1291603 九、發明說明： 【發明所屬之技術領域】 本發明係有關一種製備高分子樹脂粉體的方法，特別關於一種用於靜 電員像的反私和關於一種以新的凝聚程序(⑺pr〇cess)製造及控制 石反粉外觀、粒徑與其粒徑分佈的方法，其步驟至少包括：形成一有機相；形 成一水溶液相’其中所含之抗凝聚劑的添加量在卜加财％;後再以 600一2000_轉速’將水溶液相加入有機相混合均勻後，形成穩定分散之高 _ 分子膠體微粒水溶液，同時高分子膠體微粒中的有機溶劑將被水溶液相提 取導致微粒SHb，而挪體微粒固化的_亦_併進行微減聚合併；並 藉由水>谷液可快速過濾清洗並乾燥析出之特性，快速取得凝聚後之樹脂膠 體之顆粒，因此得以取得外觀、粒徑及其粒徑分佈受到控制之碳粉顆粒。 【先前技術】 先前技術大體上分為以下幾種： # A.傳統粉碎法製造碳粉是將高分子樹脂載體(bin㈣與各種添加劑，例 如色料、電荷控棚、離型鮮，以熱壓滾輪或擠出機將其熔融混練，然 後’將混練後冷卻之樹脂固體粉碎成粉體： 此傳、洗先天上具有不 > 特定缺點：例如賴的樹脂材料必須具有 脆性才能進行粉碎，為了翻此目的可_齡子量_七低分子量樹 脂本身對於靜電顯像上卻又具有數種缺點如： a. 低分子量樹脂在粉碎成碳粉或顯像_，傾㈣成片狀齡(flakes); b. 低分子量樹断製之碳料生雜垢，在靜·像舰份中的載 1291603 體顆粒(carrier particle)易蓋滿渣垢而失效； c·低分子量樹脂的熔融黏彈性不足，易發生載體樹脂黏覆於列印設備之 熱壓滾輪上，造成熱印偏移(hot-offset); d·低分子量樹脂的熱物性(如玻璃轉移溫度)調控較困難； 此外’傳統粉碎製程製備碳粉的通病如： a·粉碎製程所得之碳粉粒徑分佈寬廣，導致適用之碳粉粒徑產率降低， 同時增生產成本； b·碳粉粒徑外觀粗糙、不規則，造成列印品質不佳； c·粕碎過私因粒控控制不易，常產生太多微小徑之碳粉，而太小的碳粉 微粒易累積在列印設備中的顯像劑卡匣内，不利顯像劑壽命； 上述製造方法在業界產生不少困擾，無法有效提升相關產業的進步， 因此其後業界持續產生不㈤的方法，其巾主要以溶錢聚法為主，不過仍 有不少缺點： B·溶液凝聚技術係為提供一種克服先前技藝之溶融混練及粉碎程序缺 點的碳粉製造方法，其優點如下： &藉由使麟綠可以得_子形狀均-、輪徑分佈且無微粉粒之破 粉； 可以使用具靭性無法粉碎之樹脂，材料性質調控較佳，應用範圍較廣·， C•對於無法使用熱溶混練祕分解之碳粉添加劑，凝聚法亦可以使用； 基於上述理由，凝聚程序製備的碳粉較傳統粉碎法所生產的碳粉，具 有更夕的優點Μ傳統的凝聚程序是將高分子液分散於含有抗凝聚劑之連 1291603 縯相溶液中形成高分子膠體微粒分散液；藉由抗凝㈣高分子膠體微 粒間的凝聚合併赌，_控躺好賴之祕大从粒徑分佈， :。矛、门刀子膠體中的溶劑，形成固態高分子顆粒，再進行清洗、過濾 乾燥後τ以得到較傳統粉碎法更小且更窄之碳粉粒徑及粒徑分佈。 目前傳統凝聚法製造碳粉的程序中，形成高分子液的綠有三種形式： 、第種疋使用液轉體，在分散凝聚的過程同時聚合成高分子顆粒； 、、國專利第3卿153 5虎、第4816366號、第59687〇5號、第6458502號 及第6596453號所揭示，· 但以此法的仍有重大缺點，因其必紐祕殊單體及相對應之起始反 應d以進彳了〶分子财聚合反應或乳化聚合反映；所以適㈣高分子材料 受到很大親制：此法目前僅適驗壓克力_苯乙烯共聚合齡統，其他高 分子則需使轉殊單體；且聚合反縣受到碳粉其他添加獅干擾，不易 控制面分子聚合程度·，而聚合程度影響具毒性之高分子單體前的多寡， 這成產品t全上的顧慮及增加後處理困難度，亦讓業界頗感困擾。 第-種南分子液疋使用炼融態高分子，糊高溫將高分子樹脂液化， 再進行分散凝聚；如美國專利第56〇9979號、第6287742號、第6531255 號及第6582867號所揭示； 此法的主要缺點在於⑥融點之高分子概操作困難且耗能；對於融點 高於100°C之樹脂，無法使用水為加熱分散媒，導致後處理困難，相對也產 生環保處理成本；此外’對於不耐熱之碳粉添加劑，亦無法使用，造成應 用上的限制； 1291603 第三種高分子液則是使用溶劑將高分子液化得到，如美國專利第 4833060 號、第 4835084 號、第 5049469 號、5283149 號、第 5298355 號、 第 5968702 號、第 6156473 號、第 6294595 號、第 6403274 號、第 6482562 號及第6682866號所揭示； 此法的優點在於可使用的高分子材料較其它兩種方法多，且較不受製 程限制（不殘留單體及不需高溫操作）；不過，其缺點易頗多： 其一是在於為了控制碳粉粒徑大小及其粒徑分佈，需藉助 • 6000_20000rPm之高轉速均質攪拌設備，以形成膠體微粒進行凝聚合併； 其二是高分子液中的溶劑，在形成樹脂膠體顆粒後需藉由蒸發去除； 其中蒸發不能過速，因此，系統需長時間處於緩慢穩定的加熱攪拌狀態下 固化樹脂’極為耗時，且耗能；是為產能提升之重大瓶頸； 其三是在加熱攪拌的狀況下，極易導致分散穩定性下降；進而引發高 分子膠體獅再次發生凝聚合併，造絲終練及其分佈過大；品質因而 不易4控，無法有效精確提升碳粉品質，造成運用上產品易因每批碳粉品 ® 質差異’而產生機組故障率升高； 因此，為了解決第三種以溶劑配製之高分子液，在加熱移除溶劑時可 能引發的分散穩定問題，美國專利第558〇692號揭示，在高分子顆粒分散 液中以溶劑萃取(solvent extracti〇n)的方式，加入第二種溶劑萃取高分子顆粒 中的有機溶劑；此法可以在不加熱的方式將高分子顆粒中的溶劑移除，但 此法因#再加入第二種溶劑，此新加入的溶劑亦可能導致分散液不穩定； 此外’為了將高分子驗巾的溶鮮取妹，所需加人的萃取溶劑量可能 1291603 極大，導致製程所產生的廢溶劑過高， 大難題； 對生產環境不利，將形成環保的重 • 口此‘合上述凝聚法製造碳粉之先前技藝的分析得知，以第三種方 ^製備高分子液触，因為此法在材觸擇及安錄上無顯紐制，較具 肌爭性，但該方法尚須克服幾項缺點： -、疋如何降低職高分子膠職減需的高轉速顧餅力，以減 輕設備負荷與能源消耗； / -、疋如何提高移除高分子液巾的溶撇率，同時又不影響高分子膠 體的分散穩定性，以加速製程操作； 三、是如何可以更精確控制碳粉形成之粒徑，以因應不同的產品需求； 因為’如果無法_練足夠小且分散敎的高分子賴絲，則微粒進 行凝聚合併後陳徑及絲徑分佈，將無法達咖_目標；此外，微粒 中的办劑右未即時移除，則未固化之高好齡在清洗過濾的程序中，將 再二人凝聚合併，造成另一生產上的重大瓶頸； 由於碳粉的外觀、粒徑大小及其粒徑分佈，對於雷射印表機的列印品 質有顯著的影響’尤其是對灰階及全彩品f要求極高的影像列印；特別是 碳粉的外觀會影響碳_擦電帶電量、粉黯動性、清雜、堆積密度及 均勻性等，·外型越_的碳粉(如傳統碳粉），其表面縣力大，故其擦電性 及清除性佳’但是健流祕、堆前度及均勾性顺而外貌越均一， 粒徑分佈越窄的碳粉顆粒’其擦電帶電量越均勻，碳粉轉移率越高；同時， 其碳粉成像堆積密度舰，均勻性騎，但其清雑及擦電性較差：因此， 1291603. 適度的调控碳粉外貌，乃是碳粉製程上的重點，可以達到各種性質均在最 佳狀態之碳粉；粒徑不同的碳粉，在印表機碳粉卡匣作動的過程中將獲得 不同的摩擦帶電性；此差異將導致小粒徑碳粉表面帶電量過高而不易顯 像，造成列印成像時碳粉轉移不足；此外，不均的碳粉帶電量易導致碳粉 定著位置的偏差，產生列印毛邊；粒徑不均及外觀不規則的碳粉，其顯像 堆疊的碳粉層較鬆散，需較厚的碳粉層覆蓋著色，碳粉虛耗較多，較不經 濟，而粒徑均一的碳粉，其成像堆積效率、均勻度及色濃度皆較佳，所需 __像碳粉堆疊厚度亦較薄；較薄且均勻的碳麵像層，可以使得影像透 光性較佳，質感接近平版印刷，過厚的碳粉顯像層會導致影像表面粗糙， 同時易使得列印紙張捲曲；此外，較薄的碳粉顯像層，有助於提升印表機 在熱壓定著時的效率，可以降低能量消耗及加快列印速度。 簡言之，在傳_凝聚製財，無法有效生成穩定分散的高分子膠體 、、、致使用上述一種方法製造光電顯像碳粉時受到無法控制碳粉品質 _ 的_ ;均質性高品f的光賴像碳粉需要新的方法，以有效提升凝聚程 序的製程可雜’以及提供較佳的碳粉外觀、祕及其粒徑分佈的可調控 性。 【發明内容】 重 本發明之目的即為提供—種喊的凝聚方法以製造光像礙粉，其 a點在於改善製程巾必賴高速麟設備才能有效生成敎分散的高分子 膠體溶液的缺點，以及可快速歸高分子齡情麻不料分散穩定性 的方法 10 1291603* 本發明之另一目的為提供一種光電顯像設備，例如雷射印表機、影印 機、傳真機及多功能事務機等，其包括本發明之光電顯像碳粉。 本發明之又一目的為提供一種可調控碳粉外觀、粒徑及其粒徑分佈的 方法，藉由調控有機相與水溶液相間的相容性，可以控制高分子相分離形 成膠體微粒及其膠凝固化的速度，再配合抗凝聚劑的分散穩定能力，可以 有效控制碳粉顆粒外觀、粒徑及其粒徑分佈。 為了達到上述目的，本發明之一種用於製備及控制光電顯像設備用碳 粉外觀、粒徑的方法，其步驟至少包括： (1) 形成一有機相，其中組成包括高分子樹脂、可溶解高分子樹脂但與 水互溶或部分互溶之有機溶劑、色料、以及可聊性添蚊其它添加劑； (2) 形成一水溶液相，其組成包括水、抗凝聚劑、以及可選擇性添加之 其它促進劑或辅助劑，其中抗凝聚劑的添加量在卜驗％，以及； (3) 以6GG 2GGGrpm轉速，將水溶液相加入有機相混合均勻後，形成穩 定分散之高分子雜錄水溶液，同時高分子雜餘巾的有機溶劑將被 水溶液相提取導致微粒固化，而在膠體微粒固化的同時亦—併進行微粒凝 聚合併； 過滤清洗並乾燥析出之樹脂顆粒，可得外觀、粒徑及其粒徑分佈受到 控制之碳粉顆粒。 八中毛月社要特點之-為調整有機溶麵水的溶解度 ，以增進其對 Κ合液相_日及械；添加劑的相紐與高分子膠義浮液之分散穩定 性；特點之二是藉由水的作用， 置換有機相中的有機溶劑，以增加有機 1291603 相中的樹脂過飽和度並降低其溶解度，進而引發樹脂自有機相中相分離析 出凝聚成膠體微粒；其三是藉由調整適當的樹脂固含量可以有效調控碳粉 粒徑及其粒徑分佈；有機溶劑的相容性可藉由不同極性及溶解度之溶劑調 配得到’採用有機溶劑調控相容性並改變高分子樹脂分子量及其極性因而 得以更易操控凝聚製程，以達到調控碳粉外觀、粒徑及其粒徑分佈之目的。 【實施方式】 9 如圖一所示，本發明所設之一種用於製備及控制光電顯像設備用碳粉 外觀、粒徑的方法，其步驟至少包括： (1) 形成一有機相，其中組成包括高分子樹脂、可溶解高分子樹脂但與 水互溶或部分互溶之有機溶劑、色料、以及可選擇性添加之其它添加劑—例 如離型劑Mease agent)、電荷控制劑(charge c〇ntr〇1 agent，cCA)等； (2) 形成-水溶液相，其組成包括水、抗凝聚劑、以及可選擇性添加之 其匕促進劑或辅助劑-例如離子性或非離子性界面活性劑或凝集劑 _ (coagulant)等，其中抗凝聚劑的添加量在l-2〇wt%，以及； (3) 以6GG-2__轉速，將水溶液相加人有機相混合均勻後，形成穩 定分散之局分子膠體微粒水溶液，同時高分子膠體微粒中的有機溶劑將被 水驗城鱗賴粒，而挪㈣化_日轉—獅行微粒凝 聚合併； 過滤清洗並乾燥析出之樹脂顆粒，可得外觀、粒徑及其粒握分佈受到 控制之碳粉顆粒。 12 1291603 本發月中’主要疋藉由有機相裡的溶劑會溶於水相，造成高分子 t^^^(phase separation)^^^^^^(sol.gel c〇ll〇id)»i, 生成穩找散之高分子賴·水溶液；由於相分_序為自發產生，因 此生成高分子賴微_林需_高舰賴剪切力，社賴之有機相 ，齊L、尺互’谷或为互溶，因此無須藉由加熱或額外添加萃取溶劑即可將 门刀子顆粒中备劑移除，此外，由於凝聚造粒及溶劑去除可同時進行，因 此所需的製程時間大幅縮短，有利於大量生產。 本發明之新的凝聚法製程中，所謂的色料包含顏料及染料，適用於本 發明之色料必須涵色飽和度佳、耐候性強、與樹脂相容性佳且易分散等 特性；常見的顏料包括黑色顏料(碳黑及氧化鐵等）、藍色顏料(CL pigment Blue7，62，66，15:1，15:3 及 152 等）、紅色顏料(C.LPigmentRed2, 6, 48:1，57:1，8卜 122，146，184 及 221 等)及黃色顏料(C I pigment1291603 IX. Description of the Invention: [Technical Field] The present invention relates to a method for preparing a polymer resin powder, and more particularly to an anti-private method for an electrostatic image and a new coagulation procedure ((7) pr〇cess a method for producing and controlling a stone anti-powder appearance, a particle size and a particle size distribution thereof, the method comprising the steps of: forming an organic phase; forming an aqueous solution phase, wherein the amount of the anti-agglomerating agent contained therein is increased by Then, the aqueous solution phase is added to the organic phase at 600-2000 rpm to uniformly form a stable dispersion of the high molecular colloidal particle aqueous solution, and the organic solvent in the polymer colloidal particles is extracted by the aqueous phase to cause the particulate SHb, and the body is moved. The particles are solidified and subjected to micro-reduction polymerization; and the water > trough liquid can be quickly filtered and washed to dry out the characteristics of the precipitate, and the particles of the resin colloid after the coagulation are quickly obtained, thereby obtaining the appearance, the particle size and the particles thereof. The particle size is controlled by the toner particles. [Prior Art] The prior art is generally classified into the following types: # A. The conventional pulverization method is to produce a carbon resin carrier (bin) and various additives such as a colorant, a charge-controlled shed, and a fresh-type, hot-pressed. The roller or the extruder melts and kneads it, and then 'pulverizes the resin solid after cooling and kneaded into a powder: the transfer and the wash have the same color.> Specific disadvantages: for example, the resin material of the base must be brittle to be pulverized, in order to For this purpose, _ age-quantity _ seven low molecular weight resin itself has several disadvantages for electrostatic imaging, such as: a. Low molecular weight resin is pulverized into toner or imaged _, tilted (four) into sheet-like age (flakes b. Low-molecular-weight tree-cut carbonaceous material, the carrier particle in the static image ship is easily covered with slag and fails; c. Low-molecular-weight resin has insufficient melt viscoelasticity It is easy to cause the carrier resin to adhere to the hot pressing roller of the printing device, resulting in hot-offset; d. The thermal properties of the low molecular weight resin (such as glass transition temperature) are difficult to control; Process preparation carbon The common problems are as follows: a· The particle size distribution of the carbon powder obtained by the pulverization process is wide, which results in the reduction of the applicable particle size of the carbon powder and the increase of the production cost; b· The appearance of the particle size of the carbon powder is rough and irregular, resulting in no print quality. Good; c· mashed by private particles control is not easy, often produces too many small diameter toner, and too small toner particles are easy to accumulate in the imaging device cartridge in the printing equipment, unfavorable imaging agent Lifespan; The above manufacturing methods have caused many problems in the industry, and it is unable to effectively improve the progress of related industries. Therefore, the industry continues to produce the method of (5). The towel is mainly based on the method of dissolving money, but there are still many shortcomings: B The solution coagulation technique is to provide a carbon powder manufacturing method which overcomes the disadvantages of the prior art melt-kneading and pulverization process, and has the following advantages: & by making the arbor green, the _ sub-shape is uniform, the wheel diameter distribution and no fine particles Breaking powder; can use resin with toughness and can not be pulverized, better control of material properties, wide application range, C•Coagulation method can also be used for toner additives that cannot be decomposed by hot melt mixing; For the above reasons, the carbon powder prepared by the coagulation process has a better advantage than the carbon powder produced by the conventional pulverization method. The conventional coagulation procedure is to disperse the polymer liquid in the 1291603 phase-effect solution containing the anti-agglomeration agent to form a high. Molecular colloidal particle dispersion; by anticoagulation (4) agglomeration between polymer colloidal particles and gambling, _ control lies better than the particle size distribution, : spear, solvent in the knife colloid, forming solid polymer particles Then, after washing, filtering and drying, τ is used to obtain a smaller and narrower carbon powder particle size and particle size distribution than the conventional pulverization method. At present, in the conventional coagulation method for producing carbon powder, there are three forms of green forming a polymer liquid. : The first type of liquid is transferred into a polymer granule at the same time in the process of dispersing and coagulating; 、,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, As revealed, there are still major shortcomings in this method. Because of its uniqueness and the corresponding initial reaction d, it is reflected in the molecular polymerization or emulsion polymerization; therefore, it is suitable for (four) polymer materials. Subject to Very large pro-system: This method is currently only suitable for acrylic _ styrene copolymerization age, other polymers need to make the transfer of monomer; and the polymerization anti-county is interfered by other lions added by the toner, it is difficult to control the surface molecule polymerization Degree, and the degree of polymerization affects the amount of toxic polymer monomers. This is a concern for the product and the difficulty of increasing post-processing. The first type of the southern molecular liquid sputum uses a smelt-state polymer, and the paste resin is liquefied at a high temperature, and then dispersed and agglomerated; as disclosed in U.S. Patent Nos. 5,690,979, 6,278,742, 6,531,255, and 6,582,867; The main disadvantage of this method is that the polymer of 6 melting points is difficult to operate and consumes energy; for resins with melting point higher than 100 °C, water cannot be used as heating dispersing medium, which leads to difficult post-processing and relatively environmentally friendly processing costs; In addition, 'the heat-resistant toner additive can not be used, resulting in application restrictions; 1291603 The third polymer liquid is obtained by liquefying the polymer using a solvent, such as U.S. Patent No. 4,833,060, No. 4,835,084, No. 5,049,469. No. 5283149, No. 5,298,355, No. 5,968,702, No. 6,156,473, No. 6,294,595, No. 6,403,274, No. 6,482,562, and No. 6,682,866; the advantage of this method is that the polymer materials that can be used are two There are many methods, and it is not limited by the process (no residual monomer and no high temperature operation); however, its shortcomings are quite easy: one is to control The size of the powder and its particle size distribution need to be homogenized by a high-speed mixing device of 6000~0000rPm to form colloidal particles for agglomeration; the second is the solvent in the polymer liquid, which needs to be removed by evaporation after forming the resin colloidal particles. The evaporation can not be too fast, therefore, the system needs to cure the resin under a slow and stable heating and stirring state for a long time, which is extremely time-consuming and energy-consuming; it is a major bottleneck for the production capacity improvement; the third is under the condition of heating and stirring. It is easy to cause the dispersion stability to decrease; in turn, the polymer colloid lion re-agglomerates and merges, the finalization of the silk and its distribution is too large; the quality is not easy to control, and the quality of the toner cannot be accurately and accurately improved, resulting in the use of the product. The difference in the quality of the toner product is caused by the increase in the unit failure rate. Therefore, in order to solve the third type of polymer liquid prepared by solvent, the dispersion stability problem may occur when the solvent is removed by heating. U.S. Patent No. 558〇692 It is revealed that in the polymer particle dispersion, solvent extraction (solvent extracti〇n) is added, and the second solvent is added to extract high. An organic solvent in the molecular particles; this method can remove the solvent in the polymer particles without heating, but this method adds a second solvent, and the newly added solvent may also cause the dispersion to be unstable; In addition, in order to take the dissolution of the polymer test towel, the amount of extraction solvent required may be extremely large, which may cause the waste solvent generated by the process to be too high, and the big problem is unfavorable to the production environment. The analysis of the previous techniques of manufacturing the toner by the above-mentioned coacervation method shows that the third method is used to prepare the polymer liquid touch, because this method has no obvious system in the material selection and installation, and it is more competitive. Sex, but the method still has to overcome several shortcomings: - How to reduce the high-speed power of the polymer glue job to reduce equipment load and energy consumption; / -, how to improve the removal of polymer liquid The dissolution rate of the towel does not affect the dispersion stability of the polymer colloid to accelerate the process operation. Third, how can the particle size of the toner formation be more precisely controlled to meet different product requirements; because 'if not _ If the polymer lysine is small enough and disperse, the particles will be aggregated and the diameter of the wire and the diameter of the wire will not reach the coffee _ target; in addition, the right agent in the particle is not immediately removed, then the uncured high age In the process of cleaning and filtering, the two people are condensed and combined, causing another major bottleneck in production. Due to the appearance, particle size and particle size distribution of the toner, the printing quality of the laser printer is remarkable. The impact of 'especially on the grayscale and full-color f-demanding image printing; especially the appearance of toner will affect the carbon_electricity, powder turbulence, cleanliness, bulk density and uniformity, etc. The appearance of the more _ toner (such as traditional toner), its surface is strong, so its electric wiping and removal is good, but the health of the secret, the pre-stack and the uniformity of the hook and the appearance is more uniform, The narrower the particle size distribution, the more uniform the electric charge of the toner particles, and the higher the toner transfer rate. At the same time, the toner image is stacked and the density is uniform, but its cleaning and wiping performance are poor: , 1291603. Moderate regulation of the appearance of toner is on the carbon powder process Point, can achieve a variety of properties in the best state of the carbon powder; carbon powder with different particle size, will get different frictional charging in the process of the printer toner cartridge operation; this difference will lead to small particle size carbon The surface charge of the powder is too high to be easily imaged, resulting in insufficient toner transfer during printing. In addition, the uneven charge of the toner tends to cause deviation of the fixed position of the toner, resulting in printing burrs; uneven particle size and The irregular appearance of the toner, the carbon layer of the image stack is loose, the thicker carbon layer is required to cover the coloring, the carbon powder is more expensive, less economical, and the toner with uniform particle size is imaged and accumulated. Efficiency, uniformity and color density are better, and the required thickness of the toner stack is thinner. The thinner and uniform carbon image layer can make the image transmissive better, the texture is close to lithography, and the thickness is too thick. The toner imaging layer will cause the image surface to be rough and easily cause the printed paper to curl; in addition, the thinner toner imaging layer will help improve the efficiency of the printer during hot pressing and reduce energy. Consume and speed up printing. In short, in the transmission of condensed wealth, it is impossible to effectively produce a stable and dispersed polymer colloid, and the use of the above method to produce photo-image carbon powder is uncontrollable toner quality _ _; high homogeneity f The light depends on the toner to require a new method to effectively improve the process of the agglomeration process and to provide better toner appearance, secret and its particle size distribution controllability. SUMMARY OF THE INVENTION The object of the present invention is to provide a method of agglomeration to create a photo-impacting powder. The point of the invention is to improve the disadvantages of the high-speed processing equipment to effectively produce the dispersed polymer colloidal solution. And a method capable of quickly returning to the polymer age without distracting stability 10 1291603* Another object of the present invention is to provide an optoelectronic developing device such as a laser printer, a photocopier, a facsimile machine, a multifunction machine, etc. It includes the photoimageable carbon powder of the present invention. Another object of the present invention is to provide a method for regulating the appearance, particle size and particle size distribution of a carbon powder. By controlling the compatibility between the organic phase and the aqueous phase, the phase separation of the polymer can be controlled to form colloidal particles and glue thereof. The speed of solidification, combined with the dispersion stability of the anti-coagulant, can effectively control the appearance, particle size and particle size distribution of the carbon particles. In order to achieve the above object, a method for preparing and controlling the appearance and particle size of a carbon powder for an optoelectronic developing device comprises the steps of: (1) forming an organic phase in which the composition comprises a polymer resin and is soluble. An organic solvent, a water-miscible or partially miscible organic solvent, a colorant, and other additives to the mosquito; (2) forming an aqueous phase comprising water, an anti-agglomerating agent, and optionally other additives An accelerator or an auxiliary agent, wherein the anti-agglomerating agent is added in an amount of 5%, and; (3) adding the aqueous phase to the organic phase at 6 GG 2GGG rpm to form a stable dispersion of the polymer mixed aqueous solution, and at the same time high The organic solvent of the molecular waste towel will be extracted by the aqueous phase to cause the particles to solidify, and the colloidal particles will be solidified together with the particle agglomeration; the filter is washed and the precipitated resin particles are dried to obtain the appearance, the particle size and the particle size. Distribution of controlled toner particles. The characteristics of the Eighth China Maoyue Society - to adjust the solubility of organic soluble surface water, in order to enhance its dispersion of the liquid phase _ day and machinery; additives and the dispersion stability of polymer gelatin float; By replacing the organic solvent in the organic phase by the action of water, the supersaturation of the resin in the organic 1291603 phase is increased and the solubility is lowered, thereby causing the phase separation of the resin from the organic phase to form colloidal particles; the third is by Adjusting the proper resin solid content can effectively control the particle size and particle size distribution of the carbon powder; the compatibility of the organic solvent can be adjusted by solvent with different polarity and solubility to 'control the compatibility with the organic solvent and change the molecular weight of the polymer resin. Its polarity makes it easier to manipulate the coacervation process to achieve the purpose of regulating the appearance, particle size and particle size distribution of the toner. [Embodiment] 9 As shown in FIG. 1, a method for preparing and controlling the appearance and particle size of a carbon powder for an optoelectronic imaging device according to the present invention comprises the steps of: (1) forming an organic phase, wherein The composition comprises a polymer resin, an organic solvent which can dissolve the polymer resin but is mutually miscible or partially miscible with water, a colorant, and other additives which can be selectively added - such as a Mease agent, and a charge control agent (charge c〇ntr) 〇1 agent, cCA), etc.; (2) forming an aqueous phase comprising a composition comprising water, an anti-agglomerating agent, and optionally an oxime promoter or adjuvant such as an ionic or nonionic surfactant or Coagulant, etc., wherein the anti-agglomerating agent is added in an amount of 1-2% by weight, and; (3) the aqueous solution is added to the human organic phase at 6 GG-2 _ rpm to form a stable dispersion. The colloidal colloidal particles in the aqueous solution, while the organic solvent in the colloidal particles of the polymer will be granulated by the water, and the (four) _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ,grain The diameter of the particle and its particle grip are controlled by the toner particles. 12 1291603 In the middle of the month, the main solvent is dissolved in the water phase by the solvent in the organic phase, causing the polymer to be phased ^^^^^^(sol.gel c〇ll〇id)» i, the formation of a stable liquid polymer Lai · aqueous solution; because the phase separation _ sequence is spontaneous, so the formation of polymer Lai micro _ Lin needs _ Gao Shipai shear force, social organic, phase L, rule mutual 'Valley is miscible, so the preparation of the knives in the knives can be removed without heating or additional extraction solvent. In addition, since the coagulation granulation and solvent removal can be carried out simultaneously, the required processing time is greatly shortened. Conducive to mass production. In the novel coacervation process of the present invention, the so-called colorant contains pigments and dyes, and the colorant suitable for use in the present invention has good color saturation, strong weather resistance, good compatibility with resin, and easy dispersion; Pigments include black pigments (carbon black and iron oxide, etc.), blue pigments (CL pigment Blue7, 62, 66, 15:1, 15:3 and 152, etc.), red pigments (C.LPigmentRed2, 6, 48:1 , 57:1, 8 Bu 122, 146, 184 and 221, etc.) and yellow pigment (CI pigment
Yellow 12，17’ 74，83，97，136，174 及 185 等)等；適合的染料包 括分散性染料及油溶性染料等與連續相水溶液不相溶之色料；所使用的色 料相對於樹脂重量，約佔其Μ5 Μ%，較佳的色料比例在2_1〇斯％，所 使用的不溶性色料其粒徑在〇〇l_l#m，較佳的粒徑分佈在 適用於本發明之離型劑必須具有較樹脂低的熔點，較低的熔融態黏 度、凝固速率較樹脂快並能包覆於碳粉表層、熱定著時可促進礙粉與熱壓 滾筒離型等特性；常見的離型劑如矽油(siliconoil)、石蠟(paraffln)、聚乙晞 蠟(polyethylene wax)、聚丙烯躐(polypropylene wax)、硬脂酸鹽(stearate salt)、聚g旨蠘(p〇lyester wax)、長碳鏈醇(18-50個碳鏈）、長碳鏈酸(18-50個 13 1291603 石反鏈）、動植物躐及其它人工合成壤等；所添加的離型劑相對於樹脂重量， 約佔其0-20 wt%，較佳的離型劑含量約為〇_1〇斯％，離型劑的操作溫度 視靜電顯像設備的需求而定，一般較佳的操作溫度在6〇_13(rc。 適用於本發明之電荷控制劑必須具有特定的離子電荷以保持碳粉表面 帶電性及使摩擦帶電量能維持在適當範圍；常見的電荷控制劑包括四級胺 鹽(quaternary ammonium salts)、水揚酸錯合物(saliCyiic acid c〇mplex)、偶氮 金屬錯合物(azo metal-complex)、芳香族之羧酸基錯合物(aromatic carb〇xylic • comPlex)及上述化合物之衍生物等；電荷控制劑添加量相對於樹脂重量，其 所佔比例約為0-20 wt% ’較佳的添加比例在〇-1〇 wt%。 適用於本發明之高分子樹脂必須能與其它碳粉添加劑有好的相容性、 摩擦帶電性、熱壓定著性及足夠的機械強度等特性；適用的樹脂包括聚醯 胺樹脂(polyamides)、醯胺共聚合樹脂(cop〇lyamide)、聚酯樹脂(polyesters)、 壓克力樹脂(acrylic resins)、聚苯乙烯樹脂(polystyrenes)、環氧樹脂(ep0Xy resins)、苯乙烯-壓克力共聚合樹脂(styrene-acryiate c〇p〇iymers)、聚烯烴 春 （P〇ly〇lefins)、聚碳酸酯樹脂（polycarbonate)、聚丙醯胺樹脂 (polyacrylamide)、乙烯-醋酸乙烯共聚合樹脂（ethyiene_vinyl aceate copolymer)、聚氨基甲酸酯樹脂(polyurethane)、聚醋酸乙烯樹脂 ， aceate)、聚乙烯縮丁醇樹脂⑦以㈣㈣butyral)及上述樹脂之共聚物或其混合 物等’樹脂的含量佔碳粉重量的50-95 wt%，較佳的樹脂含量為70-90 wt% ; 此外，高分子樹脂的極性及分子量大小會影響凝聚製程操作，高極性與低 分子量之樹脂，其對極性有機溶劑之溶解度相對較高；因此，對凝聚製程 1291603 中的膠體析出快慢有決定性的影響；過快的樹脂析出速率，易導致谬體凝 聚結塊及產生凝膠現象；此外，樹脂的極性及分子量大小亦會影響樹脂本 身的電氣特性、以及熱壓固著時熔融快慢、黏著性、機械強度等； 適用於本發明之有機溶劑必須能溶解樹脂、與水溶液相互溶或部分互 溶、對碳粉添加劑具有相容性、易回收及分離等特性；適用的有機溶劑包 括醇類的甲醇(methano卜MeOH)、乙醇(ethanol)、正丙醇(n_pr〇pan〇i)、異 丙醇(iso-propanol，IPA)、正丁醇(n_butanol，BuOH)、異丁醇(iso_butan〇i)、 叔丁醇(tert-butanol)、丙三醇(glycerol)、乙二醇(ethylene glycol);酯類的乙 酸乙酯(ethyl acetate，EAc)、乙酸甲酯(methyl acetate)、甲酸乙酯(ethyl formate)，酮類的丙酮(acet〇ne)、甲乙酮(methyl eththyl ketone，MEK)、甲 基異 丁基酮(methyl isobutyl ketone，MIBK)、環己酮(Cyd〇hexanone);醚類 的四氫吱喃(tetrahydrofliran，THF)、二噁烧(dioxane);烷類的己烷(hexane)、 環己烷(cyclohexane);芳香類的甲苯(benzene)、二甲苯(xylene);碳氯化合 物類二氣甲烷(dichloromethane)、二氯乙烷(dichloroethane)、氯仿(chloroform) 及上述溶劑之混合溶劑等；適用於本發明之有機溶劑對樹脂及添加劑的相 容性越大越好，其對水溶液相的溶解度則需在每克水中可溶〇 〇lg有機溶劑 以上’杈佳的溶解度在每克水可溶〇 〇4 — lg有機溶劑；而完全互溶之有機 溶劑，可用於調整樹脂相分離析出速度；此外，所使用的有機相中的樹脂 固含里約為10-90 wt% ’較佳的樹脂固含量在2040^^%。 本法特點之一為調整有機溶劑對水的溶解度，以改變其對水溶液相、 樹脂及礙粉添加細相雑與高分子膠雜雜之分散敎性；對樹脂及 15 1291603 碳粉添加劑的相容性不佳或對水溶解度太大之有機溶劑，其樹脂析出速率 相對較快；而過快的樹脂析出速率，易導致高分子樹脂與添加劑間在相分 離時無法同頻出，產生未著色或包覆不完全讀脂難以及凝聚合併 時析出結塊；減的’對水溶解度太差的有機溶劑，無法有效被水溶液相 萃取以致樹脂無法固化，易導致再次凝聚而產生大粒徑顆粒；運用適當的 有機溶劑溶職，可啸制-讀崎妓目化辭，孰驢及降低粒 徑及窄化粒徑分佈；有機溶劑的相容性可藉由不同極性及溶解度之溶劑調 Φ 配得到，採用有機溶劑調控相容性較改變高分子樹脂分子量及其極性更易 操控凝聚製程，以達到調控碳粉外觀、粒徑及其粒徑分佈；此外，有機溶 劑中的樹脂固含量會影響到相分離時樹脂過飽和濃度，進而影響到樹脂析 出成核的多养，以致咼樹脂固含量的系統成核速率快(過飽和濃度高），易導 致膠凝現象造成樹脂結塊，生成大粒徑寬分佈之碳粉顆粒；但過低的樹脂 固含量，將使得一次微粒不易凝聚合併(粒子濃度太低），且所得產率不符經 濟效率，因此，適當的樹脂固含量可以有效調控碳粉粒徑及其粒徑分佈。 ^ 適用於本發明之抗凝集劑須具備有穩定分散析出之樹脂膠體粒子的能 力，以抑制樹脂膠體微粒過度凝聚造成結塊；同時必須能與水互溶或形成 均勻的水溶液分散相，常見的抗凝集劑包括高分子型穩定劑的聚乙烯醇(p〇 . lyvinyl alcoho卜 PVA)、聚乙烯基砒硌烷酮(polyvinylpyrrolidone，PVP)、 甲基纖維素(methyl cellulose)、乙基纖維素(ethyl cellulose)、羥丙基纖維素(h yroxypropyl cellulose)、羥乙基甲基纖維素(hyroxyethyl methyl cellulose)、 羥丙基乙基纖維素(hyroxypropyl ethyl cellulose)、羧甲基纖維素(carboxyme 1291603 thyl cellulose，CMC)及其鹽類(例如 CMC_Na)、羥乙基纖維素(hyr〇xyethyl cellulose ’ HEC)、聚丙烯酸鹽(p〇iyacryiic acid salt)、聚丙浠醯胺(polyacr ylic amide)、聚本乙稀石黃酸鹽(p〇iyStyrene suif〇nate)、明膠(geiatin)、阿拉伯 膠、1氧乙烯與聚氧丙烯共聚物咖17〇^故]^10116-卩(^(^卩1*(^化116(^(^ mer);無機超微粉體之穩定劑，如二氧化石夕粉體、氧化铭粉體、氧化鈦粉 體、碳酸两粉體及上述添加劑的混合物等；連續相溶液中，抗凝集劑所添 加之重量百分率為0.1-30 wt%，較佳的添加比例為1-20 wt%，值得注意的 是抗凝集劑的添加量與添加種類會依所使用的樹脂及有機溶劑系統的不同 而改變。 水溶液相中及吸附於碳粉微粒表面之抗凝聚劑，藉由溶液黏度、靜電 排斥及空間障礙等機能，可以有效抑制一次微粒過度凝聚合併形成大粒徑 寬分佈之碳粉顆粒；一般而言，抗凝聚劑濃度越高，所得之粒徑越小分佈 也較窄，但添加過多的抗凝聚劑可能導致高分子膠體微粒間不易合併成 長，以及造成後段清洗過濾程序不易處理；此外，抗凝聚劑有一定的飽和 吸附濃度，過量添加並無法有效提升其效能；因此，控制抗凝聚劑的濃度 可以得到適當凝聚合併之破粉顆粒，以獲得所需之碳粉粒徑及其粒徑分佈。 適用於本發明之促進劑必須具有降低樹脂有機相與水溶液相間的界面 張力，以促成膠體相穩定形成，常見的促進劑包括離子性界面活性的烷基 硫酸鹽（alkylsulfate)、烷基苯磺酸鹽（&11^181116)1^6)、烷基萘磺酸鹽 (alkylnaphthalenesulfonate)、脂肪酸鹽（fatty acid salt)、烷基磷酸鹽 (alkylphosphate)、烷基胺鹽(alkylaminoate);非離子性界面活性劑的烷基聚 17 Ϊ291603 氧乙烯驗（alkylpolyoxyethylene ether)、烧基紛聚氧乙浠醚(alkylpolyphenol ethoxylate)、烷基醇醯胺(alkylolamide)、山梨糖酵酐脂肪酸酯(Tween，Span) 等’促進劑的選擇隨系統而定，對於水分散於油中的系統，選擇親疏水性 平衡值（Hydrophile-lipophile Balance，HLB)在 3-6 的促進劑；對於油分 散在水中的系統則選擇HLB值在8_15之促進劑，水溶液相中，促進劑所 添加之重量百分率為〇-l〇wt°/。，較佳的添加量為〇-5加％，吸附於樹脂膠 體表面之促進劑，具有降低膠體成核之界面能量，以及穩定膠體微粒的特 性。此特性可以使得樹脂成核粒徑更小，分散更穩定，有助於生成所需次 微米尺度之一次樹脂膠體微粒，使得後續凝聚合併製程更易完成。 適用於本發明之辅助劑必須具有促進微粒間凝聚合併之能力，常見的 促進劑包括無機鹽，如氣化鈉、碳酸納、硫酸鈉、磷酸納、硝酸鈉及硫酸 鋁等；有機鹽類，如醋酸鈉及胺鹽；離子性高分子，如聚丙醯酸鈉及聚乙 酿胺鹽等；無機酸驗，如硫酸及氫氧化鈉等；適#_助劑添加濃度為 〇-20wt%，較佳的範圍為〇—1〇wt%，對於某些樹脂微粒易快速析出固化的系 統，需添加辅助_加速祕凝聚合併，以避免樹脂微粒固化後無法凝聚 合併的窘境。 本發明中所謂的水溶液相是指組成包括水、促進劑、抗凝集劑之水溶 液，水主要的作職於置換有機相中的有機溶劑，以增加有機相中的樹脂 過飽和度鱗低其溶誠，_引發樹脂自有目分離析出凝聚成膠 體微粒，g此’水溶油必須具備财機溶劑互溶或部分互溶，且與樹脂 不互溶的特性，為了有效去除樹脂液中的有機溶劑，但又需避免溶劑置換 18 1291603 速率太快導致樹脂凝膠化結塊，故水溶液相的添加量、添加速率及凝聚合 併時間必須加以控制，其範圍隨系統不同而不同，適當的水溶液相添加量 為有機相的0.5-10倍，較佳的添加量約在1-5倍；而水溶液相添加所費 的時間，牽涉到有機相樹脂過飽和濃度動態變化，而有機相過飽和濃度則 與树脂成核速率息息相關；所以，水溶液相添加費時過久(添加速率過慢) 了月b導致尚分子膠體微粒間合併成長不一，造成粒徑變大分佈變寬，以及 使得製程過於耗時，水溶液相添加過快則可能引發過多樹脂成核(nudei)， _ 造成膠凝㈣atln)現象進而導致樹脂結塊，適當的水溶液相添加所需時間在 〇-120min，較佳的時間為〇 5_6〇min，可以使碳粉粒徑及其粒徑分佈較佳； 至於適當的凝聚合併時間，可以得到碳粉粒徑及其粒徑分佈不再隨時間改 變之顆粒，適當的操作時間為1-24〇min，較佳的時間為，過短的 凝聚合併時間，一次微粒尚未凝聚合併至穩定狀態；因此粒徑及粒徑分佈 會隨時間變化，過長的凝聚合併時間，因為粒子不再凝聚合併，故浪費製 程時間。 ® 最後’以水清洗新的凝聚後的碳粉微粒，以去除微粒表面的促進劑、 抗凝集劑與殘留的溶劑；同時利用濾網將碳粉微粒由溶液中分離出來，再 藉由真空烘箱將碳粉微粒乾燥，乾燥的碳粉微粒可選擇性添加外添加劑， . 如電荷控制劑、抗結塊劑及流動促進劑等，以提升碳粉的其他特性，使其 符合光電顯像設備的需求。 本發明之新的凝聚法與傳統凝聚法之差別，主要在形成一次高分子膠 體微粒(primary colloidal particles of polymer)的機制，以及高分子顆粒中的 19 1291603 溶劑移除上有_不15]，賴凝聚法的―:欠高分子職齡形錢構，主 要起因於有機相巾的有機溶齡水·猶—定溶解度，導致有機相中高 分子濃度會逐漸高於其·和度，而魅相分離析出高分子雜微粒；此 私序為自發仃為，因此無須藉由高轉速之機械剪切力來達成，故優於傳統 凝聚法，根據先前技藝的揭示，傳統凝聚法需要6〇〇〇_2⑻⑻印瓜的高剪切 力攪拌設備，而新的凝聚法則只需要4〇〇_3〇〇〇rpm _拌設備即可，較佳 的攪拌速率範圍約在__2_啊。此外，在高分子膠體微粒分散與凝聚 口併的同時’向分子顆粒巾麟齡同步被移除至水溶液相中，不需藉由 力…、或額夕卜添力口萃取溶劑以移除南A子顆纟中之溶劑，既達到丨景多響製程 分散穩定性’且加速高分子顆粒中溶劑的去除效率，此特性顯著優於傳統 凝聚法；根據先前技藝_示，傳統凝聚法需要藉由加減發方式移除高 分子顆粒中溶劑，的加熱_需要8_施；而新的凝聚法則不需藉由 …、移除糾’整個製程只需即可，較佳的製程時間。 本發明之新峡聚法較傳麟聚法，在控制碳麵料觀、粒徑及其 粒控分佈的方法有顯著的不同，傳統凝聚法，採用抗凝聚劑以控制一次高 分子膠體微_躲合併，妙合_歧，聽狀粒社雜顆粒； 反之得到小粒徑碳粉顆粒；藉此達到控制碳粉顆粒外觀、粒徑及其粒徑分 佈。而新的凝聚法，除了可採用抗凝聚劑控制碳粉粒徑外，還可藉由控制 回刀子相分離形祕體微粒速率及其膠凝固化速率來_碳粉祕控制。 ^放粒均勻析出’所得之碳粉粒徑分佈窄；反之則粒捏分佈寬，膠體微 粒膠凝固化鱗快，所得之雜健小；反之細f大；上絲序再搭配 20 1291603 抗凝聚劑的使用可以更有效控制碳粉外觀、粒捏及其粒徑分佈，新的凝 聚法所製備的碳粉，其平均體積粒徑㈤約在4—1Q，平均數目粒徑⑽ 約在2-8卵，粒徑分佈(Dv/Dp)可達h 3町。此外，亦可控制石炭粉顆粒外 觀，由規則均一之球狀，調控改變至不規則非球狀顆粒。 以下藉由數個實施例以更進—步說明本發明之方法、特徵及優點，但 並非用於來關本發明之細，本發明之範圍應以所附之巾請專利範圍為 準： φ 實施例1 取約1000ml的容器，加入225.5g壓克力-苯乙烯樹脂P581(sekisui Chemical提供）、ll〇g甲乙酮(MEK)溶劑、22〇g乙酸乙酯(EAc)溶劑及％ Licowax S離型蠟(Clariant提供），加熱攪拌至完全溶解均勻後取出倒入分 散震盪瓶中，待其冷卻後加入13.5g PB-15:3青藍色顏料(色真顏料提供)及 4g E84 CCA(Orient Chemical提供)及300g直徑1mm的玻璃珠，封好震| 甑’以震盪機分散混合2 day後，取出塗料並濾除玻璃珠，得到以 為为政媒之總固含量約45 wt·%的青藍色有機相南分子液；其中樹脂濃度 為37.55wt%，離型蠟濃度為4.5wt%，顏料濃度為2.25wt%，CCA濃度為 0.7wt% ° • 在約500ml容器中，加入15g聚乙烯醇PVA(長春石化提供）、2gTween 20(Showa提供）及178g水，加熱攪拌至聚乙烯醇完全溶解均勻後，冷卻 至室溫得到水溶液相；其中聚乙烯醇濃度為7.5wt%，Tween 20濃度為 lwt% ； 21 1291603 取3〇g有機相高分子液倒入凝聚分散槽，於室溫下以12〇〇哪攪摔， 並等速加入水溶液相至凝聚分散槽中，使其混合均句；有機相之樹脂會隨 水溶液相的添加逐漸相分離析出，持續添加水溶液相至有機相中，直到其 變成為均勻分散的膠體水溶液後停止，此時水溶液相添加量約需6〇g，歷時 約50sec ;持續攪拌約10min，至高分子膠體微粒凝聚合併完成，再加入約 有機相添加量3倍之清水加速高分子顆粒膠凝固化。 將上述步驟所得之高分子顆粒分散液，以濾網過濾後，將所得之高分 ® 子顆粒以清水清洗數次，再以真空烘箱乾燥得到以新的凝聚法製備之碳粉 顆粒’其操作流程如圖 >-所示。 實施例2 配製本實施例之有機相與水溶液相之步驟，以及新的凝聚製程的步驟 和實施例1相同；主要不同處在於高分子液的樹脂改為壓克力樹脂 DM55(ROHM&HAAS提供）；其他不同處如有機相及水溶液相之配方請配 合參閱下表一及表二所示，相關的製程參數請參考表三所列數據。 表一、各實施例之有機相配方 貫施 t機相配方 例 高分子樹脂(wt%) 有機溶劑 色料(wt%) CCA(wt%) 離型鱲(wt%) 總固 X mi ，擁Π ，：E84 ] 含量 ^ 37.55 W&MM 45.0 2 DM55 IPA/BuOH PR-122 ——— — 28.5 4/1 1.5 0 0 30.0 % VEST雌LT171 甲醇征丁醇 ，'編|2 -·,< 寧—， 鐵纖:鑛毅孩纖鐵駿衫鐵鱗 學纖鐵纖錄錄鐵驛驗雜簿 / 7T 、、： < 19 2/1 20.0 4 P581/CPR100 MEK/EAc ΡΒ15 : 3 LicoWax S 42.5 3/4 2.5 0 5.0 ιΎο.ο 5 P581 MEK/EAc 歷5 : 3 ,:職 LicoWax S 37.55 、.:t、 ▼ Λ Ί. . "Λ 一 ϋ m 2*25 0J 八 Ί ' 145.0 22 1291603Yellow 12,17' 74,83,97,136,174 and 185, etc.); suitable dyes include disperse dyes and oil-soluble dyes and the like which are incompatible with the aqueous phase of the continuous phase; the colorants used are relative to The weight of the resin is about Μ5%, the preferred pigment ratio is 2_1 〇%, and the insoluble colorant used has a particle size of 〇〇l_l#m. The preferred particle size distribution is suitable for use in the present invention. The release agent must have a lower melting point than the resin. The lower melt viscosity and solidification rate are faster than the resin and can be coated on the surface layer of the carbon powder. When the heat is fixed, the characteristics of the powder and the hot press roll can be promoted; Release agents such as silicone oil, paraffin, polyethylene wax, polypropylene wax, stearate salt, p〇lyester wax ), long carbon chain alcohols (18-50 carbon chains), long carbon chain acids (18-50 13 1291603 stone reverse chains), animal and plant mites and other synthetic soils, etc.; added release agent relative to resin weight , about 0-20 wt%, the preferred release agent content is about 〇_1〇s%, the operating temperature of the release agent Depending on the requirements of the electrostatic imaging apparatus, a generally preferred operating temperature is 6 〇 13 (rc. The charge control agent suitable for use in the present invention must have a specific ionic charge to maintain the surface charge of the toner and to cause triboelectric charge. It can be maintained in an appropriate range; common charge control agents include quaternary ammonium salts, saliCyiic acid c〇mplex, azo metal-complex, and aromatics. a carboxylic acid-based complex (aromatic carb〇xylic • comPlex) and derivatives of the above compounds; the charge control agent is added in an amount of about 0-20 wt% relative to the weight of the resin. The ratio is 〇-1〇wt%. The polymer resin suitable for the present invention must have good compatibility with other toner additives, triboelectric chargeability, thermocompression setting and sufficient mechanical strength; Resins include polyamides, cop〇lyamides, polyesters, acrylic resins, polystyrenes, and epoxy resins (ep0Xy). Resins), benzene Styrene-acryiate c〇p〇iymers, P春ly〇lefins, polycarbonate, polyacrylamide, ethylene-vinyl acetate Ethylene-vinyl aceate copolymer, polyurethane, aceate, polyvinyl butyral resin 7 (4) (tetra) butyral) and copolymers of the above resins or mixtures thereof The content is 50-95 wt% of the weight of the toner, and the preferred resin content is 70-90 wt%; in addition, the polarity and molecular weight of the polymer resin affect the coagulation process operation, the high polarity and low molecular weight resin, The solubility of the polar organic solvent is relatively high; therefore, it has a decisive influence on the precipitation speed of the colloid in the coagulation process 1291603; too fast resin precipitation rate, easy to cause agglomeration and agglomeration of the carcass; in addition, the polarity of the resin And the molecular weight also affects the electrical properties of the resin itself, as well as the melting speed, adhesion, mechanical strength, etc. during hot pressing; The organic solvent must be capable of dissolving the resin, mutually soluble or partially miscible with the aqueous solution, compatibility with the toner additive, easy recovery and separation; suitable organic solvents include alcoholic methanol (methano MeOH), ethanol (ethanol) ), n-propanol (n_pr〇pan〇i), iso-propanol (IPA), n-butanol (BuOH), isobutanol (iso_butan〇i), tert-butanol (tert-butanol) , glycerol, ethylene glycol; ester ethyl acetate (EAc), methyl acetate, ethyl formate, ketone acetone Acet〇ne), methyl eththyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone (Cyd〇hexanone); ether tetrahydrofliran (THF), Dioxane; hexane, cyclohexane; aromatic benzene, xylene; chlorocarbon dichloromethane, dichloro Dichloroethane, chloroform, a mixed solvent of the above solvents, etc.; suitable for use in the present invention The greater the compatibility of the organic solvent with the resin and the additive, the better the solubility of the aqueous solution phase is required to be soluble in lg of organic solvent per gram of water. 'The solubility is better in each gram of water. 4 — lg The organic solvent; and the completely miscible organic solvent can be used to adjust the separation speed of the resin phase separation; in addition, the solid content of the resin used in the organic phase is about 10-90 wt% 'better resin solid content at 2040^^ %. One of the characteristics of this method is to adjust the solubility of the organic solvent in water to change the dispersion of the fine phase 雑 and the polymer glue in the aqueous phase, the resin and the powder; the phase of the resin and the 15 1291603 toner additive An organic solvent having poor or poor solubility in water has a relatively high rate of resin precipitation; and an excessively rapid rate of resin precipitation tends to cause the polymer resin and the additive to fail to phase out when phase separated, resulting in uncolored or The coating is not completely difficult to read and the agglomeration is precipitated when the agglomeration is combined; the organic solvent which is too poor in water solubility cannot be effectively extracted by the aqueous phase so that the resin cannot be solidified, which may lead to re-agglomeration and large particle size; Appropriate organic solvents can be used to smear-read the rhyme, read and reduce the particle size and narrow the particle size distribution; the compatibility of organic solvents can be obtained by adjusting the solvent of different polarities and solubility. The organic solvent is used to control the compatibility, and the molecular weight and polarity of the polymer resin are more easily manipulated to control the condensation process, so as to control the appearance, particle size and particle size distribution of the carbon powder; In addition, the solid content of the resin in the organic solvent will affect the supersaturation concentration of the resin during phase separation, which in turn affects the multi-culture of the resin nucleation, so that the nucleation rate of the solid content of the ruthenium resin is fast (high supersaturation concentration), which easily leads to glue. The condensation phenomenon causes the resin to agglomerate, and the carbon particles having a large particle size and a wide distribution are formed; however, the too low resin solid content causes the primary particles to be difficult to aggregate (the particle concentration is too low), and the yield is not economically efficient, therefore, The proper resin solid content can effectively regulate the particle size of the carbon powder and its particle size distribution. ^ The anti-aggregating agent suitable for the present invention is required to have the ability to stably disperse the precipitated resin colloidal particles to inhibit the agglomeration of the resin colloidal particles by excessive agglomeration; at the same time, it must be miscible with water or form a uniform aqueous dispersion phase, common Anti-agglomerating agents include polyvinyl alcohol (p〇. lyvinyl alcoho PVA), polyvinylpyrrolidone (PVP), methyl cellulose, ethyl cellulose. (ethyl cellulose), hydroxypropyl cellulose, hyroxyethyl methyl cellulose, hyroxypropyl ethyl cellulose, carboxymethyl cellulose (carboxyme 1291603 Thyl cellulose, CMC) and its salts (eg CMC_Na), hydroxyethyl cellulose (Hyr), polyethylation Ethyl sulphate (p〇iyStyrene suif〇nate), gelatin (geiatin), gum arabic, 1 oxyethylene and polyoxypropylene copolymer coffee 17〇^故]^10116-卩(^(^卩1* (^化116(^(^ mer); Stabilizer for ultrafine powder, such as dioxide dioxide powder, oxidized powder, titanium oxide powder, carbonic acid powder and a mixture of the above additives; in the continuous phase solution, the anti-aggregating agent is added The weight percentage is from 0.1 to 30% by weight, and the preferred addition ratio is from 1 to 20% by weight. It is worth noting that the amount of the anti-aggregating agent added and the kind to be added vary depending on the resin and the organic solvent system used. The anti-agglomerating agent in the aqueous phase and adsorbed on the surface of the carbon powder particles can effectively inhibit the excessive aggregation of the primary particles and form the carbon particles having a large particle size and wide distribution by the functions of solution viscosity, electrostatic repulsion and space barrier; The higher the concentration of the anti-agglomeration agent, the smaller the particle size obtained is, the smaller the distribution is, but the addition of excessive anti-agglomeration agent may cause the polymer colloidal particles to not easily merge and grow, and the post-cleaning filtration process is not easy to handle; The agent has a certain saturated adsorption concentration, and excessive addition can not effectively improve its efficiency; therefore, controlling the concentration of the anti-coagulant can be properly agglomerated and combined with the broken powder. Granules to obtain the desired particle size of the carbon powder and its particle size distribution. The accelerator suitable for use in the present invention must have an interfacial tension between the organic phase of the resin and the aqueous phase to promote stable formation of the colloidal phase. Common promoters include ions. Sexually interfacially active alkylsulfate, alkylbenzenesulfonate (&11^181116)1^6), alkylnaphthalenesulfonate, fatty acid salt, alkyl Alkyl polyphosphate, alkylaminoate; nonionic surfactant; alkyl polyoxyethylene ether, alkylpolyphenol ethoxylate, alkyl alcohol The choice of accelerators such as alkylolamide and sorbate fatty acid ester (Tween, Span) depends on the system. For systems with water dispersed in oil, choose Hydrophile-lipophile Balance (HLB). Promoter at 3-6; for the system in which the oil is dispersed in water, the accelerator with HLB value of 8-15 is selected. In the aqueous phase, the weight percentage of the accelerator added is 〇-l〇wt°/Preferably, the addition amount is 〇-5 plus %, and the accelerator adsorbed on the surface of the resin colloid has the characteristics of reducing the interfacial energy of the colloid nucleation and stabilizing the colloidal particles. This property can make the resin nucleation particle size smaller and the dispersion more stable, which helps to generate the primary resin colloidal particles of the submicron size required, which makes the subsequent coagulation and consolidation process easier to complete. The adjuvants suitable for use in the present invention must have the ability to promote agglomeration between particles. Common accelerators include inorganic salts such as sodium carbonate, sodium carbonate, sodium sulfate, sodium phosphate, sodium nitrate and aluminum sulfate; and organic salts, Such as sodium acetate and amine salts; ionic polymers, such as sodium polyacrylate and polyethylamine salts; inorganic acid tests, such as sulfuric acid and sodium hydroxide; suitable #_ adjuvant concentration is 〇-20wt%, The preferred range is 〇-1〇wt%. For some systems in which the resin particles are easily precipitated and solidified, it is necessary to add auxiliary _acceleration and secret condensation to avoid the cohesive environment after the resin particles are solidified. The so-called aqueous phase in the present invention refers to an aqueous solution comprising water, a promoter and an anti-aggregating agent, and the water mainly serves as an organic solvent in the organic phase to increase the supersaturation of the resin in the organic phase. Cheng, _Initiated resin separates and precipitates into colloidal particles, so the 'water-soluble oil must have the solvent of mutual solvent or partial miscibility, and is not miscible with the resin, in order to effectively remove the organic solvent in the resin liquid, but Need to avoid solvent replacement 18 1291603 The rate is too fast to cause gelation and agglomeration of the resin, so the addition amount, addition rate and coagulation time of the aqueous phase must be controlled, and the range varies with the system. The appropriate amount of the aqueous solution is organic. 0.5-10 times of the phase, the preferred addition amount is about 1-5 times; while the time required for the addition of the aqueous phase phase involves the dynamic change of the supersaturation concentration of the organic phase resin, and the supersaturation concentration of the organic phase is closely related to the nucleation rate of the resin. Therefore, the addition of the aqueous phase takes too long (the rate of addition is too slow), and the monthly b causes the colloidal particles to merge and grow. The diameter becomes larger and wider, and the process is too time consuming. If the aqueous phase is added too fast, it may cause excessive resin nucleation (nude), _ causing gelation (four) atln) and then causing resin agglomeration, and proper aqueous solution phase addition is required. The time is 〇-120min, and the preferred time is _5_6〇min, which can make the particle size and particle size distribution of the carbon powder better. As for the proper agglomeration time, the particle size and particle size distribution of the carbon powder can no longer be obtained. The particles change with time, the appropriate operation time is 1-24 〇 min, the preferred time is too short agglomeration combined time, the primary particles have not been agglomerated and merged into a stable state; therefore, the particle size and particle size distribution will change with time. Longer condensing and merging time, because the particles are no longer condensed and merged, so the process time is wasted. ® Finally 'cleans the new agglomerated toner particles with water to remove the promoter, anti-aggregating agent and residual solvent on the surface of the particles; at the same time, the filter particles are used to separate the toner particles from the solution and then by vacuum The oven dries the carbon particles, and the dried toner particles can be selectively added with external additives, such as charge control agents, anti-caking agents and flow promoters, to enhance other characteristics of the toner to meet the photoelectric imaging equipment. Demand. The difference between the new coacervation method of the present invention and the conventional coacervation method is mainly in the mechanism of forming primary colloidal particles of polymer, and the removal of 19 1291603 solvent in the polymer particles. Lai's condensed method - the owing of polymer-aged structure, mainly due to the organic solute water of the organic phase towel, the solubility of the organic phase, the concentration of the polymer in the organic phase will gradually be higher than its degree, and the charm Separation and precipitation of high-molecular particles; this private sequence is spontaneous, so it does not need to be achieved by high-speed mechanical shearing force, so it is superior to the traditional coagulation method. According to the prior art, the traditional coacervation method requires 6〇〇〇. _2 (8) (8) high shear mixing equipment for the melon, and the new coagulation method only needs 4 〇〇 _ 3 rpm _ mixing equipment, the preferred mixing rate range is about __2_ ah. In addition, while the polymer colloidal particles are dispersed and coagulated, the molecular particles are simultaneously removed into the aqueous phase, and the solvent is not removed by the force... or the extracting solvent to remove the south A. The solvent in the crucible not only achieves the dispersion stability of the smear process, but also accelerates the solvent removal efficiency in the polymer particles. This characteristic is significantly superior to the conventional coacervation method; according to the prior art, the conventional coacervation method needs to be added or subtracted. The method of removing the solvent in the polymer particles requires the application of the solvent, and the new coagulation method does not need to be removed by the process, and the process time is better. The new gorge method of the present invention is significantly different from the method for controlling the carbon fabric, the particle size and the particle-control distribution. The conventional coacervation method uses an anti-coagulant to control the primary polymer colloid. Merging, miscellaneous, ambiguous, and granules; instead, small particle size granules are obtained; thereby controlling the appearance, particle size and particle size distribution of the carbon particles. The new coacervation method, in addition to the use of anti-coagulant to control the particle size of the toner, can also be controlled by controlling the particle velocity of the knife-phase separation and the gelation rate of the gel. ^The granules are uniformly precipitated' The obtained carbon powder has a narrow particle size distribution; otherwise, the granules are widely distributed, the colloidal particles are solidified and the scales are fast, and the obtained hybrids are small; on the contrary, the fine f is large; the upper silk order is further matched with 20 1291603 The use of the agent can more effectively control the appearance of the toner, the granules and the particle size distribution. The carbon powder prepared by the new coacervation method has an average volume particle diameter (5) of about 4 to 1 Q, and an average number of particle diameters (10) of about 2 8 eggs, particle size distribution (Dv / Dp) up to h 3 town. In addition, it is also possible to control the appearance of the charcoal powder particles, which are controlled by a uniform spherical shape and changed to irregular non-spherical particles. The method, features and advantages of the present invention are described in more detail below by way of a few embodiments, but are not intended to be a limitation of the invention. The scope of the invention should be determined by the scope of the appended claims: φ Example 1 A container of about 1000 ml was taken, and 225.5 g of acrylic-styrene resin P581 (supplied by Sekisui Chemical), ll 〇g of methyl ethyl ketone (MEK) solvent, 22 〇g of ethyl acetate (EAc) solvent, and % Licowax S were added. Wax (provided by Clariant), heated and stirred until completely dissolved, then taken out into a dispersion shake flask, and after cooling, add 13.5g PB-15:3 cyan pigment (provided by color pigment) and 4g E84 CCA (Orient Chemical supplied) and 300g glass beads with a diameter of 1mm, sealed and shaken | 甑' Disperse and mix for 2 days with a shaker, remove the paint and filter out the glass beads to obtain a green color of about 45 wt·%. Blue organic phase south molecular liquid; wherein the resin concentration is 37.55 wt%, the release wax concentration is 4.5 wt%, the pigment concentration is 2.25 wt%, the CCA concentration is 0.7 wt% ° • 15 g polyethylene is added in a container of about 500 ml Alcohol PVA (provided by Changchun Petrochemical), 2g Tween 20 (provided by Showa) and 178g water, After hot stirring until the polyvinyl alcohol is completely dissolved and homogeneous, it is cooled to room temperature to obtain an aqueous phase; wherein the polyvinyl alcohol concentration is 7.5 wt%, and the Tween 20 concentration is 1 wt%; 21 1291603 3 g of the organic phase polymer liquid is poured into the coagulation Disperse the tank, stir it at room temperature at 12 Torr, and add the aqueous phase to the coagulation and dispersion tank at a constant rate to mix it; the resin of the organic phase will gradually separate and precipitate with the addition of the aqueous phase, and continue to be added. The aqueous phase is neutralized to the organic phase until it becomes a uniformly dispersed colloidal aqueous solution. At this time, the aqueous phase is added in an amount of about 6 〇g for about 50 sec; stirring is continued for about 10 minutes until the polymer colloidal particles are agglomerated and completed, and then added. About 3 times the amount of organic phase added clear water accelerates the solidification of the polymer particles. After the polymer particle dispersion obtained in the above step is filtered through a sieve, the obtained high score® sub-particles are washed several times with water, and then dried in a vacuum oven to obtain carbon powder particles prepared by a new coacervation method. The flow is shown in the figure >-. Example 2 The steps of preparing the organic phase and the aqueous phase of the present embodiment, and the steps of the new coagulation process are the same as those of the first embodiment; the main difference is that the resin of the polymer liquid is changed to the acrylic resin DM55 (ROHM & HAAS provides ); other different parts such as the organic phase and the aqueous phase of the formulation please refer to the following Table 1 and Table 2, the relevant process parameters, please refer to the data listed in Table 3. Table 1. Organic phase formulation of each example. Example of polymer phase resin (wt%) Organic solvent colorant (wt%) CCA (wt%) Release type 鱲 (wt%) Total solid X mi , Π , :E84 ] Content ^ 37.55 W&MM 45.0 2 DM55 IPA/BuOH PR-122 ——— — 28.5 4/1 1.5 0 0 30.0 % VEST Female LT171 Methanol butyl alcohol, 'Edit|2 -·, < Ning-, iron fiber: mine Yi children's fiber iron shirt iron scales academic fiber iron fiber record iron picking list / 7T,,: < 19 2/1 20.0 4 P581/CPR100 MEK/EAc ΡΒ15 : 3 LicoWax S 42.5 3/4 2.5 0 5.0 ιΎο.ο 5 P581 MEK/EAc Calendar 5 : 3 ,: LicoWax S 37.55 ,.:t, ▼ Λ Ί. . "Λ一ϋ m 2*25 0J 八Ί ' 145.0 22 1291603
6 Ρ581 MEK/EAc PB15 : 3 E84 LicoWax S 37.55 1/2 2.25 0.7 4.5 45.0 7 v:: 細 fBt5 ： 3 E84 ^ ΟcoWax S 37,55 ：- 2.25 0.7 .4S：^ 45i3 8 P581 MEK/EAc PB15 : 3 E84 LicoWax S 37.55 1/2 2.25 0.7 4.5 45.0 9 P581 MEK/EAc PB15 ·♦ 3 E84 LicoWax S 3755 1/2 125 0J 45' ' 45,0 10 P581 MEK/EAc PB15 ： 3 E84 LicoWax S 37.55 1/2 2.25 0.7 4.5 45.0 11 PB15 :3 E84，」 LicoWax S '厂' 3/4 、.V2f ' '' ϋΠ5 v ,::5 ' 50*0 12 P581 MEK/EAc PB15 : 3 E84 LicoWax S 33.4 2/5 2 0.6 4 40.0 13 P5B1 MEK/EAc 服5 : 3 腦 LicoWax S 33.4 3/4 2 0.6 4 40,0 表二、各實施例之水溶液相配方 實施 水溶液相配方 例 抗凝聚劑(wt%) 促進劑(wt%) 1 :4:':乂、Tw酿 m 、' 7 c 2 PVA — 5 0 3 PVA DowFAX2Al 緣雜 4.5 4 4 PVA Tween 20 7.5 1 PVA Tween 20 10 1 6 PVA Tween 20 10 1 7 Twrni20 , /*v |U 鑛爾纖繼^綠孩錢·錄讎簿鐵擊賴孩縫_ 8 PVA Tween 20 7.5 1 9 PVA Tween 20 7.5 1 10 PVA Tween 20 23 1291603 7.5 1 :、:1V PVA ：；；；：J^mn2Q '燦珍鑛總毅緣 10 1 ' 12 PVA Tween 20 10 1 13 PVA Tween 20 15 1 ^ s, - v / 表三、各實施例之相關製程參數6 Ρ581 MEK/EAc PB15 : 3 E84 LicoWax S 37.55 1/2 2.25 0.7 4.5 45.0 7 v:: Fine fBt5 : 3 E84 ^ ΟcoWax S 37,55 :- 2.25 0.7 .4S:^ 45i3 8 P581 MEK/EAc PB15 : 3 E84 LicoWax S 37.55 1/2 2.25 0.7 4.5 45.0 9 P581 MEK/EAc PB15 ·♦ 3 E84 LicoWax S 3755 1/2 125 0J 45' ' 45,0 10 P581 MEK/EAc PB15 : 3 E84 LicoWax S 37.55 1/ 2 2.25 0.7 4.5 45.0 11 PB15 :3 E84," LicoWax S 'Factory' 3/4 , .V2f ' '' ϋΠ5 v ,::5 ' 50*0 12 P581 MEK/EAc PB15 : 3 E84 LicoWax S 33.4 2/ 5 2 0.6 4 40.0 13 P5B1 MEK/EAc Service 5 : 3 Brain LicoWax S 33.4 3/4 2 0.6 4 40,0 Table 2, aqueous solution phase formulation of each example implementation of aqueous phase formulation anti-coagulant (wt%) promotion Agent (wt%) 1 : 4: ': 乂, Tw brewed m, ' 7 c 2 PVA — 5 0 3 PVA DowFAX2Al margin 4.5 4 4 PVA Tween 20 7.5 1 PVA Tween 20 10 1 6 PVA Tween 20 10 1 7 Twrni20 , /*v |U 矿尔纤继^Green child money · Recording book iron hit Lai _ _ 8 PVA Tween 20 7.5 1 9 PVA Tween 20 7.5 1 10 PVA Tween 20 23 1291603 7.5 1 :,: 1V PVA:;;;:J^mn2Q 'Cannic Mine Total Edge 10 1 ' 12 PVA Tween 20 10 1 13 PVA Tween 20 15 1 ^ s, - v / Table 3, relevant process parameters of each example
製程參數 實施 有機相 水溶液相 水相添加 凝聚合併 例 (g) (g) 時間（sec) 時間(min) jf:: 30 丨,'、'60 V': 10: 2 25 30 40 2 Ί , 25 30 '40二 ' 1':' 4 30 60 80 10 5 30 60 70 10 6 30 60 70 10 7 30 60 30 10 8 30 60 30 10 9 40 80 。肩 10 10 40 80 110 10 11 30 m m 10 12 30 60 60 10 13 40 80 60 10 實施例3 配製本實施例之有機相與水溶液相之步驟，以及新的凝聚製程的步驟 和實施例1相同；主要不同處在於高分子液的樹脂改為醯胺共聚合樹脂 VESTAMELT 171(Degussa提供)，其他不同處如有機相及水溶液相之配方請 見表一及表二所示，相關的製程參數請參考表三所列數據。 實施例4 24 1291603 配製本實施狀錢減核_之辣，錢_妓製程的步驟 和實施例1相同’主要不贼在於高分子樹脂㈣？581/咖_1()()(應則 提供)混合之壓克力-笨乙_脂’其重量比為4/1 :其他不同處如有機相及 水溶液相之配方請絲-及表二卿，相_製程錄請參考表三所列數 據。 資施例5 配製本實施例之有機減水溶液相之麵，以及新賴聚製程的步骤 和實關1相同，*同處在於賴之有機溶劑顯襲^的比例改變為 10/9;其他不同處如有機相及水溶液相的配方請見表—及表二所示，相關的 製程參數請參考表三所列數據。 實施例6 配製本實施例之有機相與水溶液相之步驟，以及新的凝聚製程的步驟 矛實知例5相同’不同處在於所用之有機溶劑的比例改變為Μ; 詳細之有機相及水溶液相的配方請見表—及表二所示，相關的製程參數請 參考表三所列數據。 實施例7 •配製本實施例之機她水溶_之步驟，以及新峡聚製程的步驟 例6相同；不同處在於水溶液相加人有機相所花的時間縮短為 詳、、、田之有機相及水溶液相的配方請見表一及表二所示，相關的製程 參考表三所列數據。 實施例8 25 1291603 配製本實施例之有機相與水溶液相之步驟，以及新的凝聚製程的步驟 和實施例7相同，不同處在於水溶液相的抗凝聚劑PVA濃度改變為 10wt% ’有機相及水溶液相之配方請見表一及表二所示，相關的製程表數 請參考表三所列數據。 實施例9 配製本實施例之有機相與水溶液相之步驟，以及新的凝聚製程的步驟 和實施例1相同，主要不同處在於凝聚合併的製程參數，相關的製程參數 # 請參考表二所列數據，詳細之有機相及水溶液相之配方請見表一及表二所 示。 實施例10 配製本實施例之有機相與水溶液相之步驟，以及新的凝聚製程的步驟 和實施例9相同，主要*鳴在於水溶液相加人有機相所花的時間增長為 llOsec，詳細之有機相及水溶液相之配方請見表一及表二所示，相關的製程 參數請參考表三所列數據。 _ 實施例11 配裝本實^例之有機相與水溶液相之步驟，以及新的凝聚製程的步驟 和實祕1相同’主要不同處在於有機相之固含量改變為5〇嗔，其他不 • 處如有齡及水喊相之配方請絲—絲二所示，細的製程參數請 參考表三所列數據。 實施例12 配裝本實蝴之有機相與水溶液相之步驟，以及新的凝聚製程的步驟 26 1291603 和實施例u相同，主要不同處在於有機相之固含量改變為4〇威詳★ 有機相及水溶液相之配方請見表一及表二所示，相關的製程參數請 三所列數據。 >考表 實施例13 配製本實施例之有機相與水溶液相之步驟，以及新的凝聚製程的㈣ 和實施例，主要不同處在於有機溶劑廳·的比例改變為糾， 其他不同處如有機相及水溶液相之配方請見表—及表二所示，相關的製程 馨 參數請參考表三所列數據。 比較例1 傳統凝聚法所製備之碳粉經分級篩選後之外觀、粒徑與其粒徑分佈， 如圖二所示；該碳粉為錢(CanQn)公賛生產，麟純剛公司之新型 HP CLJ2500彩色雷射印表機。 比較例2 傳統粉财碳粉經分轉驗之賴、粒健其雜分佈，如圖三所 不’該碳粉為UniNet公司所生產，用於愛普生(Eps〇n)公司之新型Eps〇n AcuLaser C900彩色雷射印表機。 比較例3 傳統凝聚法所製備之碳粉經分級賴後之外觀、減與錄徑分佈， 相關數據明見表四，該石炭粉為佳能(Can〇n)公司所生產，用於惠普(册)公司 之新型HPCLJ3500彩色雷射印表機。 27 1291603 表四、碳粉粒徑及粒徑分佈比較Process parameters implementation of organic phase aqueous phase phase water phase addition agglomeration combined (g) (g) time (sec) time (min) jf:: 30 丨, ', '60 V': 10: 2 25 30 40 2 Ί , 25 30 '40 2' 1':' 4 30 60 80 10 5 30 60 70 10 6 30 60 70 10 7 30 60 30 10 8 30 60 30 10 9 40 80 . Shoulder 10 10 40 80 110 10 11 30 mm 10 12 30 60 60 10 13 40 80 60 10 Example 3 The steps of preparing the organic phase and the aqueous phase of the present embodiment, and the steps of the new coagulation process are the same as in the first embodiment; The main difference is that the resin of the polymer liquid is changed to phthalamide copolymer resin VESTAMELT 171 (provided by Degussa). For other formulations such as organic phase and aqueous phase, please refer to Table 1 and Table 2. For related process parameters, please refer to the relevant process parameters. The data listed in Table III. Example 4 24 1291603 The preparation of the embodiment of the money reduction nuclear _ spicy, the money _ 妓 process steps the same as the first example ‘the main thief lies in the polymer resin (four)? 581/咖_1()() (supplied) Acrylic-Stupid B-lipid with a weight ratio of 4/1: other different formulas such as organic phase and aqueous phase, please note - and Table 2 Qing, phase _ process record please refer to the data listed in Table 3. Example 5 The surface of the organic water-reducing phase of the present embodiment is prepared, and the steps of the new lysing process are the same as those of the actual one, and the same place is that the ratio of the organic solvent intrusion is changed to 10/9; For the formulation of organic phase and aqueous phase, please refer to the table - and Table 2, please refer to the data listed in Table 3 for the relevant process parameters. Example 6 The steps of preparing the organic phase and the aqueous phase of the present embodiment, and the step of the new coagulation process are the same as in the case of the same example. The difference is that the ratio of the organic solvent used is changed to ruthenium; the detailed organic phase and the aqueous phase are detailed. Please refer to the table - and Table 2 for the formula. Please refer to the data listed in Table 3 for the relevant process parameters. Example 7: The procedure for preparing the water-soluble solution of the present embodiment, and the step 6 of the process of the new gorge polymerization process are the same; the difference is that the time taken for adding the organic phase to the aqueous solution is shortened to the organic phase of the detailed, For the formulation of the aqueous phase, please refer to Table 1 and Table 2. The relevant process refers to the data listed in Table 3. Example 8 25 1291603 The steps of preparing the organic phase and the aqueous phase of the present embodiment, and the steps of the new coagulation process are the same as those of Example 7, except that the concentration of the anti-coagulant PVA of the aqueous phase is changed to 10 wt% 'organic phase and The formula of the aqueous phase is shown in Table 1 and Table 2. For the number of related process tables, please refer to the data listed in Table 3. Example 9 The steps of preparing the organic phase and the aqueous phase of the present embodiment, and the steps of the new coagulation process are the same as those of the first embodiment. The main difference lies in the process parameters of the agglomeration and the associated process parameters. Please refer to Table 2 The data, detailed organic phase and aqueous phase formulation are shown in Tables 1 and 2. Example 10 The steps of preparing the organic phase and the aqueous phase of the present embodiment, and the steps of the new coagulation process are the same as those of the embodiment 9. The main reason is that the time taken for the addition of the organic phase in the aqueous solution is increased to llOsec, detailed organic See Table 1 and Table 2 for the formulation of phase and aqueous phase. For the relevant process parameters, please refer to the data listed in Table 3. _ Example 11 The steps of formulating the organic phase and the aqueous phase of the present embodiment, and the steps of the new coagulation process are the same as those of the actual one. The main difference is that the solid content of the organic phase is changed to 5 〇嗔, and the other is not For example, the formula for the age and the water shouting is shown in the silk-silf. For the detailed process parameters, please refer to the data listed in Table 3. Example 12 The step of disposing the organic phase of the actual phase with the aqueous phase, and the step of the new coagulation process 26 1291603 are the same as the example u, the main difference being that the solid content of the organic phase is changed to 4〇威详★ Organic phase For the formulation of the aqueous phase, please refer to Table 1 and Table 2. For the relevant process parameters, please refer to the data listed in III. > Test Table Example 13 The steps of preparing the organic phase and the aqueous phase of the present embodiment, and the new coagulation process (4) and the examples, the main difference is that the proportion of the organic solvent chamber is changed to correct, and other differences such as organic See the table and the table for the formulation of the phase and the aqueous phase. Please refer to the data listed in Table 3 for the relevant process parameters. Comparative Example 1 The appearance, particle size and particle size distribution of the carbon powder prepared by the conventional coacervation method after grading and screening, as shown in Fig. 2; the carbon powder is produced by CanQn, and the new HP of Linchungang Company CLJ2500 color laser printer. Comparative Example 2 The traditional powdered carbon powder was transferred to the test, and the grain was mixed. As shown in Figure 3, the toner was produced by UniNet and used in Eps〇n's new Eps〇n. AcuLaser C900 color laser printer. Comparative Example 3 The appearance, reduction and recording diameter distribution of the carbon powder prepared by the conventional coacervation method are as follows. The relevant data are shown in Table 4. The charcoal powder is produced by Canon (Can〇n) company and used for HP (book) The company's new HPCLJ3500 color laser printer. 27 1291603 Table 4, Comparison of particle size and particle size distribution
實施 樹脂種類 外觀 體積粒徑 數目粒徑 粒徑分佈 <4μπι Dv， > 15μιη 例 ϋν(μηι) ϋρ(μιη) Dy/Dp Dp(%) Dy 9 Dp(%) 1 壓克力-苯乙烯樹脂 球狀 7.3 6.2 1.18 1.0 0.2 1 P581(SEKISUI) 均一 6.9 0.01 2 壓克力樹脂DM55 球狀 17.5 12.2 1.43 0.1 66.7 (ROHM & HAAS) 均一 8.6 28.2 醯胺共聚合樹脂 球狀 1.46 0.4 15.2 3 11.4 7.8 VESTAMELT 171(DEGUSSA) 均一 10.9 1.9 壓克力-苯乙烯樹脂 球狀 0.2 1.7 4 P581(SEKISUI)/ CPRIOO(MITSUI) 均一 10.2 8.5 1.20 6.0 0.3 C 壓克力·苯乙烯樹脂 球狀 8.5 5.8 1.47 2.8 0.5 3 P581(SEKISUI) 均一 27.2 0.04 壓克力-苯乙烯樹脂 球狀 6.4 5.3 1.21 3.5 0.14 0 P581(SEKISUI) 均一 16.7 0.01 7 壓克力-苯乙烯樹脂 球狀 7.2 5.7 1.26 2.3 0.3 P581(SEKISUI) 均一 16.6 0.01 Q 壓克力-苯乙烯樹脂 球狀 8.5 6.7 1.27 1.0 0.4 〇 P581(SEKISUI) 均一 11.8 0.03 9 壓克力_苯乙烯樹脂 非球形 8.1 6.3 1.29 1.49 0.2 P581(SEKISUI) 均一 15.7 0.02 1 Λ 壓克力-苯乙烯樹脂 球狀 7.6 6.5 1.17 0.6 0.3 1U P581(SEKISUI) 均一 5.1 0.02 11 壓克力-苯乙烯樹脂 球狀 10.1 7.8 1.29 0.5 2.4 P581(SEKISUI) 均一 11.7 0.38 12 壓克力-苯乙烯樹脂 球狀 8.9 6.8 1.31 1.1 1.1 P581(SEKISUI) 均一 14.2 0.11 13 壓克力-苯乙烯樹脂 非球狀 11.2 8.2 1.37 1.7 10.2 P581(SEKISUI) 均一 8.5 0.33 比較 壓克力-苯乙烯樹脂 球狀 7.1 6.2 1.15 0.9 0.6 例1 HP2500 均一 7.0 0.04 比較 壓克力-苯乙烯樹脂 非球狀 9.1 6.6 1.38 1.1 2.1 例2 Epson C900 不均 13.4 0.19 比較 壓克力-苯乙烯樹脂 球狀 7.4 6.2 1.19 1.2 0.2 例3 HP3500 均一 9.5 0.05 比較 壓克力-苯乙烯樹脂 球狀 7.8 6.6 1.18 0.6 0.8 例4 HP4600 均一 6.1 0.06 28 1291603 比較例4 傳統凝聚法所製備之碳粉經分級篩選後之外觀、粒徑與其粒徑分佈， 相關數據請見表四；該碳粉為佳能(Can〇n)公司所生產，用於惠普(Hp)公司 之新型HPCLJ4600彩色雷射印表機。 碳粉粒徑分析： 本發明之新的凝聚法所製備之破粉的粒徑及其粒徑分佈，採用 Beckman Counter 公司的 Multisizei™ 3 COULTER c〇UNTER粒徑分析儀測 里知到，所選用的粒徑分析孔管，其孔徑為1〇〇μιη，可量測粒徑範圍 2-60μιη，粒控分析步驟如下，首先取測量杯約心7分滿之標準液進行背景 值杈正’然後滴入稀釋後的分析液至濃度強度達1〇%後，開始進行粒徑分 析，在此設定分析3萬顆碳粉後結束粒徑測量，約需5_2〇sec視分析液濃度 而疋，粒徑分析儀會將分析的結果，以體積或數目平均粒徑的累積圖顯示。 碳粉外貌觀察： 本發明各實施例所製備的碳粉顆粒，採用慶隆光機電有限公司的 PM-217T光學顯微鏡進行碳粉外觀的觀測；觀測的步驟如下，首先將粒徑分 析時所用的碳粉稀釋分析液滴在載刻上，使其均勻分佈於玻片表面並靜 置待其輪，將乾燥後含有碳粉之玻片置於顯微鏡載台上，調整適當倍率 觀察碳粉外貌；再藉由CCD將影像傳送至電腦擷取儲存。 實施例分析 各實施例所製備的碳粉顆粒外觀、粒徑及其粒徑分佈如表四所示： 實施例1、6、7及9所得之碳粉粒徑及其粒徑分佈，與傳統凝聚法如 29 1291603 比較例1、3及4採用的懸浮聚合所製備碳粉粒徑相近，但較傳統粉碎式碳 粉如比較例2，具備粒徑更小且粒徑分佈更窄的優點，如圖四所示； 而實施例13顯示，减的凝聚法可哺備非球狀外貌的碳粉，如圖五 所不，以傳統凝聚法如Canon之懸浮聚合法，將困難達到； 此外’貝婦U、2、3及4說明新的凝聚製程適用於不同高分子樹脂 或其混合物；比較實施例5及6的結果，得知不同溶解度之有機溶劑對於 新的凝聚製程有顯著的影響，如表四結果所示：適#的有機溶劑溶解度， >可以控制-次微粒析出及固化速率，降低粒徑及窄化粒徑分佈；不當的有 機溶劑溶解度，可能導致高分子樹脂與添加劑間在相分離時無法同步析 出，產生未著色或包覆不完全之樹脂微粒，以及凝聚合併時析出結塊；一 般適當的有機溶鑛水溶液相的溶解度在每克水可溶〇 〇lg有機溶劑以 上，較佳的範圍在每克水可溶0.04—lg有機溶劑；而其對高分子溶解度則 是越大越好。 丨比域細7及8魏，關抗凝聚劑濃度賴峡聚製程亦有顯著 的影響；由表四結果顯示，抗凝聚劑的添加濃度越高，粒徑越小且粒捏分 佈也較窄；但添加過多的抗凝聚劑可能導致高分子膠體微粒間不易合併成 長，以及造成後段清洗過濾程序不易處理。 比較實施例i及8、6及7或9及10，可以得到水溶液相所需的添加 時間對新的凝聚製程的影響，如表四的結果所示；適當的控制水溶液相添 加所需時間可以使碳粉粒徑及其粒徑分佈較佳，所需添加時間過久(添加速 率過慢)可能導致高分子膠體微粒間合併成長不一，造成粒徑分佈太寬，以 30 1291603 於辦，所需添加軸短(添加速率過細可能_多樹 月曰微粒_uclei)，造成膝凝㈣i雜象進而導致樹脂結塊。 新的凝πΓ^11及12 ’由表四的結果顯示，有機相的固含量越低，則 …所糾錄她及其粒徑分佈越佳；但過低的有機相固含量， 會導致製程產率下降；因此，適當的有機相固含U必須的。 因此本發明糟由掌控上述新的凝聚程序中的各種製程參數以控制高 =子相刀料絲體微粒的速率及高分子娜雜固化速率，並搭配抗凝 ，、帛可以知到有效控制碳粉外觀、粒徑及其粒徑分佈的方法，進 而付到4合錢及各鱗技€雜設備所需的雜。 為使本發明更加顯現出進步性與實用性，兹與習用碳粉製成方法作一 比較分析如下： 習用缺失： 1·耗能且耗時，無法增進產能。 2·粒徑無法精確掌控，造成品質控管不易。 3·易造成環保困擾，增加環保成本。 4·局限較大，應用範圍無法有效推展。 5·粒子表面不易控制，粉碎後多為不規則狀，造成應用困擾。 6·不同批次產品粒徑差異大，應用該碳粉之設備或機組調校不易，故 障率因此提高。 本創作之優點： 1·製程簡便，操作容易。 31 1291603 2. 不須高絲發或高速攪拌，節魏源及時間。 3. 藉由水溶賴作，賴降低環侧題，料環鐵本。 4. 可藉由精翻整因子，有財㈣作品#，_獨產品需求。 5. 產品均質性更佳且以窄粒徑分布，應聰圍更廣。 6. 不同批次產品穩定雜應狀設備轉率可大幅減少。 7·具進步性及實用性。 雖然本創作之實施例揭露如上，然其並_以限林創作，任何熟習 _此_者，林_本_之_域_，t可做各種更_不同的應 用，因此本創作之保護範圍當視後附之申請專利範圍所界定者為準。 綜上所述，本創作在突破先前之技術下，確實已達到所欲增進之功效， 且也非熟悉該項技藝者所易於思及，再者，本創作申請前未曾公開，其所 具之進步性、實用性，顯已符合發明專利之申請要件，妥依法提出發明申 請0 【圖式簡單說明】 圖一、本發明之流程示意圖。 圖二、比較例1所製備之碳粉外貌圖及其粒徑分佈圖。 圖三、比較例2所製備之碳粉外貌圖及其粒徑分佈圖。 圖四、實施例6所製備之碳粉外貌圖及其粒徑分佈圖。 圖五、實施例13所製備之碳粉外貌圖及其粒徑分佈圖。 32 1291603 【主要元件符號說明】Resin type Appearance Volume particle size Number particle size distribution <4μπι Dv, > 15μιη Example ϋν(μηι) ϋρ(μιη) Dy/Dp Dp(%) Dy 9 Dp(%) 1 Acrylic-styrene Resin spherical 7.3 6.2 1.18 1.0 0.2 1 P581 (SEKISUI) Uniform 6.9 0.01 2 Acrylic resin DM55 Spherical 17.5 12.2 1.43 0.1 66.7 (ROHM & HAAS) Uniform 8.6 28.2 Indole copolymerized resin sphere 1.46 0.4 15.2 3 11.4 7.8 VESTAMELT 171 (DEGUSSA) Uniform 10.9 1.9 Acrylic-styrene resin spherical 0.2 1.7 4 P581 (SEKISUI) / CPRIOO (MITSUI) Uniform 10.2 8.5 1.20 6.0 0.3 C Acrylic styrene resin spherical 8.5 5.8 1.47 2.8 0.5 3 P581(SEKISUI) Uniformity 27.2 0.04 Acrylic-styrene resin spherical 6.4 5.3 1.21 3.5 0.14 0 P581(SEKISUI) Uniform 16.7 0.01 7 Acrylic-styrene resin spherical 7.2 5.7 1.26 2.3 0.3 P581 (SEKISUI) Uniform 16.6 0.01 Q Acrylic-styrene resin spherical 8.5 6.7 1.27 1.0 0.4 〇P581 (SEKISUI) Uniform 11.8 0.03 9 Acrylic _ Styrene resin non-spherical 8.1 6.3 1.29 1.49 0.2 P581 (SEKISUI) Uniform 15.7 0 .02 1 Λ Acrylic-styrene resin spherical 7.6 6.5 1.17 0.6 0.3 1U P581 (SEKISUI) Uniform 5.1 0.02 11 Acrylic-styrene resin spherical 10.1 7.8 1.29 0.5 2.4 P581 (SEKISUI) Uniform 11.7 0.38 12 Pressure Kelly-styrene resin spherical 8.9 6.8 1.31 1.1 1.1 P581 (SEKISUI) Uniform 14.2 0.11 13 Acrylic-styrene resin non-spherical 11.2 8.2 1.37 1.7 10.2 P581 (SEKISUI) Uniform 8.5 0.33 Comparative Acrylic-Styrene Resin spherical 7.1 6.2 1.15 0.9 0.6 Example 1 HP2500 Uniform 7.0 0.04 Comparative Acrylic-styrene resin non-spherical 9.1 6.6 1.38 1.1 2.1 Example 2 Epson C900 Uneven 13.4 0.19 Comparative Acrylic-Styrene Resin Spherical 7.4 6.2 1.19 1.2 0.2 Example 3 HP3500 Uniform 9.5 0.05 Comparative Acrylic-Styrene Resin Spherical 7.8 6.6 1.18 0.6 0.8 Example 4 HP4600 Uniform 6.1 0.06 28 1291603 Comparative Example 4 The appearance of the carbon powder prepared by the conventional coacervation method after grading and screening, The particle size and particle size distribution, please refer to Table 4 for the relevant data; the toner is produced by Canon (CanPn) company for HP (Hp) company's new HPCLJ4600 color laser printer. Carbon particle size analysis: The particle size and particle size distribution of the powder prepared by the new coacervation method of the present invention are determined by Beckman Counter's MultisizeiTM 3 COULTER c〇UNTER particle size analyzer. The particle size analysis orifice tube has a pore size of 1 〇〇μιη, and the particle size range is 2-60 μιη. The particle size analysis step is as follows. First, the standard solution of the measuring cup about 7 minutes is used to carry out the background value 杈 positive' After dropping the diluted analysis solution to a concentration intensity of 1% by weight, the particle size analysis is started. After the analysis of 30,000 carbon powders is set, the particle size measurement is completed, and about 5 2 〇 sec is used depending on the concentration of the analysis solution. The diameter analyzer displays the results of the analysis as a cumulative plot of volume or number average particle size. Toner appearance observation: The carbon powder particles prepared in the examples of the present invention were observed by the PM-217T optical microscope of Qinglong Opto-Electronics Co., Ltd.; the observation steps were as follows, firstly, the carbon used in the particle size analysis. Powder dilution analysis of the droplets on the surface of the slide, so that it is evenly distributed on the surface of the slide and wait for its wheel, the dried glass slide containing carbon powder is placed on the microscope stage, and the appropriate magnification is adjusted to observe the appearance of the toner; Transfer images to a computer for capture by CCD. EXAMPLES The appearance, particle size and particle size distribution of the carbon powder particles prepared in each of the examples were as shown in Table 4: The particle size and particle size distribution of the carbon powder obtained in Examples 1, 6, 7, and 9 were compared with the conventional ones. Coagulation method such as 29 1291603 The suspension powders used in Comparative Examples 1, 3 and 4 have similar particle sizes, but the conventional pulverized carbon powder, like Comparative Example 2, has the advantages of smaller particle size and narrower particle size distribution. As shown in FIG. 4; and Example 13 shows that the reduced coacervation method can feed the carbon powder of the non-spherical appearance, as shown in FIG. 5, and the difficulty is achieved by the conventional cohesion method such as the suspension polymerization method of Canon; Women U, 2, 3 and 4 indicate that the new coacervation process is applicable to different polymer resins or mixtures thereof; comparing the results of Examples 5 and 6, it is known that organic solvents of different solubility have a significant effect on the new coagulation process, such as The results in Table 4 show: the solubility of organic solvent, > can control the secondary particle precipitation and solidification rate, reduce the particle size and narrow the particle size distribution; improper organic solvent solubility may lead to the interpolymer resin and additives Cannot be the same when phase separation Precipitating, producing uncolored or incompletely coated resin particles, and agglomerating and agglomerating when agglomerating; generally, the solubility of the appropriate organic mineralized aqueous phase is above lg of water soluble lg organic solvent, preferably It is soluble in 0.04 lg of organic solvent per gram of water; and its solubility to the polymer is as large as possible. The ratio of the anti-coagulant concentration to the Laixia process has a significant effect; the results in Table 4 show that the higher the concentration of the anti-agglomeration agent, the smaller the particle size and the narrower the pinch distribution. However, the addition of too much anti-agglomeration agent may cause the polymer colloidal particles to be difficult to combine and grow, and the post-cleaning filtration process is not easy to handle. Comparing Examples i and 8, 6 and 7 or 9 and 10, the effect of the addition time required for the aqueous phase on the new coagulation process can be obtained, as shown in the results of Table 4; the appropriate time for controlling the addition of the aqueous phase can be The toner particle size and particle size distribution are better, and the required addition time is too long (the addition rate is too slow), which may cause the polymer colloidal particles to grow and grow differently, resulting in a particle size distribution that is too wide, and is performed at 30 1291603. The required addition of the shaft is short (the addition rate is too fine may be _ multi-tree lunar particles _uclei), causing the knee coagulation (four) i hogs to cause resin agglomeration. The new condensed πΓ^11 and 12' are shown by the results in Table 4. The lower the solid content of the organic phase, the better the particle size distribution is, and the too low the organic solid content, which leads to the process. The yield is reduced; therefore, the proper organic phase contains the necessary U. Therefore, the present invention can control the various process parameters in the above new coagulation process to control the rate of the high-subphase knife filaments and the polymer solidification rate, and can be combined with anticoagulation, and the crucible can be effectively controlled. The method of powder appearance, particle size and particle size distribution, and then the amount of money required for 4 yuan and various scales of equipment. In order to make the present invention more progressive and practical, a comparative analysis of the conventional carbon powder production method is as follows: Lack of use: 1. Energy consumption and time consuming, unable to increase productivity. 2. The particle size cannot be accurately controlled, resulting in difficulty in quality control. 3. Easy to cause environmental problems and increase environmental protection costs. 4. The limitation is large, and the application range cannot be effectively promoted. 5. The particle surface is not easy to control, and it is often irregular after pulverization, causing application troubles. 6. The difference in particle size of different batches of products is large, and the equipment or unit to which the toner is applied is difficult to adjust, and the accident rate is thus increased. The advantages of this creation: 1) The process is simple and easy to operate. 31 1291603 2. Do not need high wire or high speed mixing, Wei Wei source and time. 3. By using water to dissolve, the lower side of the ring, the iron ring. 4. By the fine turning factor, there is a wealth (four) works #, _ independent product demand. 5. The product is more homogeneous and has a narrow particle size distribution. 6. The conversion rate of stable and mixed equipment in different batches can be greatly reduced. 7. Progressive and practical. Although the embodiment of the present invention discloses the above, it is also limited to the creation of the forest, any familiar _ this _, Lin _ _ _ _ domain _, t can do a variety of different _ different applications, so the scope of protection of this creation This is subject to the definition of the scope of the patent application. In summary, this creation has achieved the desired effect under the previous technology, and it is not easy for people who are familiar with the technology to think about it. Moreover, this creation has not been disclosed before the application, and it has Progressive and practical, it has been consistent with the application requirements of the invention patent, and the invention application is submitted according to law. [Simplified illustration of the drawing] Figure 1. Schematic diagram of the flow of the present invention. Figure 2 is a diagram showing the appearance of the carbon powder prepared by Comparative Example 1 and its particle size distribution. Fig. 3 is a top view of the carbon powder prepared by the comparative example 2 and its particle size distribution diagram. Figure 4 is a top view of the carbon powder prepared in Example 6 and its particle size distribution diagram. Figure 5 is a top view of the carbon powder prepared in Example 13 and its particle size distribution diagram. 32 1291603 [Description of main component symbols]