中，粒子爲非多孔質時，與該雷射光之測定値約 爲相同者，而粒子爲多孔質時，其粒徑外觀，呈縮小者。 多孔質活性砂酸粒子與種粒子之反應性高，附著於種 粒子後可促進粒子之成長。 做爲該活性矽酸粒子分散液者由其主要合成理由以使 用pH爲5〜1 1者。當超出此範圍時，則將不易取得充份 成長粒子之速度。 〔活性矽酸粒子分散液之製造〕 該活性矽酸粒子可以各種方法進行製造之，而，（a )以鹼使矽石氫化凝膠進行解膠、或（b)以鹼使矽石氫 化凝膠進行解膠之同時，藉由機械性進行微細化取得之活 性矽酸粒子爲理想之本發明活性矽酸粒子者。更可混合該 (a )及（b )方法取得之活性矽酸粒子使用之。 又，做爲矽石氫化凝膠者以酸中和矽酸鹼後，生成矽 石氫化凝膠者宜。此時，做爲該矽酸鹼者可使用矽酸鈉、 矽酸鉀等鹼金屬矽酸鹽，於此水溶液中可藉由加入鹽酸、 硝酸、硫酸等酸所取得者。 進行中和時之鹼金屬矽酸鹽水溶液濃度其做成SiCh 者爲1〜10重量％，更佳者爲2〜8重量％，溫度爲常溫（ 一般爲1 5〜3 5 °C )，中和後之pH爲3〜7者宜。此濃度做 成以〇2時不足1重量％則矽酸之聚合（凝膠化）將不足， 所取得活性矽酸粒子之粒徑（DLF )變小，粒子成長速度 不足。反之，此濃度做成S202超出10重量％時，則無法 均勻中和造成矽酸聚合不均，取得活性矽酸粒子之粒徑（ -12- (9) 1247723 D L F )分佈不均。 此中和取得之矽石氫化凝膠於必要時進行洗淨後使用 者宜。 做爲活性矽酸粒子分散液之第1製造方法例者如： 於矽石氫化凝膠分散液中加入鹼後使矽石氫化凝膠進行解 膠之方法例者。此時，矽石氫化凝膠分散液之濃度其做成 Si〇2者爲〇·5〜5重量％者，更佳者爲1〜4重量％。當此 濃度不足〇. 5重量％時，則所溶解矽石之比例增加，取得 活性矽酸粒子之平均粒徑（DLF )變小，不易取得加速粒 子成長速度之效果。反之，此濃度超出5重量％時，則取 得活性矽酸粒子之平均粒徑（D L F )超出5 0 n m造成不均勻 者，依種粒子尺寸之不同取得矽石溶膠之粒徑分佈亦不均 〇 做爲鹼例者可使用KOH、NaOH、等鹼金屬氫氧化物 、氫氧化銨，甚至可使用胺水溶液等。鹼之使用量以其矽 石氫化凝膠分散液中之Si〇2莫耳數（Ms)與鹼（M20代 表之）莫耳數（MA)相互之比（Ms) / (MA)爲5〜100 者，更佳者爲10〜50使用之。當該莫耳比（Ms) / (Ma )不足5時，則Na0H滴定法所測得平均粒徑（DNaF )易呈 0.9 nm以下，且，增加溶解矽石之比例，降低矽石溶膠之 生產效率、收率。反之，該莫耳比（Ms) / (MA)超出 100時，則解膠不足，該平均粒徑（DNaF)將超出6 nm， 造成降低活性矽酸粒子分散液之活性，種粒子成長中所使 用之活性矽酸粒子減少，使得所取得矽石溶膠粒徑分佈不 均。解膠時之pH爲者宜。當pH不足5時，則分散 -13- (10) 1247723 液呈高粒度化，不易取得安定之活性矽酸粒子。反 pH超出1 1則易溶解矽石呈不安定者。 以鹼進行該矽石氫化凝膠之解膠時的溫度爲5 0 -t：，更佳者爲60〜95°C。當不足50°C時，則無法取得 均勻之解膠。反之’溫度超出1 5 〇 °C則平均粒徑（D] 將超出1 0 nm，取得矽石溶膠之粒徑分佈呈不均勻。 做爲活性砂酸粒子分散液第2製造方法例者如 鹼進行矽石氫化凝膠之解膠同時’機械性微細化之方 者。微細化係於矽石氫化凝膠分散液中加入鹼後，進 膠之同時以混砂機、球磨等粉碎機進行約1 〇分鐘〜數 之處理後進行。 〔矽石溶膠之製造〕 本發明矽石溶膠之製造方法係於種粒子分散液中 活性矽酸粒子分散液進行加熱之同時，連續或間歇方 行添加之。此時種粒子分散液之溫度爲60〜160 °c， 者爲70〜120 °C。當此溫度不足60 °C時，則延遲對於 矽酸粒子種粒子表面之析出速度，因此，務必減緩活 酸粒子分散液之添加速度，其結果却阻礙種粒子之粒 速成長速度。反之，此溫度超出1 60 °C則增加種粒子 之溶解量，將產生粒子凝聚，降低矽石溶膠之收率。 ，於種粒子分散液中添加活性矽酸粒子分散液時，通 緩慢攪拌爲宜。又，必要時，此操作亦可使用高壓鍋 之。 所添加之活性矽酸粒子分散液亦可直接添加以該 之， ^150 充份 J a F ) :以 法例 行解 小時 使該 式進 更佳 活性 性矽 子迅 矽石 另外 常以 進行 方法 -14- 1247723 (11) 取得之做成S! 〇2濃度約爲0.5〜5重量％之活性矽酸 分散液者，而，必要時可使用稀釋或濃縮者。此時， 添加時活性矽酸粒子分散液之濃度做成Si〇2者爲O.f 重量％，更佳者爲〜8重量％。此濃度若不足0.5重 時’則著活性矽酸粒子分散液之添加其種粒子分散液 亦降低，加溫下進行粒子成長時，其矽石溶解上昇， 分散液呈不安定、凝膠粒子、降低收率。反之，此濃 出1 〇重量％時，則依其活性矽酸粒子分散液之添加速 同，產生新的微粒子，無法取得粒徑分佈均勻之矽石 〇 添加活性矽酸粒子分散液於種粒子分散液之比例 種粒子分散液中種粒子濃度、種粒子之粒徑、活性矽 子之聚合度及種粒子分散液之溫度等而異，通常，種 之粒徑成速度調整爲0.5〜5 nm/小時，更佳者爲1〜 /小時後進行者宜。種粒子之粒徑成長速度若不足0. /小時之活性矽酸粒子分散液添加比例時，則與先行 矽酸液之矽石溶膠製造法無太大差別，未能發揮加速 粒子速度之效果。又，種粒子之粒徑成長速度超出5 小時之活性矽酸粒子分散液添加其添加速度太快，於 活性矽酸粒子間產生新的微粒子，而無法取得粒徑分 勻之矽石溶膠。 結束活性矽酸粒子分散液之添加後，可於必要時 熟化。進行熟化後，可取得更均勻粒徑之矽石溶膠。 如此，藉由本發明矽石溶膠製造方法取得之矽石 其以雷射光動態光散射法所測之平均粒徑（DLZ )爲 粒子 進行 〜1 0 量％ 濃度 造成 度超 度不 溶膠 依其 酸粒 粒子 4 nm 5 n m 酸性 成長 nm / 相互 佈均 進行 溶膠 1 2〜 -15- (12) 1247723 2 Ο 0 n m者宜，更佳者爲1 5〜1 8 0 n m，以N a Ο Η滴定法所測 定之平均粒徑（DNaZ )爲5〜30 nm，較佳者爲5〜20 nm。 又，平均粒徑之比（DLZ ) / ( DNaZ )爲2〜30者宜， 較佳者爲2〜20。該比（DLz) / (DNaZ)不足2時，則務 必進行長時間之熟化、或高溫下之熟化，使本發明迅速成 長粒子之效果將消失，如：做爲硏磨用粒子用半導體基板 等硏磨材時，無法取得所期待之硏磨速度。 本發明矽石溶膠必要時可進行濃縮、稀釋後使用之。 做爲濃縮方法者有加熱後蒸發水份之方法，利用超速過濾 膜之方法者。此時矽石溶膠之Si〇2濃度調成10〜50重量％ 者。 本發明矽石溶膠更於必要時以有機溶媒進行溶媒取代 後亦可做成有機溶膠。做爲此溶媒取代所使用之有機溶媒者 如：甲醇、乙醇、丙醇、丁醇、二丙酮醇、糠醇、四氫康醇 、乙二醇、己二醇等醇類；醋酸甲酯、醋酸乙酯等酯類；二 乙醚、乙二醇單甲醚、乙二醇單乙醚、乙二醇單丁醚、二乙 二醇單甲醚、二乙二醇單乙醚等醚類；丙酮、丁酮、乙醯丙 酮、乙醯醋酸酯等酮類、N—甲基吡咯烷酮、二甲基甲醯胺 等醯胺類等例。此等可單獨使用，亦可混合2種以上使用之 〇 又，本發明矽石溶膠可以矽烷偶合劑進行表面處理後 ’附與疏水性後使用之，亦可於必要時，藉由離子交換樹 脂等去除矽石溶膠中之鹼後，使用之。 〔實施例1〕 -16- 1247723 (13) 以F錯由實施例進行說明本發明，惟，本發明未受限 方々此貝施例。以下實施例及比較例中，種粒子、活性矽酸 k子及ί夕石溶膠以雷射光動態光散射法測定平均粒徑（粒 徑分佈測疋裝置〔particle s丨zing systems公司製；Nicomp m 〇 d e 1 3 8 0其結果如表1所示。又，針對活性矽酸粒子 及砂石溶膠以NaOH滴定法（Sears法）進行測定由計算比 表面積所算出之平均粒徑，其結果同示於表1。 表1中更顯示以下實施例及比較例所使用之種粒子分 散液及活性矽酸粒子分散液之pH値，該活性矽酸粒子之 平均粒徑（DLF)與平均粒徑（〇NaF)相互之比（Dlf) / (D N a F )之値，及該活性矽酸粒子之平均粒徑（D L F )與 該種粒子之平均粒徑（dls)相互之比（dlf) / (dls) 之値。 〔酸性矽酸液之調製〕 以離子交換水進行稀釋SiCh之濃度爲24重量％之矽 酸蘇打水溶液（SiCh / NaiO莫耳爲3· 1 )，調製Si〇2之濃 度爲5.2重量％之稀釋砂酸蘇打水溶液。塡充氫型離子交 換樹脂（三菱化學（股份）製：Daiion SK - 1B)之柱體 中通過此溶液後’ S周製酸性砂酸液。酸性砂酸液之§丨〇2 濃度爲5.0重量％，P Η爲2 · 7。另外，以雷射光動態光散 射法所測定之平均粒徑爲1 nm者。 〔種粒子分散液（1 )之調製〕 於備有迴流器、攪拌器、溫度檢測裝置之30 L不銹鋼 -17- (14) 1247723 容器中，以2760 g離子交換水稀釋163 g之SiO:濃度爲24 重量％之矽酸蘇打水溶液（S!〇2 /Na2〇H莫耳比爲3.1) 。此液中進行混合另外調製之4 4 2 0 g該酸性矽酸液後，6 0 °C下加熱30分鐘後，調製Si〇2濃度爲4.6重量％)之種粒子 分散液（1 )。藉由雷射光動態光散射法所測定之種粒子 平均粒徑（Dls)爲5nm、SiCh /Na2〇莫耳比爲20者。 〔活性矽酸粒子分散液（1 )之調製〕 以離子交換水稀釋SiCh濃度爲24重量％之矽酸蘇打 水溶液（SiCh /Na20莫耳比爲3.1)，調製SiCh濃度爲 5.2重量％之稀釋矽酸蘇打水溶液。以水充份洗淨此矽石 氫化凝膠後，做成Si〇2濃度爲5重量％之43 kg矽石氫化 凝膠分散液後，於此加入95 5 g之濃度20重量％ NaOH水 溶液，8 0 °C下，進行解膠3小時，調製活性矽酸粒子分散 液（1 )。此時之SiCh濃度爲3重量％，Si〇2莫耳數（Ms )與鹼（M20代表之）莫耳數（MA )相互之比（Ms ) / (MA )爲1 5者。另外，以雷射光動態光散射法所測定之 平均粒徑（DLF )爲3 nm，以NaOH滴定法所測定之平均粒 徑（DNaF)爲 1 nm 者。 〔矽石溶膠（1 )之調製〕 以1個小時之時間加入4 2 7 1 6 g之活性砂酸粒子分散液 (1 )於410 g於80 t：所調製之種粒子分散液（1 )後，進 行調製矽石溶膠（1)。表1顯示矽石溶膠之SiCh濃度、 雷射光動態光散射法所測定之平均粒徑（DLZ) 、NaOH滴 -18- (15) 1247723 定法所測定之平均粒徑（DNa )及粒子成長速度。又，粒 子成長度之計算中係以雷射光動態光散射法所測定之平均 粒徑（DLZ)測定値使用之。 〔實施例2〕 〔種粒子分散液（2 )之調製〕 於具備迴流器、攪拌機、溫度檢測裝置之30 L不銹鋼 容器中，以2760 g離子交換水進行稀釋Si〇2濃度爲24重量 %之163 g矽石溶膠水溶液（Si〇2 /Na2〇莫耳比爲3.1)者 。此液中混合與實施例1同法調製之1 8200 g酸性矽酸液後 ’ 80°C下進行加熱30分鐘後調製SiCh濃度爲4.6重量％之 種粒子分散液（2 )。雷射光動態光散射法所測定之平均 粒徑（DLS )爲12 nm、Si〇2 / Na20莫耳比爲70者。 〔活性矽酸粒子分散液（2 )之調製〕 以活性矽酸粒子分散液（1 )之調製方法爲基準，除 使用濃度20重量％ 2NaOH水溶液爲4 80 g之外，同法調製 活性矽酸粒子分散液（2 )。此時Si〇2濃度爲3重量％、 SiO:莫耳數（Ms)與鹼（M2〇）之莫耳數（MO相互之 比爲30。另外，雷射光動態光散射法所測定之平均粒徑（ DLF )爲6 nm、Na〇H滴定法所測定之平均粒徑（DNaF )爲 2 nm者。 〔矽石溶膠（2 )之調製〕 以15個小時進行添加245 5 6 g活性矽酸粒子分散液（2 -19- 1247723 (16) )於溫度8 0 °C下所調製之40§種粒子分散液後’進行調製 矽石溶膠（2 )。相同於實施例1於表1顯示矽石溶膠之 Si〇2濃度，平均粒徑及粒子成長速度。 〔實施例3〕 〔活性矽酸粒子分散液（3 )之調製〕 以離子父換水進丫了稀釋Si〇2丨辰度爲24重星％之5夕酸 鈉水溶液（Si〇2 / Na2〇莫耳比爲3· 1 )後，進行調製Si〇2 濃度爲5.2重量％之稀釋矽酸鈉水溶液。此矽酸鈉水溶液 中加入硫酸進行中和後，調製矽石氫化凝膠。以水充份洗 淨此矽石氫化凝膠後，做成SiCh濃度爲 5重量％之矽石 氫化凝膠分散液，於25 kg矽石氫化凝膠分散液中加入555 g濃度20重量％之NaOH水溶液，於80°C下解膠3小時後， 調製活性矽酸粒子分散液（3 )。此時Si〇2濃度爲3重量 %、SiCh莫耳數（Ms )與鹼（M2〇 )莫耳數（Μα )相互 之比（Ms )/( Μα )爲25者。另外，雷射光動態光散射 法所測定之平均粒徑（DLF )爲4 nm、NaOH滴定法所測定 之平均粒徑（DNaF)爲2nm者。 〔矽石溶膠（3 )之調製〕 以15個小時進行添加24556 g活性矽酸粒子分散液（3 )於4 1 0 g之80 °C所調製之種粒子分散液（2 )後，進行調 製矽石溶膠（3 )。與實施例1相同於表1顯示其矽石溶膠 之Si〇2濃度、平均粒徑及粒子成長速度。 -20- 1247723 (17) 〔實施例4〕 〔活性矽酸粒子分散液（4 )之調製〕 以離子交換水進行稀釋SiCh濃度爲24重量％之5夕酸 鈉水溶液（Si〇2 / Na2〇莫耳比爲3.1 )後，進行調製Sl〇2 濃度爲5 · 2重量％之稀釋矽酸鈉水溶液。加入硫酸於此石夕 酸鈉水溶液中進行中和後，調製矽石氫化凝膠。以水充份 洗淨此矽石氫化凝膠後，做成Si〇2濃度爲5重量％之砂石 氫化凝膠分散液，添加167 g之濃度20重量％ NaOH水溶 液於35 kg矽石氫化凝膠分散液中，80 °C下解膠3小時後調 製活性矽酸粒子分散液（4 )。此時Si〇2濃度爲3重量％ 、SiCh莫耳數（Ms )與鹼（ΜΑ )之莫耳數（Μα )相互 之比（Ms )/( Μα )爲70。另外，雷射光動態光散射法 所測定之平均粒徑（DLF )爲8 nm、NaOH滴定法所測定之 平均粒徑（DNaF )爲2 nm者。 〔矽石溶膠（4 )之調製〕 以15個小時進行添加245 56 g活性矽酸粒子分散液（4 )於410 g之溫度80 °C下所調製之種粒子分散液（2 )後， 調製矽石溶膠（4 )。與實施例1相同於表1顯示其矽石溶 膠之Si〇2濃度、平均粒徑及粒子成長速度。 〔實施例5〕 〔種粒子分散液（3 )之調製〕 於具備迴流器、攪拌機、溫度檢測裝置之30 L不銹鋼 容器中以2760 g離子交換水進行稀釋Si〇2濃度爲24重量％ -21 - (18) 1247723 之1 6 3 g砂酸鈉水溶液（S i〇2 / N a 2〇莫耳比爲3 . 1 )。此液 中混合25 220 g與實施例1同法調製之酸性矽酸液，90 t下 進行加熱30分鐘後，調製Si〇2濃度爲4.6重量％之種粒子 分散液（3 )。雷射光動態光散射法所測定之種粒子平均 粒徑（DLS)爲25nm、Si〇2 /Na20莫耳比爲100者。 〔活性矽酸粒子分散液（5 )之調製〕 依活性矽酸粒子分散液（1 )之調製方法爲基準，做 成濃度20重量％之NaOH水溶液爲480 g，90Ϊ下進行解膠 之外’同法調製活性矽酸粒子分散液（5 )。此時Si〇2濃 度爲3重量％、Si〇2之莫耳數（Ms )與鹼（M2〇 )莫耳數 (Μα )相互之比（Ms ) / ( Μα )爲30。另外，雷射光動 態光散射法所測定之平均粒徑（DLF )爲12 nm、NaOH滴 疋法所測定之平均粒徑（D μ a F )爲2 n m。 〔矽石溶膠（5 )之調製〕 以17個小時進行添加123 82 g活性矽酸粒子分散液（5 )於87°C下所調製之410 g種粒子分散液（3 )，進行調製 砂石溶膠（5 )。與實施例1相同於表1顯示矽石溶膠之 SiCh濃度、平均粒徑及粒子成長速度。 〔實施例6〕 〔種粒子分散液（4 )之調製〕 於備有迴流器、攪拌機、溫度檢測裝置之30 L不銹_ 容器中’使Katal0lci SI— 8 OP (觸媒化成工業股份公司製 -22- (19) 1247723 )混合3 63 g之離子交換水後，調製Si〇2濃度爲4.6重量 %之種粒子分散液（4 )。雷射光動態光散射法所測定之 種粒子平均粒徑（DLS)爲100 nm、Si〇2 /Na20莫耳比爲 100。 〔活性矽酸粒子分散液（6 )之調製〕 依活性矽酸粒子分散液（1 )之調製方法爲基準，濃度 20重量％ 2NaOH水溶液爲320 g之外，同法調製活性矽酸粒 子分散液（6)。此時之SiCh濃度爲3重量％、SiCh莫耳數 (Ms )與鹼（M2〇 )之莫耳數（Μα )相互之比（Ms ) / ( Μα )爲45。又，雷射光動態光散射法所測定之平均粒徑（ DLF )爲20 nm、NaOH滴定法所測定之平均粒徑（DNaF )爲2 nm者0 〔矽石溶膠（6 )之調製〕 以20個小時，於溫度95 °C所調製410 g種粒子分散液（ 4 )中進行添加2728 g之活性矽酸粒子分散液（6 )’進行調 製砂石溶膠（6)。與實施例1相同於表1顯示砂石溶膠之 Sic):濃度、平均粒徑及粒子成長速度。 〔實施例7〕 〔活性矽酸粒子分散液（7 )之調製〕 以離子交換水進行稀釋SiCh濃度爲24重量％之5夕酸 納水溶液（S i 0 2 / N a2 0吴耳比爲3 .1 )後’進fj S周製S i 02 濃度爲5.2重量％之稀釋矽酸鈉水溶液。此矽酸鈉水溶液 -23- (20) 1247723 中加入硫酸進行中和後，調製矽石氫化凝膠。以水 淨此矽石氫化凝膠後，做成Sl〇2濃度爲3重量％之 化凝膠分散液，以粉碎機（安川電機（股份）製： )進行處理5小時，調製活性矽酸粒子分散液（7 ) 之S10 2濃度爲3重量％、雷射光動態光散射法所測 均粒徑（D l f )爲3 n m、N a Ο Η滴定法所測定之平均 D ν a f )爲 1 n m 者。 〔矽石溶膠（7 )之調製〕 以11小時於溫度80°C所調製之410 g種粒子分f )中添加427 1 6 g活性矽酸粒子分散液（7 )後，調 溶膠（7 )。與實施例1相同於表1顯示矽石溶膠 濃度、平均粒徑及粒子成長速度。 〔實施例8〕 〔種粒子分散液（5 )之調製〕 依種粒子分散液（4 )之調製方法爲基 sphelicaslali — 100P (觸媒化成工業股份公司製 kataloid SI— 80P之外，同法調製種粒子分散液（ΐ 時之S】〇2濃度爲4.6重量％、雷射光動態光散射法 之平均粒徑（DLS )爲120 nm。Si〇2 / Na2〇莫耳ί 〔活性矽酸粒子分散液（8 )之調製〕 依活性矽酸粒子分散液（1)所調製之方法爲 充份洗 石夕石氫 混砂機 。此時 定之平 粒徑（ ί液（1 製矽石 之Sl〇2 準，以 )取代 )。此 所測定 匕爲100 基準， -24- (21) 1247723 濃度20重量％ 2NaOH水溶液爲2 8 5 g之外，同法調整活性 矽酸粒子分散液（8 )。此時之SiCh濃度爲3重量％、Si〇: 莫耳數（Ms )與鹼（m2〇 )之莫耳數（Μα )相互之比（Ms )/( MO爲1 5。又，雷射光動態分散射法所測定之平均 粒徑（DLF )爲40 nm、NaOH滴定法所測定之平均粒徑（ DNaF)爲 2 nm者。 〔矽石溶膠（8 )之調製〕 以20個小時於150°C所調製之410 g種粒子分散液（5 )中添加1 600 g之活性矽酸粒子分散液（8 )後，進行調 製矽石溶膠（8 )。與實施例1相同於表1顯示矽石溶膠之 Si〇2 /濃度、平均粒徑及粒子成長速度。 〔比較例1〕 〔活性矽酸粒子分散液（9 )之調製〕 依活性矽酸粒子分散液（1 )之調製方法爲基準，濃 度20重量％之NaOH水溶爲950 g之外，同法調製活性矽酸 粒子分散液（9 )。此時SiCh濃度爲3重量％、SiO:之莫 耳數（Ms )與鹼（M2〇 )之莫耳數（Μα )相互之比（Ms ) / ( Μα )爲15。又，雷射光動態之平均粒徑（DLF )爲3 nm、NaOH滴定法所測定之平均粒徑（DNaF )爲2 nm者。 〔矽石溶膠（9 )之調製〕 以15個小時於溫度80°C所調製之400 g種粒子分散液 (2 )中進行添加1 744 g之活性矽酸粒子分散液（9 )，調 -25- 1247723 (22) 製矽石溶膠（9 )。與實施例1相同於表1顯示石夕 s 1〇2濃度、平均粒徑及粒子成長速度。 〔比較例2〕 〔活性矽酸粒子分散液（1 0 )之調製〕 依活性矽酸粒子分散液（1 )之調製方法爲a 度20重量％ 2Na〇H水溶液爲240 g之外，同法調馨 酸粒子分散液（10 )。此時Si〇2濃度爲3重量$ 莫耳數（Ms )與鹼（M2〇 )之莫耳數（Μα )相互5 )/( Μα )爲60。又，雷射光動態分散射法所測另 粒徑（DLF )爲80 nm、NaOH滴定法所測定之平玲 D>jaF)爲 2 nm者。 〔矽石溶膠（10 )之調製〕 以15個小時於87°C所調製之 400 g種粒子分 )中進行添加1 744 g之活性矽酸粒子分散液（1〇 ) 矽石溶膠（1〇)。與實施例1相同於表1顯示矽ί S2 02濃度、平均粒徑及粒子成長速度。 溶膠之 準，濃 活性矽 、Si〇2 比（Ms 之平均 粒徑（ 散液（3 ，調製 Ϊ溶膠之 -26- 1247723 (23) 矽石溶膠 S1O2 1濃度 |重量％ 3均粒徑| dlz/ 丨 〇NaF CO 寸 00 CO CO CD CO CO OJ X— h- τ— 〇NaZ nm 00 CN CD CD ο Ο 00 σ) CNI 寸 CD 丨、i N Q nm 艺 CO CO TO g 160 140 卜 溫度 〇〇 s S g S 00 m ⑦ S 150 § CO -V S δ g g § S 粒子 成長 速度 nm/hr 卜 τ— ^r c\i c\i Tj- (\i CN CO ΙΟ C0 d d 添加 時間 τ— ^— in l〇 in 卜 τ— ΙΟ ΙΟ 11.0 10.0 10.8 o od 10.2 00 σί 10.5 10.7 11.0 活性矽酸粒子分散名 Si〇2 /m2〇 1莫耳比I m o ΙΟ (50)*1 ΙΟ § P均粒徑關係 DLF/ Dls 0.60 0.50 _ 0.33 I 0.67 i I_ 0.48 0.20 0.60 0.33 0.25 3.20 Dlf/ DnsF CO CO CNJ CD ο CO ιο ο 〇NaF nm χ— CM CM CNI CNJ CM τ— CN CN CNJ LL. nm CO CD 寸 00 eg CO Ο 00 g δ δ g g T" 種粒子分散液 00 σί 10.0 10.0 10.0 00 oi CD σ> 00 σί 10.3 10.0 CO σ> Si〇2 /m2〇 1莫耳比1 o ο o 100 100 100 ο 100 Si〇2濃 度 I重量％ 1 CD 七 CD 七 CD 七 <D 七 CD CD CD 七 CO CD 七 CD 七 平均 粒徑 (Dls) nm LO CN CM 04 in CNJ 100 in 120 Csl ΙΟ CM 1 S δ δ δ g S δ 實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 實施例 6 實施例 7 實施例 8 比較例 1 比較例 2 il - r -27- 1247723 (24) 〔產業上可利用性〕 本發明矽石溶膠特別適於做爲透明塑料、玻璃等透明 基材之硬塗層劑、塑料塡充劑、透鏡、聚矽氧晶圓等硏磨 材之使用。The particle size of the NaOH titration method is determined by the Sears method and then calculated by the following formula (1): D]\ia = 6000 / ( 2.2xSAn3) . ..... (1) In equation (1), the fixed number 2.2 is the true proportion of the meteorite. NaOH titration -11 - 1247723 (8) In the measurement of the method, when the particles are non-porous, the measurement of the laser light is about the same, and when the particles are porous, the appearance of the particle size is reduced. The porous active oleic acid particles have high reactivity with the seed particles, and adhesion to the seed particles promotes the growth of the particles. As the active citric acid particle dispersion, the main reason for the synthesis is to use a pH of 5 to 1 1 . When it is outside this range, it will not be easy to obtain the speed of sufficient growth of the particles. [Production of Active Citrate Particle Dispersion] The active citric acid particles can be produced by various methods, and (a) degumming the vermiculite hydrogenated gel with a base or (b) hydrogenating the vermiculite with a base. The active phthalic acid particles obtained by mechanically refining the gel at the same time as the gelation are preferably the active citric acid particles of the present invention. It is also possible to mix the active tannic acid particles obtained by the methods (a) and (b). Further, as a vermiculite hydrogenated gel, it is preferred to form a vermiculite hydrogenated gel after neutralizing the phthalic acid base with an acid. In this case, an alkali metal citrate such as sodium citrate or potassium citrate can be used as the citric acid base, and an acid such as hydrochloric acid, nitric acid or sulfuric acid can be obtained from the aqueous solution. The concentration of the alkali metal citrate aqueous solution during neutralization is 1 to 10% by weight, more preferably 2 to 8% by weight, and the temperature is normal temperature (generally 1 5 to 3 5 ° C). And the pH after the application is 3~7. When the concentration is less than 1% by weight in the case of 〇2, the polymerization (gelation) of citric acid will be insufficient, and the particle size (DLF) of the obtained active citric acid particles will be small, and the growth rate of the particles will be insufficient. On the other hand, when the concentration of S202 exceeds 10% by weight, the polymerization of citrate cannot be uniformly neutralized, and the particle size (-12-(9) 1247723 D L F ) of the active citric acid particles is unevenly distributed. The vermiculite hydrogenated gel obtained by this neutralization is preferably washed after use. As an example of the first production method of the active citric acid particle dispersion, a method of dissolving a vermiculite hydrogenated gel by adding a base to a vermiculite hydrogenated gel dispersion is described. In this case, the concentration of the vermiculite hydrogenated gel dispersion is 〇·5 to 5 wt%, more preferably 1 to 4 wt%, in the case of Si〇2. When the concentration is less than 5% by weight, the proportion of the dissolved vermiculite increases, and the average particle diameter (DLF) of the active tannic acid particles becomes small, and the effect of accelerating the growth rate of the particles is not easily obtained. On the other hand, when the concentration exceeds 5% by weight, the average particle diameter (DLF) of the active tannic acid particles exceeds 50 nm to cause unevenness, and the particle size distribution of the vermiculite sol is not uniform depending on the particle size. As the alkali example, an alkali metal hydroxide such as KOH, NaOH, or the like, ammonium hydroxide, or an aqueous amine solution or the like can be used. The amount of alkali used is the ratio (Ms) / (MA) of the Si〇2 molar number (Ms) to the base (M20 represented by the molar number) in the vermiculite hydrogenated gel dispersion (Ms) / (MA) is 5~ 100, the better is 10 to 50. When the molar ratio (Ms) / (Ma ) is less than 5, the average particle size (DNaF ) measured by the Na0H titration method tends to be 0.9 nm or less, and the proportion of dissolved vermiculite is increased to reduce the production of vermiculite sol. Efficiency, yield. On the other hand, when the molar ratio (Ms) / (MA) exceeds 100, the gelation is insufficient, and the average particle diameter (DNaF) exceeds 6 nm, resulting in a decrease in the activity of the active ceric acid particle dispersion, and the growth of the seed particles. The active tannic acid particles used are reduced, so that the obtained vermiculite sol particle size distribution is uneven. The pH at the time of degumming is suitable. When the pH is less than 5, the dispersion of -13-(10) 1247723 is high in particle size, and it is difficult to obtain stable active citric acid particles. If the pH exceeds 1 1 , it will dissolve the vermiculite and become unstable. The temperature at which the vermiculite hydrogenated gel is degummed with a base is 50 - t: and more preferably 60 to 95 °C. When it is less than 50 °C, uniform disintegration cannot be obtained. On the other hand, if the temperature exceeds 15 °C, the average particle size (D) will exceed 10 nm, and the particle size distribution of the vermiculite sol will be uneven. The second method for producing the active sand acid particle dispersion is as a base. The degumming of the vermiculite hydrogenated gel is carried out simultaneously with the mechanical micronization. The micronization is carried out by adding a base to the vermiculite hydrogenated gel dispersion, and then feeding the mixture with a pulverizer such as a sand mixer or a ball mill. 1 〇 minutes to several times after the treatment. [Production of vermiculite sol] The method for producing the vermiculite sol of the present invention is to continuously or intermittently add the active citric acid particle dispersion in the seed particle dispersion while heating. At this time, the temperature of the seed dispersion is 60 to 160 ° C, which is 70 to 120 ° C. When the temperature is less than 60 ° C, the precipitation rate on the surface of the ceric acid particle particles is delayed, so it is necessary to slow down. The addition rate of the active acid particle dispersion, as a result, hinders the particle growth rate of the seed particles. Conversely, when the temperature exceeds 1 60 ° C, the amount of the seed particles is increased, and particle agglomeration is generated to lower the yield of the vermiculite sol. , in the seed When the active citric acid particle dispersion is added to the sub-dispersion, it is preferred to slowly stir. Further, if necessary, the operation may also use an autoclave. The added active citric acid particle dispersion may be directly added thereto, ^ 150 Fully J a F ) : Use the law to solve the hour to make the formula into a better active 矽 矽 矽 另外 另外 另外 另外 另外 另外 -14 -14 -14 -14 -14 -14 -14 -14 -14 -14 -14 -14 -14 -14 -14 -14 -14 -14 -14 -14 浓度 浓度 浓度 浓度 浓度0.5 to 5% by weight of the active citric acid dispersion, and if necessary, diluted or concentrated. At this time, the concentration of the active citric acid particle dispersion at the time of addition is 0.1% by weight, more preferably 8% by weight, based on Si〇2. When the concentration is less than 0.5, the addition of the active citric acid particle dispersion reduces the dispersion of the seed particles. When the particles are grown under heating, the dissolution of the vermiculite increases, and the dispersion is unstable, gel particles, Reduce the yield. On the other hand, when this concentration is 1% by weight, new particles are generated depending on the rate of addition of the active ceric acid particle dispersion, and it is impossible to obtain a fine particle size distribution of the fluorite, and the active ceric acid particle dispersion is added to the seed particles. The proportion of the dispersion liquid varies depending on the particle concentration of the seed particles, the particle size of the seed particles, the polymerization degree of the active tweezers, and the temperature of the seed particle dispersion. Generally, the particle size is adjusted to a speed of 0.5 to 5 nm. /hour, the better one is suitable for 1~ / hour. When the growth rate of the particle diameter of the seed particles is less than 0. /hour, the ratio of the active phthalic acid particle dispersion is not much different from that of the prior ruthenium silicate solution, and the effect of accelerating the particle velocity is not exhibited. Further, the active citric acid particle dispersion having a particle growth rate of the seed particles exceeding 5 hours is added too fast, and new fine particles are generated between the active citric acid particles, and the vermiculite sol having a uniform particle size cannot be obtained. After the addition of the active citric acid particle dispersion is completed, it can be aged if necessary. After aging, a more uniform particle size of the vermiculite sol can be obtained. Thus, the vermiculite obtained by the method for producing vermiculite sol of the present invention has a mean particle diameter (DLZ) measured by a laser light dynamic scattering method as a particle, and a concentration of ～10% by weight causes a degree of excess of sol-gel particles. 4 nm 5 nm Acidic growth nm / mutual cloth sol 1 2~ -15- (12) 1247723 2 Ο 0 nm should be better, preferably 1 5~1 8 0 nm, by N a Ο Η titration method The average particle diameter (DNaZ) determined is 5 to 30 nm, preferably 5 to 20 nm. Further, the ratio (DLZ) / (DNaZ) of the average particle diameter is preferably from 2 to 30, preferably from 2 to 20. When the ratio (DLz) / (DNaZ) is less than 2, it is necessary to perform aging for a long period of time or aging at a high temperature, and the effect of rapidly growing particles of the present invention is lost, for example, as a semiconductor substrate for honing particles or the like. When honing the material, the desired honing speed cannot be obtained. The vermiculite sol of the present invention can be used after concentration and dilution as necessary. As a method of concentration, there is a method of evaporating water after heating, and a method of using an ultrafiltration membrane. At this time, the concentration of Si〇2 of the vermiculite sol is adjusted to 10 to 50% by weight. The vermiculite sol of the present invention can also be made into an organosol after being substituted with a solvent in an organic solvent if necessary. For the organic solvent used for this solvent replacement, such as: methanol, ethanol, propanol, butanol, diacetone alcohol, decyl alcohol, tetrahydrococitol, ethylene glycol, hexanediol and other alcohols; methyl acetate, acetic acid Ester such as ethyl ester; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and other ethers; acetone, butyl Examples of ketones such as ketone, acetamidineacetone and acetamidine acetate, amides such as N-methylpyrrolidone and dimethylformamide. These may be used singly or in combination of two or more kinds. The vermiculite sol of the present invention may be subjected to surface treatment with a decane coupling agent, and may be used after being attached to hydrophobicity, and may also be used by ion exchange resin if necessary. After removing the base in the vermiculite sol, use it. [Embodiment 1] -16 - 1247723 (13) The present invention will be described by way of example with reference to F. However, the present invention is not limited thereto. In the following examples and comparative examples, the average particle diameter of the seed particles, the active citrate k and the smectite sol was measured by a laser light dynamic scattering method (particle size distribution measuring device [part s丨zing systems]; Nicomp m 〇de 1 3 8 0 The results are shown in Table 1. Further, the average particle diameter calculated by calculating the specific surface area was measured by the NaOH titration method (Sears method) for the active citric acid particles and the sand sol. In Table 1, Table 1 further shows the pH 値 of the particle dispersion and the active citric acid particle dispersion used in the following examples and comparative examples, and the average particle diameter (DLF) and average particle diameter of the active citric acid particles ( 〇NaF) ratio of each other (Dlf) / (DN a F ), and the ratio of the average particle diameter (DLF) of the active citric acid particles to the average particle diameter (dls) of the particles (dlf) / ( [dls) 〔 [Modulation of acid citrate solution] The concentration of Si 〇 2 is adjusted by distilling water with a concentration of 24% by weight of SiCh soda aqueous solution (SiCh / NaiO molar is 3.1). 5.2% by weight of aqueous solution of diluted soda ash. Hydrogen-charged ion exchange The acid (the Mitsubishi Chemical (stock): Daiion SK - 1B) column passed through this solution after the 'S week-made acid sand acid solution. The acid sand acid solution § 2 concentration is 5.0% by weight, P Η is 2 · 7. In addition, the average particle size measured by laser light dynamic scattering method is 1 nm. [Modulation of seed particle dispersion (1)] 30 L stainless steel equipped with a reflux device, a stirrer, and a temperature detecting device -17- (14) 1247723 In a container, dilute 163 g of SiO with 2760 g of ion-exchanged water: a concentration of 24% by weight aqueous solution of citrate soda (S!〇2 /Na2〇H molar ratio is 3.1). After mixing 4 4 2 0 g of the acid citric acid solution, the mixture was heated at 60 ° C for 30 minutes, and then a seed particle dispersion (1) having a Si〇 2 concentration of 4.6% by weight was prepared. The average particle diameter (Dls) of the seed particles measured by the laser light dynamic scattering method was 5 nm, and the SiCh / Na 2 〇 molar ratio was 20. [Preparation of active citric acid particle dispersion (1)] A citric acid soda aqueous solution (SiCh / Na20 molar ratio of 3.1) having a SiCh concentration of 24% by weight was diluted with ion-exchanged water to prepare a dilution SiC having a SiCh concentration of 5.2% by weight. Acid soda aqueous solution. After the vermiculite hydrogenated gel was sufficiently washed with water, a 43 kg vermiculite hydrogenated gel dispersion having a Si〇2 concentration of 5% by weight was prepared, and then 95 5 g of a 20% by weight aqueous NaOH solution was added thereto. At 80 ° C, degumming was carried out for 3 hours to prepare a reactive citric acid particle dispersion (1). The SiCh concentration at this time was 3% by weight, and the ratio (Ms) / (MA ) of the Si〇2 molar number (Ms) to the base (M20 represented) molar number (MA) was 15%. Further, the average particle diameter (DLF) measured by the laser light dynamic scattering method was 3 nm, and the average particle diameter (DNaF) measured by the NaOH titration method was 1 nm. [Preparation of vermiculite sol (1)] Add 4 2 7 1 6 g of active sand acid particle dispersion (1) to 410 g at 80 t: prepared seed dispersion (1) in 1 hour. Thereafter, the vermiculite sol (1) is prepared. Table 1 shows the SiCh concentration of the vermiculite sol, the average particle diameter (DLZ) measured by the laser light dynamic scattering method, the average particle diameter (DNa) measured by the NaOH drop -18-(15) 1247723 method, and the particle growth rate. Further, in the calculation of the particle length, the average particle diameter (DLZ) measured by the laser light dynamic scattering method was used. [Example 2] [Preparation of seed particle dispersion (2)] In a 30 L stainless steel container equipped with a reflux, a stirrer, and a temperature detecting device, the concentration of Si〇2 was diluted by 2760 g of ion-exchanged water to 24% by weight. 163 g of talc sol aqueous solution (Si〇2 / Na2 molar ratio of 3.1). This solution was mixed with 1 8200 g of an acidic citric acid solution prepared in the same manner as in Example 1 and heated at 80 ° C for 30 minutes to prepare a particle dispersion (2) having a SiCh concentration of 4.6% by weight. The average particle size (DLS) measured by the laser light dynamic scattering method was 12 nm, and the Si〇2 / Na20 molar ratio was 70. [Preparation of active citric acid particle dispersion (2)] Based on the preparation method of the active citric acid particle dispersion (1), the active citric acid was prepared by the same method except that the concentration of 20% by weight of 2 NaOH aqueous solution was 480 g. Particle dispersion (2). At this time, the concentration of Si〇2 is 3% by weight, the number of moles of SiO:mol (Ms) and alkali (M2〇) (the ratio of MO to each other is 30. In addition, the average particle measured by laser light dynamic scattering method The diameter (DLF) is 6 nm, and the average particle size (DNaF) measured by the Na〇H titration method is 2 nm. [Preparation of vermiculite sol (2)] 245 5 6 g of active tannic acid is added in 15 hours. The particle dispersion (2 -19-1247723 (16)) was prepared by modulating 40 § kinds of particle dispersions at a temperature of 80 ° C. The ruthenium sol (2 ) was prepared. The same as in Example 1 is shown in Table 1. Si 〇 2 concentration, average particle diameter and particle growth rate of the stone sol. [Example 3] [Preparation of active citric acid particle dispersion (3)] Divided Si 〇 2 丨 度 24 After the heavy star sodium 5 Sodium sulphate aqueous solution (Si〇2 / Na2〇 molar ratio is 3.1), a diluted sodium citrate aqueous solution having a Si〇2 concentration of 5.2% by weight was prepared. After neutralization with sulfuric acid, a vermiculite hydrogenated gel was prepared, and the vermiculite hydrogenated gel was washed with water to prepare a vermiculite hydrogen having a SiCh concentration of 5% by weight. The gel dispersion was added to a 25 kg vermiculite hydrogenated gel dispersion with 555 g of a 20% by weight aqueous NaOH solution, and after degumming at 80 ° C for 3 hours, a reactive citric acid particle dispersion (3) was prepared. When the Si〇2 concentration is 3% by weight, the SiCh Molar number (Ms) and the base (M2〇) molar number (Μα) are mutually proportional (Ms)/( Μα ) is 25. In addition, the laser light dynamic light scattering The average particle diameter (DLF) measured by the method is 4 nm, and the average particle diameter (DNaF) measured by the NaOH titration method is 2 nm. [Preparation of vermiculite sol (3)] 24556 g of active hydrazine is added in 15 hours. The acid particle dispersion (3) was prepared by dispersing the particle dispersion (2) at a temperature of 80 ° C at 40 ° C, and then preparing the vermiculite sol (3). The same as in Example 1 shows the vermiculite sol in Table 1. Si〇2 concentration, average particle diameter, and particle growth rate. -20- 1247723 (17) [Example 4] [Preparation of active citric acid particle dispersion (4)] Dilute SiCh concentration by ion exchange water to 24 weight After the % sodium citrate aqueous solution (Si〇2 / Na2 〇 molar ratio is 3.1), the dilution of SS〇2 concentration of 5.2% by weight is prepared. After adding sodium sulfate to the aqueous solution of sodium sulphate for neutralization, a vermiculite hydrogenated gel was prepared, and the vermiculite hydrogenated gel was washed with water to prepare a concentration of SiO 2 of 5% by weight. The sandstone hydrogenated gel dispersion was prepared by adding 167 g of a 20% by weight aqueous NaOH solution to a 35 kg vermiculite hydrogenated gel dispersion, and degumming at 80 ° C for 3 hours to prepare a reactive citric acid particle dispersion (4). At this time, the Si〇2 concentration was 3% by weight, the SiCh mole number (Ms) and the base (ΜΑ) molar number (Μα) were mutually ratio (Ms)/( Μα ) of 70. Further, the average particle diameter (DLF) measured by the laser light dynamic scattering method was 8 nm, and the average particle diameter (DNaF) measured by the NaOH titration method was 2 nm. [Preparation of vermiculite sol (4)] After adding 245 56 g of active citric acid particle dispersion (4) at a temperature of 80 ° C at a temperature of 80 ° C for 15 hours, the preparation was carried out. Vermiculite sol (4). The Si〇2 concentration, the average particle diameter, and the particle growth rate of the vermiculite sol were shown in Table 1 in the same manner as in Example 1. [Example 5] [Preparation of seed particle dispersion (3)] The concentration of Si〇2 was diluted to 25% by weight with 2760 g of ion-exchanged water in a 30 L stainless steel container equipped with a reflux, a stirrer, and a temperature detecting device. - (18) 1247723 of 1 6 3 g sodium silicate aqueous solution (S i 〇 2 / N a 2 〇 molar ratio is 3.1). 25 220 g of the acidic citric acid solution prepared in the same manner as in Example 1 was mixed with this solution, and after heating at 90 t for 30 minutes, a particle dispersion (3) having a Si〇2 concentration of 4.6% by weight was prepared. The average particle diameter (DLS) of the seed particles measured by the laser light dynamic scattering method was 25 nm, and the Si〇2 / Na20 molar ratio was 100. [Preparation of active citric acid particle dispersion (5)] Based on the preparation method of the active citric acid particle dispersion (1), NaOH solution having a concentration of 20% by weight is made into 480 g, and degumming is carried out at 90 Torr. The active citric acid particle dispersion (5) is prepared by the same method. At this time, the Si〇2 concentration was 3% by weight, the molar ratio (Ms) of Si〇2 and the molar number (Ms) of the base (M2〇) (Μα) were 30 ((α). Further, the average particle diameter (DLF) measured by the laser photo-scattering method was 12 nm, and the average particle diameter (D μ a F ) measured by the NaOH drip method was 2 n m. [Preparation of vermiculite sol (5)] Adding 123 82 g of active citric acid particle dispersion (5) to 410 g of particle dispersion (3) prepared at 87 ° C for 17 hours to prepare sand and gravel Sol (5). The SiCh concentration, the average particle diameter, and the particle growth rate of the vermiculite sol are shown in Table 1 in the same manner as in Example 1. [Example 6] [Preparation of seed particle dispersion (4)] In a 30 L stainless _ container equipped with a reflux device, a stirrer, and a temperature detecting device, 'Katal Olci SI-8 OP (manufactured by Catalyst Chemical Industries, Ltd.) -22- (19) 1247723) After mixing 3 63 g of ion-exchanged water, a particle dispersion (4) having a Si〇2 concentration of 4.6% by weight was prepared. The average particle size (DLS) of the particles measured by the laser light dynamic scattering method was 100 nm, and the Si〇2/Na20 molar ratio was 100. [Preparation of active citric acid particle dispersion (6)] Based on the preparation method of the active citric acid particle dispersion (1), the active citric acid particle dispersion was prepared in the same manner as the concentration of 20% by weight of 2 NaOH aqueous solution was 320 g. (6). The SiCh concentration at this time was 3% by weight, and the molar ratio (Ms) / (?α) of the Moth number (Ms) of the SiCh to the base (M2〇) was 45. Further, the average particle diameter (DLF) measured by the laser light dynamic scattering method is 20 nm, and the average particle diameter (DNaF) measured by the NaOH titration method is 2 nm. 0 [Modulation of vermiculite sol (6)] 20 In an hour, a dispersion of 2728 g of the active phthalic acid particle dispersion (6) was added to a 410 g particle dispersion (4) prepared at a temperature of 95 ° C to prepare a sand sol (6). The Sic) of the sand sol is shown in Table 1 in the same manner as in Example 1. The concentration, the average particle diameter, and the particle growth rate. [Example 7] [Preparation of active citric acid particle dispersion (7)] An aqueous solution of sodium bismuthate having a SiCh concentration of 24% by weight was diluted with ion-exchanged water (S i 0 2 / N a2 0 ohm ratio was 3 .1) After the 'fj S weekly S i 02 concentration of 5.2% by weight of diluted sodium citrate aqueous solution. This sodium citrate aqueous solution -23-(20) 1247723 was neutralized with sulfuric acid to prepare a vermiculite hydrogenated gel. After the vermiculite hydrogenated gel was purified by water, a gel dispersion having a concentration of 3% by weight of S1〇2 was prepared, and treated with a pulverizer (manufactured by Yaskawa Electric Co., Ltd.) for 5 hours to prepare active citric acid particles. The concentration of S10 2 of the dispersion (7) is 3% by weight, the average particle diameter (D lf ) measured by the laser light dynamic scattering method is 3 nm, and the average D ν af measured by the N a Ο Η titration method is 1 nm. By. [Preparation of vermiculite sol (7)] After adding 427 1 6 g of active citric acid particle dispersion (7) to 410 g of particle fraction f) prepared at a temperature of 80 ° C for 11 hours, the sol (7) was adjusted. . The garnet sol concentration, the average particle diameter, and the particle growth rate are shown in Table 1 in the same manner as in Example 1. [Example 8] [Preparation of seed particle dispersion (5)] The preparation method of the seed particle dispersion (4) is based on the sphelicaslali - 100P (Kataloid SI-80P manufactured by Catalyst Chemical Industries, Ltd.) The particle dispersion (S? 〇2 concentration is 4.6% by weight, and the average particle diameter (DLS) of the laser light dynamic scattering method is 120 nm. Si〇2 / Na2 〇 Mo ί [Active citrate particle dispersion Preparation of liquid (8)] The method prepared by the active ceric acid particle dispersion (1) is a full-washing stone shisha hydrogen sand mixer. At this time, the flat particle size is determined ( ί液(1矽矽石的Sl〇) 2 quasi, replace with). The measured enthalpy is 100 basis, -24- (21) 1247723 concentration 20% by weight 2 NaOH aqueous solution is 2 8 5 g, the same method adjusts the active citric acid particle dispersion (8). At this time, the SiCh concentration is 3% by weight, the Si〇: the number of moles (Ms) and the molar number of the base (m2〇) (Μα) are mutually proportional (Ms)/(MO is 15. Further, the laser light dynamics The average particle size (DLF) measured by the fractional scattering method is 40 nm, and the average particle diameter (DNaF) measured by the NaOH titration method is 2 nm. Preparation of sol (8)] After adding 1 600 g of the active citric acid particle dispersion (8) to 410 g of the particle dispersion (5) prepared at 150 ° C for 20 hours, the ruthenium sol was prepared ( 8) The same as in Example 1, Table 1 shows the Si〇2/concentration, average particle diameter, and particle growth rate of the vermiculite sol. [Comparative Example 1] [Preparation of active tannic acid particle dispersion (9)] The preparation method of the citric acid particle dispersion (1) is based on the preparation, and the concentration of 20% by weight of NaOH is dissolved in water to 950 g, and the active ceric acid particle dispersion (9) is prepared by the same method. At this time, the SiCh concentration is 3% by weight, SiO. The ratio of the molar number (Ms) to the molar number of the base (M2〇) (Mα) / ( Μα ) is 15. Further, the average optical particle diameter (DLF) of the laser light is 3 nm. The average particle diameter (DNaF) measured by the NaOH titration method is 2 nm. [Preparation of vermiculite sol (9)] It is carried out in 400 g of particle dispersion (2) prepared at a temperature of 80 ° C for 15 hours. 1 744 g of the active citric acid particle dispersion (9) was added, and the iridium sol sol (9) was adjusted to -25 - 1247723 (22). The same as in Example 1 shows the stone in Table 1. s 1 〇 2 concentration, average particle diameter, and particle growth rate. [Comparative Example 2] [Preparation of active citric acid particle dispersion (10)] The preparation method of the active citric acid particle dispersion (1) is a degree 20 The weight % 2Na〇H aqueous solution is 240 g, and the same method is used to adjust the acid dispersion (10). At this time, the concentration of Si〇2 was 3 wt%, the molar number (Ms) and the molar number of the base (M2〇) (Μα) were 5 (/α) of 60. Further, the laser light dynamic scattering method measured a particle size (DLF) of 80 nm, and the NaOH titration method determined by Pingling D>jaF) was 2 nm. [Preparation of vermiculite sol (10)] Add 1 744 g of active citric acid particle dispersion (1 〇) ochre sol (1 以 in 400 g of particles prepared at 87 ° C for 15 hours) ). The same as in Example 1 is shown in Table 1. The concentration of 矽ί S2 02, the average particle diameter, and the particle growth rate. The sol is quasi-concentrated, concentrated active 矽, Si〇2 ratio (average particle size of Ms (dispersion liquid (3, Ϊ 之 sol -26-1247723 (23) 矽石Sol S1O2 1 concentration|% by weight 3 average particle size | dlz /丨〇NaF CO inch 00 CO CO CD CO CO OJ X— h- τ—〇NaZ nm 00 CN CD CD ο Ο 00 σ) CNI inch CD 丨, i NQ nm Art CO CO TO g 160 140 s S g S 00 m 7 S 150 § CO -VS δ gg § S Particle growth rate nm/hr Bu τ — ^rc\ic\i Tj- (\i CN CO ΙΟ C0 dd Add time τ— ^—in l 〇in 卜τ— ΙΟ ΙΟ 11.0 10.0 10.8 o od 10.2 00 σί 10.5 10.7 11.0 Active citrate particle dispersion name Si〇2 /m2〇1 Mo Er ratio I mo ΙΟ (50)*1 ΙΟ § P-average particle size relationship DLF / Dls 0.60 0.50 _ 0.33 I 0.67 i I_ 0.48 0.20 0.60 0.33 0.25 3.20 Dlf/ DnsF CO CO CNJ CD ο CO ιο ο 〇NaF nm χ— CM CM CNI CNJ CM τ — CN CN CN LL. nm CO CD 00 00 eg CO Ο 00 g δ δ gg T" Seed dispersion 00 σί 10.0 10.0 10.0 00 oi CD σ> 00 σί 10.3 10.0 CO σ> Si〇2 /m2〇1 molar ratio 1 o ο o 100 100 100 ο 100 Si〇2 concentration I wt% 1 CD Seven CD Seven CD Seven<D Seven CD CD CD Seven CO CD Seven CD seven average particle size (Dls) nm LO CN CM 04 in CNJ 100 in 120 Csl CM CM 1 S δ δ δ g S δ Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 il - r -27- 1247723 (24) [Industrial Applicability] The vermiculite sol of the present invention is particularly suitable as a hard coating agent for transparent substrates such as transparent plastics and glass. The use of honing materials such as plastic enamels, lenses, and polysilicon wafers.