1250970 Λ7 B7 五、發明說明（1 ) 本發明係有關做爲化粧品、顏料、塗料等添加劑者有 用之粒卞狀，特別是超微粒子高度白色氧化鋅，其粒子形 狀特別爲四腳狀或針狀之超微粒子狀高度白色氧化鋅及其 製造方法者。更詳細者係有關鋅蒸氣隨不活性氣體之攜帶 氣體噴出反應器後，使鋅蒸氣氧化後，急劇冷卻後取得之 微粒子狀高度白色氧化鋅及其製造方法者。其中超微粒子 之1次粒徑雖不明確，一般之超微粒針對微粒子爲約 〇.l//m以下之微粒子者。 先行技術中，氧化鋅係做爲橡膠之加硫促進劑、觸媒 、電子零件材料、塗料、顏料、化粧品、塑料、橡膠補強 材料等使用之。此等氧化鋅之製造方法通常分成液相法與 氣相法。液相法係將草酸鋅、氫氧化鋅、鹽基性碳酸鋅等 以液相進行合成，沈澱後、濾別、洗淨之後，熱分解下取 得氧化鋅。液相法中雖易取得微粒子之一次粒子，由於含 液相合成，過濾，乾燥等步驟，因此所取得氧化鋅易成凝 聚體。使用氧化鋅時，務必與呈塗料、顏料、化粧品等同 時與其他液體進行生料化者，或呈橡膠、塑料之補強材料 往其他固體混煉混合者，呈電子零件材料與其他粉體進行 混合者。此時，凝聚粒之存在明顯阻礙組成之均一性，或 分散性。公知者該微粒子愈形成其均一性，分散性更良好 者。又呈超微粒子時，若使用化粧材料時針對透明性其紫 外線遮掩能可明顯提昇同時亦可附與其特性。因此，鬆開 凝聚，或爲取得微粒子之目的下務必進行粉碎處理。惟， 此時易引起由容器、粉碎球等之污沾，粒子其粒度分佈亦 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 「裝—— (請先閱讀背面之注意事項再填寫本頁} 4^1. 經濟部智慧財產局員工消費合作社印製 -4 - 1250970 Λ7 B7 五、發明說明（2 ) 呈廣泛分佈造成使用上之不便，微粒子化有限界，無法取 得超微粒子。亦即，液相法中欲取得超微粒子高度白色氧 化鋅者極爲不易。 做爲取得氧化鋅粉體之方法者有氣相法者。氣相法中 ’以法國法、美國法最常見者（日本化學會誌，1 9 8 4 年’ P 8 3 7〜8 4 2 )係氧化鋅蒸氣後，取得氧化鋅者 。美國法係含還原氣體之鋅蒸氣經氧化之方法者，亦可取 得針狀之氧化鋅、惟，易含鉛、鎘等，造成純度上問題。 另外，亦易混入團塊狀之粒子。法國法係金屬鋅蒸氣經氧 化後，製造氧化鋅之方法者，比起美國法較易取得高純度 之氧化鋅，惟，此氧化鋅係由針狀晶所成長之團塊狀粒子 ，無法取得單純之針狀製品。 做爲取得四腳狀（tetra pod )或針狀之氧化鋅方法者 ，如：特開平3 — 1 5 0 2 9 9號公報中所記載之將耐熱 性容器內氣氛之溫度設定於所定溫度後，藉由緩慢冷卻取 得之鋅蒸氣後，促進針狀晶之成長之氧化鋅晶鬚之製造方 法者。惟，藉由此製造方法所取得之氧化鋅其粒粒爲5〜 8 0 // m之較大四腳狀（tetra pod )粒子者。且，上述製 造方法爲分批式製造法者，易出現不適量產之問題。又’ 特開平4 一 3 4 9 1 1 8號公報中所記載之以階段性沿著 流動路線添加鋅蒸氣後，取得針狀氧化鋅之方法者’惟’ 藉由此方法所取得之粒子其粒徑爲1〜2 0 V m之大粒子 者。 做爲取得微粒四腳狀（tetra pod )氧化鋅之方法者’ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 「裝 (請先閱讀背面之注意事項再填寫本頁) 1T--------- 經濟部智慧財產局員工消費合作社印製 -5- 1250970 Λ7 B7 五、發明說明（3 ) (請先閱讀背面之注意事項再填寫本頁) 如：特公昭6 0 - 5 5 2 9號公報所載之將鋅蒸氣氧化燃 燒後，以4 8 0 °C /秒以上之速度進行冷卻後，取得針狀 氧化鋅之方法者。惟，此時微粒子之大小亦頂多平均粒徑 爲0 . 2〜1 μ m者。爲更使此進行微粒則冷卻速度將大 至極限被考量之。惟，如此將使鋅蒸氣之氧化呈不足，呈 混合未反應之鋅，取得之粉體著色呈灰色，極不易取得超 微粒子高度白色氧化鋅者。又，特開平7 - 1 1 8 1 3 3 號公報記載有藉由B E T點法所測定之比表面積爲7 0〜 1 1 0 m 2 / g之超微粒氧化鋅之製造法者，惟，如此做爲 極端超微粒子與化粧材料使用時雖可提昇氧化鋅懸浮液之 透明性，卻易造成降低紫外線遮掩功能之問題。 本發明目的係爲提供一種做爲化粧品、顏料、塗料等 添加劑有用之高度白色氧化鋅微粒子，特別是其粒子形狀 爲四腳狀或針狀之微粒子狀，超微粒子狀之（含超微粒子 亦稱微粒子者。）高度白色氧化鋅者。 經濟部智慧財產局員工消費合作社印製 本發明之其他目的係提供一種可製造高純度且高收率 之微粒子狀高度白色氧化鋅者，更對於工業上有用之製造 方法者。 特別是提供做爲此等添加劑使用時，不但透明性佳， 紫外線遮掩功能亦高之高度白色氧化鋅微粒子及其製造方 法者。 本發明者爲解決上述問題進行精密硏討後結果發現， 紫外線遮掩功能高之特定粒徑域，亦即，藉由B E T —點 法測定之比表面積（J I S R 1 6 2 6 )後可取得換算 本紙張尺度適用中國國家標準（CNS)A4規格(210 X 297公釐) ΓΤΊ 1250970 Λ7 B7 五、發明說明（4 ) 請先閱讀背面之注意事填寫本頁) 平均粒徑爲1 5 n m〜5 5 n m之亨特多用途比色計所示 L値爲9 0以上之微粒子狀高度白色氧化鋅者，以及因此 務必確ία ( 1 )於短時間內完全氧化辞蒸氣，與（2 )辞 蒸氣之氧化反應結束點止，爲避開生成氧化鋅粒子之衝突 ，熔融於氧化結束後立即停止反應者，進而完成本發明。 亦即，本發明之特徵係其藉由B E T —點法所測定之 比表面積之換算平均粒徑爲1 5 nm〜5 5 nm者，亨特 多用途比色計所示之L値爲9 0以上者，較佳者其粒子形 狀爲四腳狀（tetra pod )或針狀者爲其特徵之微粒子之高 度白色氧化鋅及以氧化性氣體完全且迅速氧化鋅蒸氣者與 抑制粒子成長，凝聚者之製造微粒子高度白色氧化鋅之方 法者。 經濟部卞曰慧財產局員工消費合作社印製 爲取得以亨特多用途比色計所示之L値爲9 0以上爲 其特徵之微粒子狀氧化鋅者，其重點爲反應器中以氧化性 氣體迅速氧化鋅蒸氣者。爲此發現以氣化器蒸發鋅，以設 於後步驟之加熱器使氣體過熱爲極有效者，且以密緻質碳 化矽製陶瓷做爲其加熱器材材質使用者爲極有效。氣化原 料氣體後，導入碳化矽陶瓷製加熱器後可達到先行技術所 無法到達往反應器之原料氣體噴出時溫度呈高溫者，亦即 ，可有效達到9 5 0 °C以上者，且，同材質加熱器於氧化 性氣體亦適用之，可於往反應器之噴出口充份加熱至9 0 〇°C以上。更發現使氧化性氣體組成於特定範圍下可迅速 氧化該加熱之原料氣體呈極均勻者°以有關此原料氣體與 氧化性氣體之新發現爲基準’更發現可極迅速完全氧化鋅 本紙張尺度適用中國國家標準（CNS)A4規格（2[0 X 297公釐） 1250970 Α7 Β7 五、發明說明（5 ) 蒸氣，可取得高白色微粒子氧化鋅者。又’由可如此迅速 鋅蒸氣之氧化者，比起先行技術明顯出現即使反應部縮短 亦不引起製品之著色，由B E T —點法所測定之比表面所 換算平均粒徑爲1 5 nm〜5 5 nm者，亨特多用途比色 計所示L値爲9 0以上者，較佳者其粒子形狀呈四腳狀（ tetra pod )或針狀之微粒子狀高度白色氧化鋅被取得。 本發明上述及其他目的、效果、特徵及優點可由參考 添附圖面之以下說明理解之。 〔發明實施之最佳形態〕 以下以添附圖面爲基準詳細說明本發明。 -經濟部智慧財產局員工消費合作社印製 圖1係代表適用於製造本發明微粒子狀高度白色氧化 鋅之裝置組成例所示之流程圖。裝置組成係由原料（鋅） 供給器1，原料（鋅）氣化器2，不活性氣體預熱器3， 原料（鋅）氣體加熱器4，原料氣體加熱器之噴出口 4A ’氧化性氣體加熱器5，氧化性氣體加熱器之噴出口 5 A ’反應器6，反應器之出口 6 A，冷卻器7及製品收集器 8所組成者。 藉由原料供給器1後，做爲原料之金屬鋅（Ζ η )被 供給於原料氣化器2中。供於原料氣化器2之鋅形態亦可 爲粉末狀、線狀者。不活性氣體亦可同時與原料金屬鋅供 於原料氣化器2中。此不活性氣體係做爲鋅蒸氣之攜帶氣 體’或導入原料時密封氣體之作用者。做爲不活性氣體者 如·氣、氦、氬、等例，惟，並非僅限於此，不活性氣體 本紙張尺度適用令國國家標準（CNS)A4規格（21〇 χ 297公釐） 1250970 A7 五、發明說明（6 ) 最好於導入原料氣化器2之前預先加熱爲宜。此時，不活 性氣體於不活性氣體預熱器3以5 〇 〇〜i 〇 〇 〇 I進行 預熱後’供入原料氣化器2。導人商伞、丨h /f 付热亿益z 辱人原枓氣化器2之不活性 氣體濃度針對Z n與不活性氣體之總莫耳數其莫耳數之比 ，即Z n / ( Ζ η +不活性氣體）爲3莫耳％〜7 Q莫耳 %之範圍者宜。此濃度與生產性關係密切，亦影響所取得 氧化鋅粒子之大小。 又，Q不活性氣體之鋅蒸氣，亦即原料氣體係由原料 氣化器2導入原料氣體加熱器4。原料氣化器2與原料氣 體加熱器4呈一體化亦無妨。爲原料氣體加熱器4或原料 氣化器2與原料氣體加熱器4被一體化之加熱裝置中其氣 體務必快速充份加熱之。其理由係若加熱不足則做爲加熱 器者將無法充份作用，於噴嘴噴出口 4之前，或吹塑後於 反應器6之中其鋅蒸氣爲液化或固化，進而造成系統阻塞 之原因，無法安定運轉，未能取得所期待品質之氧化鋅。 另外，即使未阻塞，取得之氧化鋅亦極可能含未反應鋅之 灰色者。 爲取得該Β Ε Τ —點法所測定比表面積之換算平均粒 徑爲1 5 nm〜5 5 nm之超微粒子，其所含鋅蒸氣之氣 體噴出口 4 A之溫度務必爲9 5 0 °C以上，較佳爲1 0〇 0 °C以上者。當此溫度低於9 5 0 t時，則氧化不足，爲 充份氧化則需增長滯留時間，因而易引起微粒子成長或微 粒子相互撞擊、融合，而無法取得所期待之微粒子。另外 ，此溫度愈高氧化反應更快，可達成完全氧化因此’均勻 「裝--- (請先閱讀背面之注意事項再填寫本頁) 訂· 經濟部智慧財產局員工消費合作社印製 私紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -9 1250970 Λ7 B7 五、發明說明（7 ) 性、分散性良好。爲使充份進行加熱可適用玻璃、陶瓷製 加熱器，特別以碳化矽陶瓷製加熱器之使用者佳。此理由 係碳化矽陶瓷於耐高溫之各種材料其熱傳導率特別大，碳 化砂爲黑灰色者，熱線之吸收率、輻射率高，因此易於氣 體供應熱能者。如上述，含鋅蒸氣之氣體噴出口 4A之溫 度愈高愈好，惟，爲實現此高溫之原料氣體加熱器4之耐 熱材料受限於耐熱性，熱傳導率，因此，此吹塑口之溫度 實用上以1 1 5 〇°C以下者。當然藉由改善原料氣體加熱 器4之傳熱材料耐熱性後，可使用高於上述溫度之高溫者 〇 更且，將傳熱媒體塡充於此加熱器4中則可更有效增 進往原料氣體之傳熱。做爲傳熱媒體者如：陶瓷、玻璃等 之耐熱材料者，特別以石英、碳化矽製陶瓷爲佳。傳熱媒 體之形狀爲考慮其傳熱效率以圓環、篩環、蜂窩狀、拉西 環等者宜。做爲傳熱媒體之塡充量者以藉由熱膨脹後不損 其加熱器之程度下大量塡充者宜。 _經濟部智慧財產局員工消費合作社印製 此原料氣體加熱器4之噴出口中原料氣體之溫度爲 9 5 0 °C以上，較理想者使呈1 〇 〇 〇 t以上之決定加熱 器直徑（內徑）及長度者宜。若使用碳化矽製陶瓷與鋁管 等相比可使加熱器4變小，且，可加熱至1 2 0 0 °C之高 溫。 如此含被加熱之鋅蒸氣氣體被導入反應器6。另外， 此鋅經氧化之氣化性氣體藉由氣體性氣體加熱器5被加熱 後，導入反應器6。針對氣化性氣體加熱器5可限定充份 -10- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）1250970 Λ7 B7 V. DESCRIPTION OF THE INVENTION (1) The present invention relates to a granule shape useful as an additive for cosmetics, pigments, paints, and the like, particularly ultra-fine particles of highly white zinc oxide, the particle shape of which is particularly four-legged or needle-shaped. Ultrafine particle-like highly white zinc oxide and its method of manufacture. More specifically, it is a microparticulate highly white zinc oxide which is obtained by oxidizing zinc vapor with zinc vapor after the carrier gas is discharged from the reactor, and is rapidly cooled. The primary particle size of the ultrafine particles is not clear, and the general ultrafine particles are particles having a particle size of about 〇.l//m or less. In the prior art, zinc oxide is used as a rubber vulcanization accelerator, a catalyst, an electronic component material, a paint, a pigment, a cosmetic, a plastic, a rubber reinforcing material, and the like. The method for producing such zinc oxide is generally classified into a liquid phase method and a gas phase method. In the liquid phase method, zinc oxalate, zinc hydroxide, and zinc-based zinc carbonate are synthesized in a liquid phase, and after precipitation, filtration, washing, and thermal decomposition, zinc oxide is obtained. In the liquid phase method, it is easy to obtain the primary particles of the fine particles, and since the liquid phase is synthesized, filtered, dried, and the like, the zinc oxide obtained is liable to form agglomerates. When using zinc oxide, be sure to mix it with other liquids such as paints, pigments, cosmetics, etc., or mix the rubber and plastic reinforcing materials with other solids, and mix the electronic parts with other powders. By. At this time, the presence of the agglomerated particles significantly hinders the homogeneity or dispersibility of the composition. It is well known that the fine particles form uniformity and are more dispersible. When ultrafine particles are used, if the cosmetic material is used, the ultraviolet ray shielding for transparency can be significantly improved and can be attached to its characteristics. Therefore, it is necessary to carry out the pulverization treatment for the purpose of loosening the agglomeration or for obtaining the fine particles. However, it is easy to cause contamination by containers, crushing balls, etc., and the particle size distribution of the particles is also applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). "Installation - (Please read the back Note: Please fill out this page again} 4^1. Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed -4 - 1250970 Λ7 B7 V. Invention Description (2) Widely distributed, causing inconvenience in use, limited granules, impossible to obtain Ultrafine particles, that is, in the liquid phase method, it is extremely difficult to obtain ultra-fine particles of highly white zinc oxide. As a method for obtaining zinc oxide powder, there is a gas phase method. In the gas phase method, the French law and the American law are the most Commonly known (Nippon Chemical Society, 1 1984 'P 8 3 7~8 4 2 ) is a zinc oxide vapor obtained from zinc oxide. The method of oxidation of zinc vapor containing reducing gas in the US law system is also It can obtain needle-shaped zinc oxide, but it is easy to contain lead, cadmium, etc., which causes problems in purity. In addition, it is easy to mix into agglomerated particles. The French legal system metal zinc vapor is oxidized to produce zinc oxide. Easier than American law High-purity zinc oxide is obtained, but this zinc oxide is agglomerated particles grown by needle crystals, and it is impossible to obtain a simple needle-like product. As a tetrapod or needle-shaped zinc oxide method For example, the temperature of the atmosphere in the heat-resistant container is set to a predetermined temperature as described in Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei. The method for producing zinc oxide whiskers. However, the zinc oxide obtained by the production method has a larger tetrapod particle of 5 to 80 // m. The method is a batch-type manufacturing method, and it is prone to the problem of unsuitable mass production. Moreover, the zinc vapor is added along the flow path in stages as described in the Unexamined-Japanese-Patent No. 4-34 9 1 18, and the needle shape is obtained. The method of zinc oxide is 'only'. The particles obtained by this method have a particle size of 1 to 2 0 V m. As a method for obtaining tetrapod zinc oxide, the paper is obtained. The scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Packing (please read the notes on the back and fill out this page) 1T--------- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed -5 - 1250970 Λ7 B7 V. Invention Description (3) (Please Read the precautions on the back and fill in this page. For example, after the zinc vapor is oxidized and burned as described in the special report No. 60 0-5 5 2 9 , the needle is cooled at a speed of 480 ° C / sec or more. For the method of zinc oxide, the size of the microparticles is also at most 0. 2~1 μ m. In order to make the particles more, the cooling rate will be considered to the limit. However, in this way, the oxidation of the zinc vapor is insufficient, and the unreacted zinc is mixed, and the obtained powder is grayish in color, and it is extremely difficult to obtain ultra-fine particles of highly white zinc oxide. Further, Japanese Laid-Open Patent Publication No. Hei 7- 1 1 8 1 3 3 discloses a method for producing ultrafine zinc oxide having a specific surface area of 70 to 1 10 m 2 /g as measured by the BET point method. Although it is used as an ultra-fine particle and a cosmetic material to enhance the transparency of the zinc oxide suspension, it is likely to cause a problem of lowering the ultraviolet shielding function. The object of the present invention is to provide a highly white zinc oxide microparticle useful as an additive for cosmetics, pigments, paints and the like, in particular, a particle shape of a tetrapod or a needle-like particle, and an ultrafine particle shape (including ultrafine particles also known as Microparticles.) Highly white zinc oxide. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives of the Ministry of the Invention The other object of the present invention is to provide a highly transparent and high-yield fine-grained high-white zinc oxide, and more industrially useful manufacturing methods. In particular, it is a highly white zinc oxide fine particle which is excellent in transparency and high in ultraviolet shielding when used as an additive for such an additive, and a method for producing the same. In order to solve the above problems, the inventors of the present invention have found that the specific particle size range in which the ultraviolet shielding function is high, that is, the specific surface area (JISR 1 6 2 6 ) measured by the BET-point method, can be obtained. Paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ΓΤΊ 1250970 Λ7 B7 V. Invention description (4) Please read the note on the back. Fill in this page) Average particle size is 1 5 nm~5 5 The nm-Hunt multi-purpose colorimeter shows that the L値 is more than 90% of the particulate-like highly white zinc oxide, and therefore it is necessary to confirm that ία(1) completely oxidizes the vapor in a short time, and (2) the vapor When the oxidation reaction is completed, the present invention is completed by avoiding the conflict between the formation of zinc oxide particles and melting the reaction immediately after the completion of the oxidation. That is, the present invention is characterized in that the converted average particle diameter of the specific surface area measured by the BET-point method is from 15 nm to 55 nm, and the L値 shown by the Hunter multipurpose colorimeter is 90. In the above, a highly white zinc oxide characterized by a tetrapod or a needle shape, and a zinc oxide vapor which is completely and rapidly oxidized by an oxidizing gas and suppresses particle growth, and agglomerates The method of manufacturing microparticles of white zinc oxide. The Ministry of Economic Affairs, the Huihui Property Bureau, and the Staff Cooperatives Co., Ltd. printed the particles of zinc oxide, which is characterized by more than 90% of the L値 shown in the Hunter Multipurpose Colorimeter, with a focus on oxidation in the reactor. The gas is rapidly oxidized by zinc oxide. For this reason, it has been found that the vaporization of the zinc by the gasifier is extremely effective in heating the gas by the heater provided in the subsequent step, and it is extremely effective to use the ceramic made of dense carbonized tantalum as the material of the heating device. After the gasification of the raw material gas, the introduction of the cerium carbide ceramic heater can reach a temperature at which the temperature of the raw material gas which is not reachable to the reactor is high, that is, it can effectively reach 950 ° C or higher, and The same material heater is also suitable for oxidizing gas, and can be heated to more than 90 〇 °C at the discharge port of the reactor. It has been found that the composition of the oxidizing gas can be rapidly oxidized and the heating of the raw material gas is extremely uniform. Based on the new discovery of the raw material gas and the oxidizing gas, it is found that the zinc oxide can be extremely rapidly and completely oxidized. Applicable to China National Standard (CNS) A4 specification (2[0 X 297 mm) 1250970 Α7 Β7 V. Inventive Note (5) Vapor, which can obtain high white fine particle zinc oxide. Moreover, it is obvious that the oxidation of zinc vapor can be so rapid compared to the prior art, even if the reaction portion is shortened, the color of the product is not caused, and the average particle diameter converted by the BET-point method is 15 nm to 5 nm. For 5 nm, the Hunter multi-purpose colorimeter shows that L値 is more than 90%. Preferably, the particle shape is tetrapod or needle-like fine-grained highly white zinc oxide. The above and other objects, effects, features and advantages of the present invention will be understood by reference to the appended claims. BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to the drawings. - Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative Printed Fig. 1 is a flow chart showing a composition example of a device suitable for producing the particulate high white zinc oxide of the present invention. The device consists of a raw material (zinc) feeder 1, a raw material (zinc) gasifier 2, an inert gas preheater 3, a raw material (zinc) gas heater 4, and a raw material gas heater discharge port 4A 'oxidizing gas The heater 5, the oxidizing gas heater discharge port 5 A 'reactor 6, the reactor outlet 6 A, the cooler 7 and the product collector 8 are comprised. After the raw material feeder 1, the metal zinc (?n) as a raw material is supplied to the raw material vaporizer 2. The form of zinc supplied to the material vaporizer 2 may also be powdery or linear. The inert gas can also be supplied to the raw material gasifier 2 simultaneously with the raw material metal zinc. This inactive gas system acts as a carrier gas for zinc vapor or as a sealing gas when introducing a raw material. As inactive gases such as gas, helium, argon, etc., but not limited to this, inactive gas paper size applies to the national standard (CNS) A4 specification (21〇χ 297 mm) 1250970 A7 5. Description of the Invention (6) It is preferable to preheat the material before it is introduced into the raw material gasifier 2. At this time, the inert gas is supplied to the raw material vaporizer 2 after being preheated by the inert gas preheater 3 at 5 〇 i i i 〇 〇 I. Leading merchant umbrella, 丨h /f paying heat billion benefits z Insulting gasifier 2 inactive gas concentration for the ratio of the total number of moles of Z n to the inert gas, the number of moles, ie Z n / ( Ζ η + inactive gas) is preferably in the range of 3 mol % to 7 Q mol %. This concentration is closely related to productivity and also affects the size of the zinc oxide particles obtained. Further, the zinc vapor of the Q inert gas, that is, the raw material gas system is introduced into the material gas heater 4 from the raw material vaporizer 2. It is also possible that the raw material gasifier 2 is integrated with the raw material gas heater 4. In the heating device in which the material gas heater 4 or the material gasifier 2 and the material gas heater 4 are integrated, the gas must be rapidly and sufficiently heated. The reason is that if the heating is insufficient, the heater will not be fully charged, and the zinc vapor in the reactor 6 is liquefied or solidified before the nozzle discharge port 4 or after the blow molding, thereby causing the system to be blocked. Unable to stabilize the operation, failed to obtain the zinc oxide of the expected quality. In addition, even if it is not blocked, the obtained zinc oxide is likely to contain gray of unreacted zinc. In order to obtain the ultrafine particles having a specific surface area converted to an average particle diameter of 15 nm to 5 5 nm, the temperature of the gas ejection port 4 A of the zinc vapor contained therein must be 950 ° C. The above is preferably 10 〇 0 ° C or higher. When the temperature is lower than 950 Torr, the oxidation is insufficient, and for the sufficient oxidation, the residence time is increased, so that the growth of the fine particles or the collision and fusion of the fine particles are liable to occur, and the desired fine particles cannot be obtained. In addition, the higher the temperature, the faster the oxidation reaction, and the complete oxidation can be achieved, so the 'eventy' is installed--- (please read the note on the back and fill out this page). · Department of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed Private Paper The scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -9 1250970 Λ7 B7 V. Inventive Note (7) Good properties and dispersibility. For full heating, glass and ceramic heaters can be used. In particular, the user of the tantalum carbide ceramic heater is preferred. The reason is that the tantalum carbide ceramic has a particularly high thermal conductivity in various materials with high temperature resistance, and the carbonized sand is black gray, and the absorption rate and the emissivity of the hot wire are high, so that the gas is easy to be gas. As described above, the higher the temperature of the gas discharge port 4A containing zinc vapor, the better, but the heat resistant material of the material gas heater 4 for realizing this high temperature is limited by heat resistance and thermal conductivity, and therefore, this is blown. The temperature of the plastic port is practically lower than 1 5 5 ° C. Of course, by improving the heat resistance of the heat transfer material of the material gas heater 4, it is possible to use a temperature higher than the above temperature. Moreover, by transferring the heat transfer medium to the heater 4, the heat transfer to the material gas can be more effectively enhanced. As a heat transfer medium, such as ceramics, glass, etc., especially made of quartz or tantalum carbide. Ceramics are preferred. The shape of the heat transfer medium is considered to be the heat transfer efficiency of the ring, sieve ring, honeycomb, Raschig ring, etc. As a heat transfer medium, the charge is not damaged by thermal expansion. The temperature of the heater is suitable for a large number of heaters. _ The Ministry of Economic Affairs, the Intellectual Property Bureau, the employee consumption cooperative, the temperature of the raw material gas in the discharge port of the raw material gas heater 4 is above 950 °C, preferably 1 〇. It is advisable to determine the heater diameter (inner diameter) and length above 〇〇t. If the ceramic made of tantalum carbide is used, the heater 4 can be made smaller than that of the aluminum tube, and it can be heated to 1 2 0 0 °C. The heated zinc vapor gas is introduced into the reactor 6. The oxidized gasification gas is heated by the gas gas heater 5 and then introduced into the reactor 6. The gasification gas is heated. 5 can be fully qualified -10- the paper size is suitable Chinese National Standard (CNS) A4 size (210 X 297 mm)
經濟部智慧財產局員工消費合作社印製 1250970 五、發明說明（8 ) 加熱之結構並未受限，惟，一般以具有與原料氣體加熱器 4相同結構者宜。 氧化性氣體其於氣化性氣體加熱器5噴出口 5 A中之 溫度務必爲9 〇 〇 °C以上。更佳者爲1 〇 〇 〇 t以上者。 其理由係當低於9 0 0 °C時，接觸時氧化性氣體使原料氣 體呈冷卻，進而造成原料鋅蒸氣之液化或固化。做爲原料 氣體者依所含鋅蒸氣之氣體溫度提昇氧化性氣體溫度者宜 氧化性氣體之使用量爲鋅蒸氣所需氧化理論量之 1 · 2倍〜150倍者’較佳者爲50倍〜1〇〇倍者。 做爲氧化性氣體組成者其氧務必爲1 〇體積％〜1 〇 〇體 積％者，水蒸氣爲〇體積％〜9 0體積％者，且，氧與水 蒸氣之和爲1 0體積％〜1 0 0體積％者。添加水蒸氣之 理由係藉由添加水蒸氣於氧化性氣體後則明顯出現提前氧 化之效果。 當原料氣體與氧化性氣體分別爲上述溫度域時，無論 同軸平行流、交叉流、斜交流等任何吹塑形態均呈快速氧 化，而，噴出口 4 A，5 A則以同軸平行流噴嘴者宜。用 軸平行流噴嘴以雙重管及三重管使用之。吹塑後由通過反 應器6之氣體流量與反應器6之容積所計算之反應部滯留 時間換算成標準狀態後，使呈〇 · 1秒以下，較佳者爲 0 . 0 5秒以下之反應器6之大小’決定原料氣體及氧化 性氣體之吹塑流速。 反應器6之形狀無特定’惟’圓柱狀可抑制污垢附著 (請先閱讀背面之注意事氣再填寫本頁)Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives 1250970 V. INSTRUCTIONS (8) The structure of heating is not limited, but it is generally preferred to have the same structure as the material gas heater 4. The temperature of the oxidizing gas in the discharge port 5 A of the gasifying gas heater 5 must be 9 〇 〇 ° C or more. The better one is 1 〇 〇 〇 t or more. The reason is that when it is lower than 9000 °C, the oxidizing gas causes the raw material gas to cool upon contact, thereby causing liquefaction or solidification of the raw material zinc vapor. As a raw material gas, according to the temperature of the gas containing zinc vapor, the temperature of the oxidizing gas should be increased. The amount of oxidizing gas used is 1 - 2 times to 150 times the amount of oxidation required for zinc vapor. ~1〇〇 times. As the oxidizing gas component, the oxygen must be 1 〇 vol% to 1 〇〇 vol%, the water vapor is 〇 vol%% to 9.0 vol%, and the sum of oxygen and water vapor is 10 vol%~ 1 0 0% by volume. The reason for adding water vapor is that the effect of pre-oxidation is apparent after the addition of water vapor to the oxidizing gas. When the material gas and the oxidizing gas are respectively in the above temperature range, any blow molding forms such as coaxial parallel flow, cross flow, oblique AC, etc. are rapidly oxidized, and the discharge ports 4 A, 5 A are coaxial parallel flow nozzles. should. Parallel flow nozzles are used in double tubes and triple tubes. After the blow molding, the reaction time of the reaction portion calculated from the gas flow rate of the reactor 6 and the volume of the reactor 6 is converted into a standard state, and then the reaction is performed for 1 second or less, preferably 0.50 seconds or less. The size of the device 6 determines the blowing flow rate of the material gas and the oxidizing gas. The shape of the reactor 6 is not specific 'only' cylindrical shape can inhibit the adhesion of dirt (please read the back of the note first and then fill out this page)
本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -Π - 1250970 A7 B7 五、發明說明（9 ) -1 --- (請先閱讀背面之注意事項再填寫本頁) 於內部等爲較理想者。反應器6之材質針對其鋅蒸氣氧化 反應時之耐熱性、鋅考慮其耐蝕性等後再進行選擇。使用 附帶外套式冷卻於不銹鋼製圓柱管者其成本面，維持管理 上均較爲理想者。 經濟部智慧財產局員工消費合作社印製 此鋅蒸氣之氧化反應雖於高溫反應器6內進行，惟， 控制滯留時間後爲抑制微粒子之凝聚成長及/或衝突，於 所定位置務必使反應氣體混合物進行急冷。具體而言，採 取反應器6之出口 6 A隨後導入冷卻用氣體等之適於此目 的之方法者。冷卻用氣體係採用空氣、氮等者，反應器6 之出口 6A隨後之平均氣體溫度以1 〇 〇°C〜4 5 0°C吹 塑冷卻氣體。4 5 0 °C以下係指於反應器6所生成之氧化 鋅微粒子藉由溫度未出現凝聚成長之溫度者謂之。此溫度 愈低、急速冷卻愈良好，惟，需要大量冷卻用氣體及爲防 止氣體中之水份結露之目的，仍以上述溫度域者宜。如此 取得之氧化鋅於袋濾器等之製品收集器8中被收集之。另 外，氧化鋅Z換算平均粒徑可改變吹塑氣體溫度，反應器 滯留時間進行控制之。吹塑氣體溫度愈高，滯留時間愈短 、平均粒徑則愈小。 藉由取決以上製造條件及裝置構成後可取得以B E T 一點法所測定之比表面積所換算平均粒徑爲1 5 n m〜 5 5 n m者，享特多用途比色計所示L値爲9 0以上，較 佳者其粒子形狀爲四腳狀或針狀之微粒子狀高度白色氧化 鋅者。 -12- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1250970 A7 B7 五、發明說明（〗〇 ) 實施例 (請先閱讀背面之注意事項再填寫本頁) 以貫施例及比較例進行本發明之說明，惟，本發明並 非僅限於此等實施例者。 實施例1 使金屬鋅以2 k g/h r ，同時使加熱9 〇 〇°c之氮 氣體以8 Nm3/h r供入原料氣化器中。使由氣化器釋出 所含鋅蒸氣之氣體導入密度3 · 1 g/cm3，S l C純度 9 9 · 8%之密緻質碳化矽陶瓷製加熱器中。此加熱器爲 外熱式者，被塡充與加熱器相同材質之碳化矽陶瓷塊者。 此加熱器中氣體滯留時間爲7秒（氣體於標準狀態下算出 )。該取得之氣體溫度於反應器噴出口爲1〇〇 〇°C者。 另外，使水蒸氣5體積％，氧9 5體積％之氧化性氣體計 2 5 N m 3 / h I*於外熱式加熱器進行加熱。加熱器爲密度 •經濟部智慧財產局員工消費合作社印製 3 · 1 g / c m 3，S 1 C純度9 9 · 8 %之密緻質碳化矽 陶瓷製者。此仍被塡充與原料氣體加熱器相同材質之碳化 矽製陶瓷塊者。藉此所加熱之氣體溫度於反應器之噴出口 爲1 0 3 0 °C者。兩氣體之噴出形態爲同軸平行流者。反 應器中平均滯留時間爲0 . 0 2秒，反應器出口隨後吹塑 室溫空氣，氣體溫度做成3 0 0 °C以下。之後，袋濾器中 所收集之氧化鋅其L値9 6藉由一點法求取之B E T比表 面積所換算平均粒徑爲含2 4 n m針狀氧化鋅之四腳狀高 度白色氧化鋅超微粒子者。 -13- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1250970 A7 ___B7______ 五、發明說明（11 ) 實施例2 (請先閱讀背面之注意事項再填寫本頁) 使金屬鋅以2 k g / h r ，同時使加熱9 〇 〇 °C之氮 氣體以8 N m 3 / h r供入原料氣化器。由氣化器釋出所含 鋅蒸氣氣體導入密度3 · lg/cm3，S 1 C純度 9 9 . 8 %之密緻質碳化矽陶瓷製加熱器中。此加熱器爲 外熱式者，被塡充與加熱器相同材質之碳化矽陶瓷塊。此 加熱器中氣體之滯留時間爲7秒（氣體於標準狀態算出） 。此取得之氣體溫度於反應器噴出口爲1 〇 0 〇°C者。另 外，使水蒸氣5體積％ ’氧9 5體積％之氧化性氣體計 2 5 Nm3/h r於外熱式加熱器進行加熱。加熱器爲密度 3 . 1 g / c m 3，S i C純度9 9 · 8 %之密緻質碳化矽 陶瓷製者。此仍與原料加熱器相同材質之碳化矽製陶瓷塊 被塡充。藉此，所加熱之氣體溫度於反應器噴出口爲 1 0 3 0 °C者。兩氣體之噴出形態爲同軸平行流者。反應 經濟部智慧財產局員工消費合作社印製 器中平均滯留時間爲〇 · 〇 〇 8秒者，反應器出口隨後吹 塑室溫空氣，使氣體溫度爲3 0 0 °C以下。此後，於袋濾 器中被收集之氧化鋅其L値9 5藉由一點法所求取B E T 比表面積所換算平均粒徑爲含1 7 nm之針狀氧化鋅之四 腳狀高度白色氧化鋅超微粒子者。 實施例3 使金屬鋅以5 k g / h r ，同時使加熱9 0 0 °C之氮 氣體以14Nm3/hr ，供入原料氣化器。由氣化器釋出 含鋅蒸氣之氣體導入密度3 · 1 g / c m 3 ’ S i C純度9 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -14 - 1250970 A7 B7 五、發明說明（12 ) (請先閱讀背面之注意事項再填寫本頁) 9 . 8 %之粗、緻質碳化政陶瓷製之加熱器中。此加熱器爲 外熱式者’其中被塡入與加熱器相同材質之碳化砂陶瓷塊 。此加熱器中氣體滯留時間爲5秒（氣體於標準狀態算出 )。此所取得之氣體溫度於反應器噴出口爲9 6 0 者。 另外，使水蒸氣4體積％ ’氧9 6體積％之氧化性氣體計 3 3 N m 3 / h r於外熱式加熱器進行加熱。加熱器爲密度 3 · 1 g / c m ’ S i C純度9 9 · 8 %之密緻質碳化石夕 陶瓷製者。其中被塡充與加熱器相同材質之碳化矽陶瓷塊 。藉此，所加熱氣體之溫度於反應器噴出口爲9 8 0 t者 。兩氣體噴出形態爲同軸平行流者。反應器中平均滯留時 間0 · 0 2秒者，反應器出口隨後吹塑室溫空氣，使氣體 溫度爲3 0 0 °C以下者。此後，於袋濾器中被收集之氧化 鋅L値9 4藉由一點法求取之B E T比表面積所換算平均 粒徑爲含4 0 n m之針狀氧化鋅之四腳狀高度白色氧化鋅 超微粒子者。 比較例1 經濟部智慧財產局員工消費合作社印製 使金屬鋅以2kg/hr ，同時使加熱900°C之氮 氣體以8 N m 3 / h r供入原料氣化器。由氣化器釋出之氣 體立刻於反應器噴出，噴出口之氣體溫度爲8 0 0°C者。 另外，氧化體2 5 N m 3 / h r於外熱式加熱器進行加熱。 加熱器爲石英製者，其中被塡充石英塊。被加熱之氣體溫 度於反應器噴出口爲9 9 0 r者。兩氣體之噴出形態爲同 軸平行流者。反應器中平均滯留時間爲3秒者，反應器出 -15- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1250970 Λ7 B7 五、發明說明（13 ) (請先閱讀背面之注意事項再填寫本頁) 口隨後吹塑室溫空氣，氣體溫度使做成3 0 0 °C以下者。 此後，於袋濾器中被收集之氧化鋅其L値9 5藉由一點法 求取B E T比表面積所換算平均粒徑爲1 3 5 nm之粒狀 氧化鋅者。 比較例2 使金屬鋅以2 k g / h r ，同時使加熱9 0 0 t：之氮 氣體以8Nm3/h r供入原料氣化器。由氣化器釋出之氣 體於反應器噴出，噴出口氣體之溫度爲8 0 0°C者。另外 ，氧氣體2 5 Nm3/h I*於外熱式加熱器進行加熱。加熱 器密度爲石英製者，其中被塡充石英塊。被加熱氣體之溫 度於反應器噴出口爲9 9 0 °C者。兩氣體噴出形態爲同軸 平行流者。反應器中平均滯留時間爲2 . 1秒，反應器出口 隨後吹塑室溫空氣，氣體溫度使做成3 0 0 °C以下者。此 後，於袋濾器中被收集之氧化鋅L値8 7藉由一點法求取 B E T比表面積所換算平均粒徑爲9 0 n m之粒狀氧化鋅 者。 經濟部智慧財產局員工消費合作社印製 比較例3 使金屬鋅以5 k g / h r ，同時使加熱9 0 0 °C之氮 氣體以1 4 N m 3 / h r供入原料氣化器。於氣化器取得之 氣體於反應器噴出，噴出口氣體之溫度爲7 5 Ot者。另 外，氧氣體3 3 N m 3 / h r於外熱式加熱器進行加熱。加 熱器中被塡充石英塊。藉此被加熱氣體之溫度於反應器噴 -10- 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） 1250970 Λ7 B7 五、發明說明（14 ) (請先閱讀背面之注意事項再填寫本頁) 出口爲9 8 0 °C者。兩氣體之噴出形態爲同軸平行流者。 反應器中平均滯留時間爲1 . 8秒者，反應器出口隨後吹 入室溫空氣，氣體溫度使做成3 〇 〇。(：以下者。此後，於 袋濾器中被收集之氧化鋅其L値8 5藉由一點法求取 B E T比表面積所換算平均粒徑爲6 5 nm之棒狀氧化鋅 者。 ， 〔產業上可利用性〕 本發明之氧化鋅係未經過粉碎等步驟之高純度微粒子 者。由於平均粒徑小，對於水系溶媒，樹脂等其分散性極 爲良好，極易作成均質混合體之氧化鋅者。用於化粧材料 等使用時，使用感極爲良好。且，白色度高，因此，化粧 品、樹脂等，與其他物質進行懸浮、混煉時易於調整色調 。另外，本發明可提供該微粒子狀高度白色氧化鋅於工業 量產水準下，可連續性，製造安定品質之製造方法者，其 實用價値極高。 經濟部智慧財產局員工消費合作社印製 本發明未跳脫其本質特徴亦可於其他特定實施形態下 進行之。因此，本實施形態爲任何點之示例者，無特別限 定，本發明範圍之上述說明更代表添附請求範圍者，亦即 ，含於申請範圍之均等範圍所有變更均含於本發明者。 〔圖面之簡單說明〕 圖1係代表適用於製造本發明微粒子狀高度白色氧化 辞之裝置組成例所不之流程圖。 -17- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) - Π - 1250970 A7 B7 V. Invention description (9 ) -1 --- (Please read the note on the back and fill out this page) It is ideal for the interior. The material of the reactor 6 is selected in consideration of the heat resistance during the zinc vapor oxidation reaction, the corrosion resistance of zinc, and the like. The use of jacket-type cooling in stainless steel cylindrical tubes is cost-effective and is ideal for maintenance management. The oxidation reaction of the zinc vapor printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs is carried out in the high temperature reactor 6. However, after controlling the residence time, it is necessary to suppress the aggregation growth and/or collision of the fine particles, and the reaction gas mixture must be made at a predetermined position. Quenching. Specifically, the outlet 6 A of the reactor 6 is taken, and then a method suitable for the purpose of the cooling gas or the like is introduced. The cooling gas system uses air, nitrogen, etc., and the outlet gas 6A of the reactor 6 is followed by an average gas temperature of 1 〇 〇 ° C to 4500 ° C to blow the cooling gas. 4 50 ° C or lower means that the zinc oxide fine particles generated in the reactor 6 are said to have a temperature at which the temperature does not agglomerate and grow. The lower the temperature, the better the rapid cooling, but the need for a large amount of cooling gas and the purpose of preventing condensation in the gas is still in the above temperature range. The zinc oxide thus obtained is collected in a product collector 8 such as a bag filter. In addition, the average particle size of zinc oxide Z can be controlled by changing the temperature of the blowing gas and the residence time of the reactor. The higher the temperature of the blowing gas, the shorter the residence time and the smaller the average particle size. Depending on the above manufacturing conditions and device configuration, the average particle size measured by the specific surface area measured by the BET method can be obtained from 15 nm to 55 nm, and the multi-purpose colorimeter shows L値 as 90. As described above, it is preferred that the particle shape is a tetradentate or needle-like fine particle-like highly white zinc oxide. -12- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1250970 A7 B7 V. Invention description (〗 〖) Example (please read the note on the back and fill in this page) The examples and comparative examples are illustrative of the invention, but the invention is not limited to the examples. Example 1 A metal zinc was supplied at 2 k g/h r while a nitrogen gas heated at 9 m 〇 °c was supplied to the raw material gasifier at 8 Nm 3 /h. The gas for releasing the zinc vapor contained in the gasifier is introduced into a heat-density tantalum carbide ceramic heater having a density of 3 · 1 g/cm 3 and a purity of 9 9 · 8%. This heater is an external heat type, and is filled with a tantalum ceramic block of the same material as the heater. The gas residence time in this heater was 7 seconds (the gas was calculated under standard conditions). The obtained gas temperature is 1 〇〇 ° C at the reactor discharge port. Further, an oxidizing gas of 5 vol% of water vapor and 9.5 vol% of oxygen was heated in an external heat heater. Heater for density • Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, printed 3 · 1 g / c m 3, S 1 C purity 9 9 · 8 % dense tantalum carbide ceramic manufacturer. This is still a carbonized tantalum ceramic block of the same material as the raw material gas heater. The temperature of the gas heated thereby is 1030 ° C at the discharge port of the reactor. The two gas discharge forms are coaxial parallel flow. The average residence time in the reactor was 0.02 seconds, and the reactor outlet was subsequently blown at room temperature air, and the gas temperature was made below 300 °C. Thereafter, the zinc oxide collected in the bag filter has an average particle diameter converted from a BET specific surface area obtained by a one-point method to a four-foot-shaped highly white zinc oxide ultrafine particle containing 24 μm of acicular zinc oxide. . -13- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1250970 A7 ___B7______ V. Description of invention (11) Example 2 (Please read the note on the back and fill out this page) The zinc was fed at 2 kg / hr while the nitrogen gas heated at 9 ° C was supplied to the feed gasifier at 8 N m 3 /hr. The zinc vapor gas contained in the gasifier is introduced into a ceramic heater having a density of 3 · lg/cm 3 and a purity of 9 9 . 8 % in a dense tantalum carbide ceramic. This heater is an external heat type and is filled with a silicon carbide ceramic block of the same material as the heater. The residence time of the gas in this heater is 7 seconds (the gas is calculated in the standard state). The gas temperature obtained is 1 〇 0 〇 °C at the reactor discharge port. Further, an oxidizing gas meter of 5 vol% of water and 9.5 vol% of oxygen was heated to an external heat heater. The heater is made of a dense tantalum carbide of a density of 3.1 g / c m 3 and a purity of 9 9 · 8 % of the ceramic. The carbonized tantalum ceramic block of the same material as the raw material heater is filled. Thereby, the temperature of the heated gas is 1 0 30 ° C at the reactor discharge port. The two gas discharge forms are coaxial parallel flow. Response The average residence time in the printers of the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs is 〇 · 〇 〇 8 seconds. The reactor outlet is then blown with room temperature air to make the gas temperature below 300 °C. Thereafter, the zinc oxide collected in the bag filter is obtained by a one-step method to obtain a BET specific surface area, and the average particle diameter is a four-foot-like high white zinc oxide super-containing zinc oxide containing 17 nm. Microparticles. Example 3 A metal zinc was supplied at 5 k g / h r while a nitrogen gas heated at 90 ° C was supplied to the raw material gasifier at 14 Nm 3 /hr. The gas introduced by the gasifier releases zinc-containing vapor at a density of 3 · 1 g / cm 3 ' S i C purity 9 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -14 - 1250970 A7 B7 V. INSTRUCTIONS (12) (Please read the notes on the back and fill out this page) 9. 8 % of the thick, quality carbonized ceramic ceramic heater. This heater is an externally heated type of carbonized sand ceramic block in which the same material as the heater is inserted. The gas residence time in this heater was 5 seconds (the gas was calculated in the standard state). The gas temperature obtained was 960 at the reactor discharge port. Further, an oxidizing gas meter 3 3 N m 3 / h r of 4% by volume of water vapor and 6% by volume of oxygen was heated by the external heat heater. The heater is a dense carbon carbide ceramic manufacturer having a density of 3 · 1 g / c m ' S i C purity of 9 9 · 8 %. Among them, the tantalum ceramic block is filled with the same material as the heater. Thereby, the temperature of the heated gas is 880 t at the reactor discharge port. The two gas ejection modes are coaxial parallel flow. If the average residence time in the reactor is 0 · 0 2 seconds, the reactor outlet is then blown with room temperature air so that the gas temperature is below 300 °C. Thereafter, the zinc oxide L値9 4 collected in the bag filter has a BET specific surface area obtained by one-point method and the average particle diameter is a four-legged high-white zinc oxide ultrafine particle containing 40 mm of acicular zinc oxide. By. Comparative Example 1 Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives, the metal zinc was supplied to the raw material gasifier at 2 kg/hr while the nitrogen gas heated at 900 °C was supplied at 8 N m 3 / h r . The gas released from the gasifier is immediately ejected from the reactor, and the gas temperature at the discharge port is 80 °C. Further, the oxidant 2 5 N m 3 / h r is heated by an external heat heater. The heater is made of quartz, which is filled with quartz blocks. The temperature of the heated gas was 909 r at the reactor discharge port. The discharge pattern of the two gases is parallel flow in the same axis. The average residence time in the reactor is 3 seconds, and the reactor is -15-. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1250970 Λ7 B7 V. Invention Description (13) (Read first Note on the back side of this page.) The mouth is then blown with room temperature air, and the gas temperature is made below 300 °C. Thereafter, the zinc oxide collected in the bag filter was subjected to a one-step method to obtain a granular zinc oxide having an average particle diameter of 135 nm converted from a specific surface area of B E T . Comparative Example 2 The metal zinc was supplied at 2 k g / h r while the nitrogen gas heated at 9000 t was supplied to the raw material gasifier at 8 Nm 3 /h. The gas released by the gasifier is ejected in the reactor, and the temperature of the outlet gas is 80 °C. Further, the oxygen gas 2 5 Nm3/h I* is heated by the external heat heater. The heater density is quartz, which is filled with quartz blocks. The temperature of the heated gas was 190 ° C at the reactor discharge port. The two gas ejection modes are coaxial parallel flow. The average residence time in the reactor was 2.1 seconds, and the reactor outlet was subsequently blown with room temperature air, and the gas temperature was made to be below 300 °C. Thereafter, the zinc oxide L 値 8 7 collected in the bag filter was obtained by one-step method to obtain a granular zinc oxide having an average particle diameter of 90 nm as a specific surface area of B E T . Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives. Comparative Example 3 The metal zinc was supplied at 5 k g / h r while the nitrogen gas heated at 90 ° C was supplied to the raw material gasifier at 1 4 N m 3 / h r . The gas obtained in the gasifier is ejected in the reactor, and the temperature of the outlet gas is 75 Torr. Further, the oxygen gas 3 3 N m 3 / h r is heated by the external heat heater. The heater is filled with quartz blocks. The temperature of the heated gas is applied to the reactor. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 x 297 mm). 1250970 Λ7 B7 5. Inventive Note (14) (Please read the back of the note first. Please fill out this page again. The exit is 9 80 °C. The two gas discharge forms are coaxial parallel flow. When the average residence time in the reactor was 1.8 seconds, the reactor outlet was then blown into room temperature air, and the gas temperature was made 3 〇. (The following is the case. Thereafter, the zinc oxide collected in the bag filter is obtained by a single method to obtain a rod-shaped zinc oxide having an average particle diameter of 65 nm converted by a BET specific surface area. Availability The zinc oxide of the present invention is a high-purity fine particle which has not been subjected to a step such as pulverization, etc. Since the average particle diameter is small, the dispersibility of the resin such as a water-based solvent is extremely excellent, and it is easy to form a zinc oxide of a homogeneous mixture. When it is used for a cosmetic material or the like, the feeling of use is extremely good, and the whiteness is high. Therefore, it is easy to adjust the color tone when suspending and kneading with other substances such as cosmetics, resins, etc. Further, the present invention can provide the microparticle-like high white color. Zinc oxide is a manufacturing method with stable quality and stable quality under the industrial production level. Its practical price is extremely high. The Ministry of Economic Affairs, the Intellectual Property Bureau, the employee consumption cooperative, printed the invention, and the nature of the invention is not In the embodiment, the present embodiment is not limited to the examples, and the above description of the scope of the present invention is more representative. Included in the scope of the application, all changes are included in the scope of the application. [Simplified description of the drawings] Fig. 1 represents a composition example of a device suitable for producing the highly granular white oxide of the present invention. Flowchart -17- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm)