TW394705B - Process for preparing a concentrated aqueous suspension of a finely ground particulate material and the product thereof - Google Patents
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-———— 五、發明説明（11 ) 成量之(2/D X 100)%。較佳地，在每一加成位置都加入等 量之分散劑。 根據本發明之方法，此含水懸浮液在一或多個研磨階 段中研磨處理時，其pH在8.5至9.8的範圍内，更希望pH 範圍在8.5至9.5之間，特別在8.8至9.2之間。 圖式之簡單說明 圖1表示研磨過程之流程圖。 主要部分代表符號 1〜導管，2〜導管，3〜第一溼研磨機，4〜葉輪，5〜直 立轴，6〜微粒研磨介質’ 7〜筛子’ 8~出口，9〜導管，10〜 導管，11〜第二研磨機，12〜出口，13〜導管，14〜混合 槽，15~導管，16~出口。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 本發明之方法中，以各種明顯用於習知技術上處理無 機礦物懸浮液方法之一，將pH調整至所需範圍内。因此， 在實施例1的方法中，為了確認完全研磨後的pH值控制在 所需的範圍中，一種水溶性酸的分散劑加入懸浮液中，接 著並加入一鹼，如氫氧化鈉的處理。當顆粒變小時處理過 之顆粒表面上之可利用的陽離子數目增加，在許多階段中 鹼所加入的量，也可逐階段的減少，使得水相的pH值維持 在所需的範圍中。 在第二個實施例中，一種聚羧酸鹽的鹽類，例如聚羧 酸鈉，在研磨完成之後加入，且含水介質以水進行稀釋來 降低pH值，然後較佳地由一已知的脫水步驟再濃縮，如過 濾作用。稀釋方法及再濃縮的方法於本案申請人之英國專 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央標準局員工消費合作社印製 .A7 ______^___B7____ 五、發明説明（1 ) 本發明係有關於一種製備具穩定流變性，一種無機之 微粒物質的濃縮含水懸浮液，如分割地很細微的鹼土金屬 顏料的方法。 爲了製造與分散鹼土金屬顏料或填充物，特別是以紙 類及水爲基礎的塗料工業，以一濃縮懸浮一液的型式在水中 通常較有利的。使用者獲得此種型式之鹼土金屬顏料後， 可避免高能量及資本之消耗，此耗費包含一乾燥材質與水 混合形成懸浮液，且若此鹼土金屬顏料是由一溼路徑所產 生’則此生產者可避免材質完全乾燥的浪費。一濃縮之含 水懸浮液也較易處理及傳送，並且没有灰塵的問題。 驗土金屬顏料含水懸浮液之流變性質與數個因素有 關，包括固體材質在懸浮液之濃度，固體材質顆粒大小之 分布，如所顯示的例如當量球體直徑小於2μπι之顆粒之重 量百分比，及所使用分散劑之型式及劑量。通常當固體濃 度增加或當量球體直徑小於2μιη之顆粒的重量百分比增 加’則懸浮液變得較黏稠，流體較少。且此懸浮液亦有隨 貯存時間增加，而黏稠度增加之傾向。假設可獲得一供鹼 土金屬顏料用之有效分散劑，將適量分散劑加至懸浮液 中’則可產生最大的流體性及最大的流變穩定性，而其他 因素保持不變。 歐洲專利ΕΑ-Ρ-〇216〇〇2描敘一種方解石(caicite：^ 製程，包括將濃縮的方解石顆粒泥漿移入多階段的研磨步 驟中，即從上游的研磨階段經由下游的一或多個研磨階 段，其中每個下游研磨步驟充滿了研磨介質，此研磨介質 m· 1 nn In· ^m· n -n I I J (請先閲讀背¾.之注意»-項再填寫本頁)-———— V. Description of the invention (11) (2 / D X 100)% of the amount. Preferably, an equal amount of dispersant is added at each addition position. According to the method of the present invention, when the aqueous suspension is ground in one or more grinding stages, its pH is in the range of 8.5 to 9.8, more preferably in the range of 8.5 to 9.5, especially between 8.8 and 9.2. . Brief description of the drawings Figure 1 shows a flowchart of the grinding process. The main part represents the symbol 1 ~ duct, 2 ~ duct, 3 ~ first wet grinder, 4 ~ impeller, 5 ~ upright shaft, 6 ~ particulate grinding medium '7 ~ sieve' 8 ~ outlet, 9 ~ duct, 10 ~ duct , 11 ~ second grinder, 12 ~ outlet, 13 ~ duct, 14 ~ mixing tank, 15 ~ duct, 16 ~ outlet. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). In the method of the present invention, the pH is adjusted by one of various methods that are obviously used in conventional techniques for processing inorganic mineral suspensions. To the required range. Therefore, in the method of Example 1, in order to confirm that the pH value after being completely ground is controlled in a desired range, a dispersant of a water-soluble acid is added to the suspension, and then a base such as sodium hydroxide is added to the treatment. . When the particles become smaller, the number of available cations on the surface of the treated particles increases, and the amount of alkali added in many stages can also be reduced step by step, so that the pH of the aqueous phase is maintained in the required range. In a second embodiment, a salt of a polycarboxylate, such as sodium polycarboxylate, is added after the milling is completed, and the aqueous medium is diluted with water to reduce the pH, and then preferably from a known The dehydration step is then concentrated, such as by filtration. The dilution method and the reconcentration method are applied to the applicant's UK-specific paper size. The application is based on the Chinese National Standard (CNS) A4 (210X297 mm). Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. (1) The present invention relates to a method for preparing a concentrated aqueous suspension with stable rheology, an inorganic particulate material, such as a finely divided alkaline earth metal pigment. In order to make and disperse alkaline earth metal pigments or fillers, especially the paper and water-based coating industry, it is generally advantageous to use a concentrated suspension in a liquid form in water. After the user obtains this type of alkaline earth metal pigment, he can avoid high energy and capital consumption. This cost includes mixing a dry material with water to form a suspension, and if the alkaline earth metal pigment is generated by a wet path, then this Producers can avoid the waste of completely dry materials. A concentrated aqueous suspension is also easier to handle and transport, and has no problem with dust. The rheological properties of the soil metal pigment aqueous suspension are related to several factors, including the concentration of the solid material in the suspension, the particle size distribution of the solid material, as shown, for example, the weight percentage of particles with an equivalent sphere diameter less than 2 μm, and Type and dosage of dispersant used. Generally, as the solid concentration increases or the weight percentage of particles with an equivalent sphere diameter less than 2 µm increases, the suspension becomes thicker and less fluid. And this suspension also tends to increase in viscosity with storage time. Assuming that an effective dispersant for alkaline earth metal pigments is available, adding an appropriate amount of dispersant to the suspension 'will produce maximum fluidity and maximum rheological stability, while other factors remain unchanged. European patent EA-P-02216002 describes a process of calcite (caicite: ^), which includes moving a concentrated calcite particle slurry into a multi-stage grinding step, that is, from an upstream grinding stage through one or more downstream grinding stages Stage, in which each downstream grinding step is filled with grinding medium, this grinding medium m · 1 nn In · ^ m · n -n IIJ (please read the note of the back ¾. »-Item before filling this page)
1T 參' .1 (2—1T ref '.1 (2—
五、發明説明$1-1) 利 PCT/GB95/00563(WO 95/25146)中有描敘。 在第三個實施例，將不同的分散劑加至不同的加成階 段。因此在研磨期間，將完全被中和的聚羧酸鹽加入以作 為分散劑，而在研磨完成之後，將一酸型式之分散劑加入。 較佳地，在每一個實施例中，不同分散劑之鹼性聚合物或 共聚物為相同的。 第四個實施例中，將不同分散劑的化合物在研磨完全 ---------.^------^-I1T------ /! , (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 14-1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） A7 B7 五、發明説明'（2 ) ~ 的顆粒大小比前-個上游研磨步驟的研磨介質還要小 揭露之研磨介質包括氧隸，氧絲/二氧财，或氧化供 /二氧化妙。-分散劑，例如一種水溶性聚丙稀酸鹽的水： 液，如聚丙烯酸鈉，最好在研磨前就加至泥漿中。崎 錢專利USA4325514係揭露—種研衫法，—積物 在第-研磨室中缺乏研磨介質時，且在澄的狀況下 磨。此被研磨的礦物進一步在第二研磨室中有研磨介 經研磨。在第-研磨室中必須使用一分散劑。在第二研 室也可以選擇使用分散劑。 71启 歐洲專利EP士〇59則係揭露一種研磨方法，其中— ，簡擴物(如碳_)…薄轉物(如高鱗土)與-塑膠 研磨前及最後-研磨階段，用一研磨試劑_起進行 磨、，且這兩者皆被導入相同的研磨容器中。最後研磨階 可於膠態保護試劑之下進行處理。 又 f們發現習知技術中描敍的方法，即由研磨方式處理 ^的雜㈣如碳仙爲不適當的，因此本發明對研磨 的操作方式有多處改進。 =發明之方法所形成之一微粒無機材質經濃縮過之含 ☆二 > 液例如一鹼土金屬顏料，其與市面上所購得之终 Ϊίί比之下，若固定絲性，當量球體直徑小於2_顆 ,重量百分比及分散劑劑量，則有一較高之固體濃 亩策或口足'儿動性，固體濃度及分散劑劑量，則當量球體 ===於2μιη顆粒佔一較高的重量百分比，或在固定的重 刀比，固體濃度及分散劑劑量，則有一較高的流動性， 5 齋 Μ βΑΤ ^ -a 五、發明説明（14 ) 0.079% ° 將經過研磨的無機材質之懸浮液脫水，其方法與昔知 技術相似，例如使用熱蒸發作用，過濾，或使用離心機。 若在步驟（c)中於脫水前加入分散劑，則較佳的脫水步驟是 經膜過濾進行較有效率。此懸浮液脫水至濃度至少為乾顏 料重之75%為佳。 為了使本發明更容易了解，及表示本發明如何產生作 用，依本發明之方法則晝出一圖解的流程圖，如第一圖所 示0 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 一鹼土金屬顏料的懸浮液經初步粉碎之後，經由導管1 導入第一個溼研磨機3 。一個大體上完全被中和之聚羧 酸鹽分散劑的溶液也經由導管2導入其中。此研磨機中有 一葉輪4，此葉輪藉由一合適的啟動裝置（沒有標示出）於 一直立軸5上旋轉。在研磨機進行研磨之前，此研磨機内 充滿微粒研磨介質6，其包含的顆粒範圍在0.5至1.0mm 之間。在此鹼土金屬顏料經一次研磨後，當量球體直徑小 於2μιη顆粒所佔之重量比例降低，降至一適中的值，此懸 浮液經篩子7之0.25mm小篩孔收回鹼土金屬顏料之懸浮 液而留下研磨介質，經由出口 8及導管9，導入第二研磨 機11，此研磨機與第一研磨機完全相同。而經由導管10 將大體上完全中和的聚羧酸鹽分散劑之溶液導入第二研磨 機内。在此鹼土金屬顏料經研磨達最後所需之細微程度之 後，將顏料之懸浮液拉引經出口 12，此出口有研磨材質殘 留在篩子上，並經導管13導至混合槽14。經由導管15 17 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） A7 經濟部中央標準局員工消費合作社印製 發明説明（3) 或者對一特定的當量球體直徑小於2 μ m顆粒所佔百分比及 固體濃度及流動性，則有-較小的分散劑劑量。 依本發明<第—個觀點，有-種製備質地細微微粒物 質之濃縮含水懸浮液的方法，此方法包括： ⑷製備種含水懸浮液，其包含粗糙微粒型式的微粒 物質至少佔重量之20% ; ⑻在供微粒物質収㈣酸鹽分散蚊下，對步驟⑷ 中所形成之懸浮液進行研磨； ⑷進步將聚竣酸鹽分散劑加至步踩⑼所形成之研 磨材質的懸浮液中； ^特徵在於步驟⑷所形成之含水懸浮液，其pH値在Μ ί i且聚羧酸鹽分散劑在步驟⑷中進行加成 後^于液就不進行研磨。若適當的話，經研 浮液可脱去水份，若雲I沾％ ^ M 1 之㈣的濃度。要的心可使之乾燥到至少爲乾 么本發明《王要成份爲經研磨之無機微粒物質，如驗土 金屬顏料’其在Μ酸鹽分散#rt及完全研磨 進=添加聚竣酸鹽分散劑，此聚羧酸鹽分散劑可與步 ⑷中所使用之分散劑相同或不同，步二 控制在8 5至9 8，較佳爲8·5至”，最佳二3則 將阳控制在所需職之方法在下切有描述/ 2。 研磨步驟(b)爲-單一研磨步驟或者可包含 研磨階段(多階段研磨），如歐洲專利即各咖口乃 專利USA43225H。在研磨操作時 2及吴國 馬X將分散劑導入懸 懸 重 再 驟V. Description of the invention $ 1-1) It is described in PCT / GB95 / 00563 (WO 95/25146). In a third embodiment, different dispersants are added to different addition stages. Therefore, during the grinding, a fully neutralized polycarboxylate is added as a dispersant, and after the grinding is completed, an acid type dispersant is added. Preferably, in each embodiment, the basic polymers or copolymers of different dispersants are the same. In the fourth embodiment, the compounds of different dispersants are completely ground ---------. ^ ------ ^-I1T ------ /!, (Please read the back first Please pay attention to this page, please fill in this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs, 14-1 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 V. Description of the invention '(2) ~ of The particle size is smaller than that of the grinding medium of the previous upstream grinding step. The grinding mediums disclosed include oxygen ions, oxygen filaments / dioxins, or oxidizing / dioxide. -A dispersant, such as a water-soluble polyacrylic acid salt: liquid, such as sodium polyacrylate, is preferably added to the slurry before grinding. Saki-chan patent USA4325514 discloses-a method of grinding a shirt,-when the grinding medium is lacking in the first grinding chamber, and is ground under a clear condition. The ground mineral is further ground by a grinding medium in a second grinding chamber. A dispersant must be used in the first grinding chamber. Alternatively, a dispersant can be used in the second laboratory. 71 Kai European Patent EP 059 discloses a grinding method, in which-, simple expansion (such as carbon) ... thin turning (such as high scale soil) and-plastic grinding before and finally-grinding stage, using a grinding Reagents are ground, and both are introduced into the same grinding container. The final grinding stage can be processed under a colloidal protective reagent. We also found that the method described in the conventional technology, that is, the processing of the impurities such as carbon immortal by the grinding method is not appropriate, so the present invention has several improvements in the operation method of the grinding. = Concentrated one of the fine particles of inorganic material formed by the method of the invention. Contains ☆ two > liquids such as an alkaline earth metal pigment. Compared with the commercially available end products, if the silk is fixed, the diameter of the equivalent sphere is less than 2_ particles, weight percentage and dispersant dose, there is a high solid concentration or mouth and foot's mobility, solid concentration and dispersant dose, then the equivalent sphere === at 2μιη particles account for a higher weight Percentage, or at a fixed heavy knife ratio, solid concentration and dispersant dosage, there is a higher fluidity, 5 ZM βΑΤ ^ -a 5. Description of the invention (14) 0.079% ° Suspension of the ground inorganic material Dehydration of liquids is done in a similar way to previous techniques, such as using thermal evaporation, filtering, or using a centrifuge. If a dispersant is added before dehydration in step (c), the preferred dehydration step is more efficient through membrane filtration. The suspension is preferably dehydrated to a concentration of at least 75% by weight of the dry pigment. In order to make the present invention easier to understand, and to show how the present invention works, according to the method of the present invention, a diagrammatic flowchart is displayed daily, as shown in the first figure. 0 (Please read the notes on the back and fill in this page again) After a preliminary pulverization of the alkaline earth metal pigment suspension, it is introduced into the first wet grinder 3 through the conduit 1. A solution of the polycarboxylate dispersant which is substantially completely neutralized is also introduced into it via the catheter 2. The grinder has an impeller 4 which is rotated on a vertical shaft 5 by a suitable starting device (not shown). Before the grinder is ground, the grinder is filled with a particulate grinding medium 6 containing particles ranging from 0.5 to 1.0 mm. After the alkaline earth metal pigment is ground once, the weight ratio of particles with an equivalent sphere diameter less than 2 μιη is reduced to a moderate value. The suspension is recovered through a small 0.25 mm sieve of the sieve 7 to recover the suspension of the alkaline earth metal pigment. The grinding medium is left, and is introduced into the second grinding machine 11 through the outlet 8 and the duct 9. This grinding machine is completely the same as the first grinding machine. A solution of the substantially completely neutralized polycarboxylate dispersant is introduced into the second mill through the conduit 10. After the alkaline earth metal pigment has been ground to the last required degree of fineness, the pigment suspension is drawn through an outlet 12 where the ground material remains on the sieve and is guided to the mixing tank 14 through a conduit 13. Via a conduit 15 17 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 Printed by the Consumers ’Cooperative of the Central Bureau of Standards of the Ministry of Economics (3) or a specific equivalent sphere with a diameter less than 2 μm particles The percentage and solids concentration and flowability are-smaller dispersant doses. According to the present invention < a first aspect, there is a method for preparing a concentrated aqueous suspension of finely particulate matter, the method comprising: ⑷ preparing an aqueous suspension containing at least 20% by weight of a coarse particulate type of particulate matter %; 研磨 grinding the suspension formed in step 下 under the condition that particulate matter is used to disperse the mosquito salt to disperse the mosquito; ⑷ progressively add a polyacrylic acid salt dispersant to the suspension of the grinding material formed by stepping cymbals ^ Characterized in that the aqueous suspension formed in step 其 has a pH of Μ ii and the polycarboxylate dispersant is added in step ^ and is not ground in the liquid. If appropriate, the researched float can remove water, if the cloud I is at a concentration of% ^ M 1. It can be dried to at least the dryness of the present invention. "The main ingredients of the present invention are ground inorganic particulate materials, such as soil test metal pigments, which are dispersed in the M acid salt #rt and fully ground into the addition of polyunsaturated acid. Dispersant, this polycarboxylate dispersant can be the same as or different from the dispersant used in step ，, step 2 is controlled to 8 5 to 9 8, preferably 8 · 5 to ", the best 2 3 will be Yang The method of controlling the required position is described below. 2. Grinding step (b) is-a single grinding step or may include a grinding stage (multi-stage grinding), such as the European patent, that is, the coffee mouth is the patent USA43225H. During the grinding operation 2 and Wu Guoma X introduce dispersant into suspension
本紙張跋適财關家轉（CNS ) A4規格（210X297^5 (請先閱讀背面之注意事項再填寫本頁) ------裝----·!·—訂 —.—---------This paper, Ba Shi Cai Guan Jia Zhuan (CNS) A4 specification (210X297 ^ 5 (Please read the precautions on the back before filling out this page) ------ Installation ---- ·! · —Order —.—- --------
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nn. I 第85111170號說明書修正頁 A> B7 五、發明説明（15 ) 定量之聚鲮酸鹽分散劑導入其中 1辩f明示—正後是否變—i 經濟部中央標準局員工消費合作社印t 法調至約PH9。若需要添加其他松且將pH值*如上ϋ 藉由導管15加^於混合—段時^例如制Η，也可 酸鹽分散劑散佈在整個顏料的懸^此部分中和之聚缓 定流變性的顏料懸浮液被拉引至出口 Μ，為-流體及具穩 在其他的實施例中（沒有表 殺，軔4认μ· “ ^ 丁出來）’更多的研磨階 共至少有三個研磨階段，其與研磨㈣狀況 本發明由下列實施例來作進一步的說明。實施例 天然大理石質地之粉末的樣品，其顆粒大小分布是 使传大體上全部顆粒都比53μ則、，將此樣品與含有大理 石乾重之0.2%之完全中和之平均分子量& &⑼的聚丙稀 酸納分_之核合。如麟形叙懸雜含有65%重量 比的，大理石。使用具有大體上直捏在。5 至i 〇 mm 之球狀顆粒的二氧化矽沙作為研磨介質*以將此懸浮液予 以研磨。研磨將持續進行直到大理石之顆粒分佈情況為具 當量球體直徑小於2μηΐ2顆粒佔重量之4〇%才停止。 進一步加入大理石乾重之〇.1%的相同分散劑量，並將 經研磨之大理石懸浮液通入至第二研磨階段，且使用與第 個研磨階段相同等級之二氧化發沙顆粒。此研磨作用將 持續進行直到大理石之顆粒分佈情況為當量球體直徑小於 2μΓη之顆粒佔重量之90%才停止。質地报細微之大理石懸浮液分成Α與Β兩部分。對nn. I No. 85111170 Revised Sheet A > B7 V. Description of the invention (15) Introduction of quantitative polyphosphonate dispersant 1 of which is clearly stated-whether it will change after the positive-i Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Adjust to about pH9. If you need to add other pine and add the pH value * as above, add it through the conduit 15 to the mixing stage ^ such as making Η, or the acid dispersant can be dispersed throughout the suspension of the pigment ^ this part of the neutralized polymer flow The denatured pigment suspension is drawn to the outlet M, which is-fluid and stable in other examples (no surface killing, 轫 4 认 μ · "^ Ding out) 'more grinding stages with a total of at least three grinding The present invention is further explained by the following examples. The sample of natural marble texture powder has a particle size distribution such that substantially all particles are smaller than 53 μ. Contains 0.2% of the completely neutralized average molecular weight of the dry weight of marble & & < " > Squeeze. Silica sand with spherical particles of 5 to 10 mm is used as the grinding medium * to grind this suspension. The grinding will continue until the particle distribution of the marble is equivalent to a spherical diameter of less than 2μηΐ2 particles account for the weight of 40% before stopping. Further add the same dispersing amount of 0.1% of the dry weight of the marble, and pass the ground marble suspension to the second grinding stage, and use the same grade of dioxide as the first grinding stage. Sand particles. This grinding will continue until the distribution of marble particles is equivalent to 90% by weight of particles with an equivalent sphere diameter less than 2μΓη. The fine-grained marble suspension is divided into two parts, A and B.
A 請 先 閲 讀 面 之 注 項 再i% i 本 -% 訂 1 \w 18 本紙張尺度朗中H國家轉（CNS )纟4胁（2丨Gx297公着） 經濟部中央標準局員工消費合作社印製 A7 _____B7 五、發明説明（4 ) 浮液，分散劑的加成位置可與各個研磨階段聯結在一起。 每個分散劑加成位置可包含一研磨容器或磨子，在容器戈 磨子内進行研磨，但是我們較喜歡在懸浮液到達研磨階段 之前將分散劑加入懸浮液中，例如在一與幫浦結合的位 置，此幫浦用來將懸浮液打入位於懸浮液下游研磨階段 中。 根據本發明，一额外的分散劑加成位置可位於最後一 個研磨階段的下游，來導入更多的分散劑及其他添加物（若 有需要時）至被研磨之懸浮液中。 將被研磨微粒物質之懸浮液的所在階段進行脱水，（若 有需要的話）脱水使之至少佔乾物重之65%的濃度，或者不 用如此嚴苛。因此，研磨後聚羧酸鹽分散劑之添加可在步 驟(C)的脱水前或之後進行。 此無機微粒物質可包含一鹼土金屬之不溶性鹽類，如 鈣的不溶性鹽類。此材質經本發明之方法處理後可用來作 爲一種顏料，特別是一種紙類塗覆顏料，其可形成一已知 之紙類塗覆組成物的成分。 在步驟(a)之懸浮液中，此微粒無機材質的濃度較佳爲 重量之40%，更佳的範圍在重量之6〇至8〇%之間。 根據本發明之方法可以一連續方式或批次方法來進 行。較佳地，此製程爲一多階段研磨連續的方式，其中經 處理之含水懸浮液連續地通入研磨階段間，此研磨階段爲 各別.，但互相連接的容器來進行。此一速續方式已知是一 種大量落下進行研磨的方式，研磨成較細微之固體材質才 良紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 、τ 五、發明説明（16 ) 部分，加入早期階段所使用之相同分散劑，其量佔大理石 乾重之0·25%，對B部分則加入平均分子量為6500的聚丙 (請先閲讀背面之注意事項再填寫本頁) 稀酸（為完全中和之型式），且無其他的添加物，及對Β部 份添加平均分子量為6500的聚丙烯酸鹽分散劑並調整此 懸浮液pH值大約在pH 9，例如pH 8.8至9.2。所加入.的 量是使得，對於每單位重量之乾色素所加入的缓酸基莫耳 ¥ 數，和A部分是相同的。每一部分皆經膜過濾作用脫去水 份，使固體濃度為大理石乾重之76%，且每個懸浮液在脫 水後立即以一 Brookfield黏度計配合3號軸，速度為 lOOOrpm，進行黏稠度的偵測。再於懸浮液分別靜置1小 時及24小時後，再測量懸浮液的黏度。 為了用作比較，將大理石以研磨介質研磨至顆粒大小 分佈為使得具當量球體直徑小於2μηι之顆粒佔重量之 90%，以製備另一懸浮液。然而，在此例中，在研磨操作 開始時，加入在Α部分所使用之完全中和分散劑，其量為 乾大理石重量之0.55%重量比。 - 所得之結果詳列於下表中。 Α部分 於下列時間1 0小時 185 1所測之黏度值 1小時 330 (mPa*s) 24小時 640 B部分 150 210 350 比較組 220 600 1360 這些結果表示，對於被研磨成顆粒大小分佈為90%重 量為當量球體直徑小於2 μιη的顆粒之含有76%重量比之 大理石的懸浮液，當其在研磨後以聚羧酸鹽分散劑作處 19 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（5 ) 能通入研磨鏈下游的懸浮液中。在研磨階段之間與選擇性 地在最後一個研磨階段裝置之後，有一種依顆粒大小來分 離固體材質之裝置，如篩或篩網，使得只有較細之分離部 分可以通過。 在每一個研磨階段可被導入至一或多個研磨容器。例 如第一階段可被導入單一容器及在複數個，例如二或三容 器之串聯或並聯方式連接的容器中導入一或多個隨後的階 段。 在每一研磨階段進行研磨尚包含(3)使用一已知的介 質，如氧化鋁或二氧化矽的顆粒或氧化物混合系統；或者 (b)研磨顆粒時，彼此没有添加研磨介質之自動研磨。在至 少在此過程之最後一階段包含供研磨之今質。 在每一研磨階段之中，此懸浮液被供磨碎的介質所研 磨，較佳是以一微粒研磨介質進行研磨，其中顆粒不太於 2mm且也不小於〇.lmm來進行研磨。研磨介質之顆粒更佳 地爲不大於1mm及不小於0.25麵。在每個供磨碎的研磨 階段之後，這被磨碎的微粒物質則與研磨介質分離。& 於每一加成位置，分散劑的添加可以單—劑量進行， 或者若此製程爲一連續製程，則由複數個分離劑量或作 —連續加成。 依照本發明之方法，可由包含至少一個初步粉碎步驟 或多個其他處理步驟於研磨階段之前先行進行。例如 此轶機顆粒進入第一個研磨階段時之顆粒大小分布如此地 大使得當量球體直徑小於10μιη之顆粒至少佔重量之 ( CNS ) Α4» ( 210X297^" (請先閎讀背面之注意事項再填寫本頁〕 •裴_ -訂_ ,In - _ mi . IB7 06· — 6 芩酌无 五、發明説明（17 ) 理，並將pH調整為pH 8.8至9.2時，與當其以當量劑量之 k- 完全中後和之聚羧酸分散劑作處理，並且不控制pH時來 作比較，可發現以前者方式處理的懸浮液具有較低的初始 黏度，並且較不易凝膠，或較不易在靜置後黏度增加。而 且，對於在研磨後再以加入另外劑量之分散劑來處理的兩 懸浮液，與在研磨開始時即以單獨劑量方式加入相同總量 的分散劑所製得的研磨大理；懸浮液相比較，前者顯現出 較優異的流變性。 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（6 ) 30%(最佳不超過75%)及當量球體直徑小於2(^111之顆粒比 例上不會小於20%。這些顆粒可由礦物削片處理來獲得， 例如白堊化（chalk)或大理石的處理，直徑最大至1〇〇mm， 正常直徑範圍是在l〇mm至30mm之間。礦物削片包括在 磨子中一初步滿合步驟之處理，例如一錘磨機或如美國專 利4325514或初步溼研磨之自動溼磨機。 在初步溼研磨步驟中，由懸浮液之固體濃度來決定是 否使用分散劑。若固體濃度之重量百分比在5〇%以上，則 正常狀況下會使用分散劑。此分散劑在此一初步步驟中最 好爲聚羧酸鹽。 舉例而言，此初步研磨步驟可爲下列步驟之任一個： —加分散劑之自動溼研磨狀況，其爲高固體濃度（重量百 分比50%以上，較佳爲65%至8〇%); —不加分散劑之自動溼研磨狀況，具低固體濃度（重量百 分比5G%以下）但包含或不含—化學組成之研磨介質且此 介質與微粒物質之研磨介質不同；在此情況下，根據本發 明之方法是需要-脱水步躁，較佳時機是在第一分散劑之 前進行；或 —没有分散劑之乾研磨來進行，接著用包含分散劑之水 進行混合或者隨後加入分散劑形成一高固體濃度懸浮液。 "本發明較佳^方法是在—至少有三個研磨階段中進 仃，其中最後三個階段皆爲介質磨碎研磨階段，且每一個 都在分散劑加成之後進行。 這三個階段可在初步步驟之其中一個之前進行，例如A Please read the above note before i% i this-% order 1 \ w 18 paper size Langzhong H country transfer (CNS) 纟 4 threats (2 丨 Gx297) Printed by the staff of the Central Standards Bureau of the Ministry of Economic Affairs System A7 _____B7 V. Description of the Invention (4) Floating liquid, the addition position of the dispersant can be linked with each grinding stage. Each dispersant addition site may contain a grinding container or mill, which is ground in the container, but we prefer to add the dispersant to the suspension before the suspension reaches the grinding stage, such as in a pump. In combination, this pump is used to drive the suspension into the grinding stage located downstream of the suspension. According to the present invention, an additional dispersant addition site may be located downstream of the last milling stage to introduce more dispersant and other additives (if necessary) into the suspension being milled. The stage of suspension of the ground particulate material is dehydrated (if necessary) to a concentration of at least 65% by weight of the dry matter, or not so severe. Therefore, the addition of the polycarboxylate dispersant after grinding may be performed before or after the dehydration in step (C). The inorganic particulate material may include an insoluble salt of an alkaline earth metal, such as an insoluble salt of calcium. This material can be used as a pigment, especially a paper coating pigment, which can be used as a component of a known paper coating composition. In the suspension of step (a), the concentration of the particulate inorganic material is preferably 40% by weight, and a more preferred range is between 60 and 80% by weight. The method according to the invention can be carried out in a continuous manner or in a batch process. Preferably, the process is a multi-stage continuous grinding method, in which the treated aqueous suspension is continuously passed between the grinding stages, and the grinding stages are carried out in separate but interconnected containers. This one-speed method is known to be a method of grinding in a large number of drops. It can be ground into a finer solid material. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm). (Please read the precautions on the back first. Fill out this page), τ 5. In the description of the invention (16), add the same dispersant used in the early stage, which accounts for 0.25% of the dry weight of the marble. For part B, add polypropylene with an average molecular weight of 6,500 (please Read the precautions on the back before filling this page) Dilute acid (for a completely neutralized form), without other additives, and add a polyacrylate dispersant with an average molecular weight of 6500 to Part B and adjust the pH of this suspension The value is around pH 9, for example pH 8.8 to 9.2. The amount of. Is added so that the number of retarded mols per unit weight of dry pigment added is the same as that of Part A. Each part is dehydrated by membrane filtration, so that the solid concentration is 76% of the dry weight of the marble, and each suspension is dehydrated immediately with a Brookfield viscosity meter and a No. 3 shaft at a speed of 1000 rpm for viscosity. Detect. After the suspension was allowed to stand for 1 hour and 24 hours, the viscosity of the suspension was measured again. For comparison, the marble was ground with a grinding medium to a particle size distribution such that particles with an equivalent sphere diameter of less than 2 μm accounted for 90% by weight to prepare another suspension. However, in this example, at the beginning of the grinding operation, the completely neutralizing dispersant used in part A was added in an amount of 0.55% by weight based on the weight of the dry marble. -The results obtained are detailed in the table below. Part A is at the following time 10 hours 185 1 The measured viscosity value is 1 hour 330 (mPa * s) 24 hours 640 Part B 150 210 350 Comparative group 220 600 1360 These results indicate that the size distribution of the particles being ground is 90% A suspension containing 76% by weight of marble containing granules with an equivalent sphere diameter less than 2 μιη. After grinding, it is treated with a polycarboxylate dispersant. 19 This paper applies the Chinese National Standard (CNS) A4 specification ( 210 × 297 mm) A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (5) Can be passed into the suspension downstream of the grinding chain. Between the grinding stages and optionally after the last grinding stage device, there is a device that separates solid materials according to particle size, such as a sieve or screen, so that only the finer separation parts can pass. It can be introduced into one or more grinding vessels at each grinding stage. For example, the first stage can be introduced into a single container and one or more subsequent stages can be introduced into a plurality of containers connected in series or in parallel, such as two or three containers. Grinding at each grinding stage also includes (3) the use of a known medium such as alumina or silica particles or an oxide mixing system; or (b) automatic grinding of particles without the addition of grinding media to each other . Include at least the last stage of the process the nature of grinding. In each grinding stage, the suspension is ground by a grinding medium, preferably by a particulate grinding medium, where the particles are not less than 2 mm and not less than 0.1 mm for grinding. The particles of the grinding medium are more preferably not larger than 1 mm and not smaller than 0.25 sides. After each grinding stage, the ground particulate matter is separated from the grinding medium. & At each addition position, the dispersant can be added in a single dose, or if the process is a continuous process, a plurality of separate doses or a continuous addition is made. The method according to the invention may be carried out before the grinding stage by including at least one preliminary comminuting step or a plurality of other processing steps. For example, the particle size distribution of this Yiji particle when entering the first grinding stage is so large that particles with an equivalent sphere diameter less than 10 μιη account for at least weight (CNS) Α4 »(210X297 ^ " (Please read the precautions on the back first) (Fill in this page again) • Bae _-order _, In-_ mi. IB7 06 · — 6 芩 芩 芩 芩 五 五 五 五 五 发明 发明 发明 发明 发明 发明 理 理 理 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 理 理 理 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 ， 发明 发明 发明 发明 发明 发明 发明 发明 发明 and adjust the pH to pH 8.8 to 9.2. The dose of k- completely neutralized polycarboxylic acid dispersant was treated and compared without controlling the pH. It can be found that the suspension treated in the former method has a lower initial viscosity and is less prone to gelation, or It is not easy to increase the viscosity after standing. Moreover, the two suspensions treated by adding another dose of dispersant after grinding are prepared by adding the same total amount of dispersant in a single dose at the beginning of grinding. Grinding Dali; compared with suspension liquid phase, the former shows better rheology. (Please read the precautions on the back before filling this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This paper is suitable for China Standard (CNS) A4 (210X297 mm) A7 B7 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (6) 30% (best not more than 75%) and equivalent sphere diameter less than 2 (^ 111 of The proportion of particles is not less than 20%. These particles can be obtained by mineral shaving treatment, such as chalk or marble treatment, the diameter is up to 100mm, and the normal diameter range is between 10mm and 30mm Mineral shavings include a preliminary full-closing step in a mill, such as a hammer mill or an automatic wet mill such as US Patent 4,325,514 or preliminary wet grinding. In the preliminary wet grinding step, the solid concentration of the suspension To determine whether to use a dispersant. If the solid concentration is above 50% by weight, a dispersant is normally used. This dispersant is preferably a polycarboxylate in this preliminary step. For example, this The preliminary grinding step may be any one of the following steps:-the condition of automatic wet grinding with a dispersant, which has a high solid concentration (more than 50% by weight, preferably 65% to 80%);-without a dispersant Automatic wet Grinding conditions, with low solids concentration (less than 5G% by weight) but with or without-grinding media with chemical composition and this medium is different from grinding media with particulate matter; in this case, the method according to the present invention requires-dehydration Step by step, the preferred time is before the first dispersant; or-dry milling without dispersant, followed by mixing with water containing dispersant or subsequently adding dispersant to form a high solids suspension. &Quot; The preferred method of the present invention is to carry out in at least three grinding stages, of which the last three stages are medium grinding and grinding stages, and each is performed after the dispersant addition. These three stages can be performed before one of the preliminary steps, such as
本紙張尺度關家髀（CNS 210X297公釐） (請先閲讀背面之注意Ϋ-項再填寫本頁) ί -裝-----—ΐτ----- 經濟部中央標準局員工消費合作社印製 A7 __________—_B7 五、發明説明（~~ ^- 上id之初ν磨細步驟之則。若一初步磨細步驟包含在内的 話，則我們希望它是-自動的澄研磨步碌。本發明整個製 程則包含（至少）四研磨階段製程。 在此三或四個階段製程中，當最後三個研磨階段的第 -個階段做爲進料裝置的懸浮液，微粒物質在含水懸浮液 經研磨锋之顆粒大小分佈是如此典型以致於當量球狀直徑 ㈣)小於2μηι之顆粒，重量百分比至少估廳，及一㈤ 小於ΙΟμηι之顆粒，好佔3〇%(較佳爲不超過75%)，其爲Guan Jiayu of this paper (CNS 210X297 mm) (please read the note on the back-and then fill out this page) ί -Installation --------- ΐτ ----- Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Print A7 __________—_ B7 V. Description of the invention (~~ ^-The first ν grinding step of the last id. If a preliminary grinding step is included, we hope that it is an automatic clear grinding step. The entire process of the present invention includes (at least) a four-grinding stage process. In this three- or four-stage process, when the first stage of the last three grinding stages is used as the suspension of the feeding device, the particulate matter is in an aqueous suspension. The particle size distribution of the milled front is so typical that the equivalent spherical diameter ㈣) is less than 2 μηι, and the weight percentage is at least estimated, and 1㈤ is less than 10 μηι, which accounts for 30% (preferably not more than 75%). ), Which is
經由 Micrometries Corporation 所製造之一 SEDIGRApH 5000機器所測得。由此研磨階段至下一個研磨階段之進料 裝置，有-較佳地顆粒大小分佈爲esd小於2μπι之顆粒， 佔重量百分比50%至80%之間，而esd小於ΐμιη者至少佔 40%。較佳&，此進料裝置對下一（上一）研磨階段有一顆粒 大小分佈，使得esd少於2μπι者重量百分比不會少於9〇% 及esd小於1 μπι者至少佔60%。 根據本發明之方法，此唯一或最後一個研磨階段可接 著由一或多個之步驟進一步進行處理。舉例來説，經研磨 的微粒物質之含水懸浮液可經由英國專利中 所述之泡沫浮選法（frothfIoati〇n)來處理，而將細部分產物 分離出，此細部分產物之顆粒，其esd小於者至少有 9Q%，及esd小於Ιμπι者至少有6〇%。 在上述本發明實施例中之較佳的三個或四個研磨階段 製程中，在最後三個研磨階段的第一個進料懸浮液中所含 之微粒無機固體物質，至少佔重量之4〇%，較佳地至少佔 i·—— I I n ϋ n 1 Γ i n —l· n HI 一 J (請先閱讀背面之注意事項再填寫本頁) 10Measured on a SEDIGRApH 5000 machine manufactured by Micrometries Corporation. The feeding device from the grinding stage to the next grinding stage has-preferably, particles with a particle size distribution of esd less than 2 µm, which accounts for 50% to 80% by weight, and those with esd less than ΐµm at least 40%. Preferably &, this feeding device has a particle size distribution for the next (previous) grinding stage, so that the weight percentage of esd less than 2 μm will not be less than 90%, and esd less than 1 μm will account for at least 60%. According to the method of the present invention, this single or last grinding stage can be further processed by one or more steps. For example, an aqueous suspension of milled particulate matter can be treated by frothfloat (FothfIoation) described in the British patent to separate the fine part of the product, the particles of the fine part of the product, the esd Less than 9Q%, and at least 60% for esd less than 1 μm. In the preferred three or four grinding stage processes in the above embodiments of the present invention, the particulate inorganic solid matter contained in the first feed suspension of the last three grinding stages accounts for at least 4% by weight. %, Preferably at least i · —— II n ϋ n 1 Γ in —l · n HI a J (Please read the precautions on the back before filling this page) 10
A7 A7A7 A7
五、發明説明（， 重量之5〇%，最佳的至少姑重量之6〇%(以其乾重爲基準）。 通常在那個階段，含水懸浮液是不可能含有此微粒 過 80%。 ^ —裝--- - 乙 . (請先閱讀背面之法意事項再填寫本頁) 此唯一或最後-個階段的研磨持續進行直到被研磨的 微粒物質之顆粒大小分佈情況於當量球此直徑小於_之 顆粒至少佔重量之65%才停止。 由本發明之方法所處理之微粒物質可包括一個或多個 的碳酸心硫酸鹤’硫酸鋇切酸鎂，全部爲球或合成 的’例如沈澱的或原始的。較佳的物質是來自礦石中，如 白t (chalk)或大理石中之天然碳酸鈣。此原始的礦石包含 其他成分之次多含量（例最多占重量之1〇%)例，長石及石 英。 若在一個多階段研磨方式中，步驟0)與0)可結合在 一起，使得此含水懸浮液在單一研磨室或第一個研磨階段 中形成。 步驟（a)中的聚羧酸鹽分散劑較佳爲完全被中和的聚 羧酸鹽。此狀況下，懸浮液之pH値仍維持在ι〇 ι或接近 10.0。 經濟部中央標準局員工消費合作社印製 依據本發明之方法，在各種不同之加成位置加入聚羧 酸孤刀散劑，其可以爲相同或不同物質（稍後再進一步討 論）’較佳地包含一均聚物或包含一個或多個單體單位之共 聚物，其中之單體包含一乙烯基或豨烴基圏，此烯烴基團 可用至少一羧酸基團來取代，或其中之水溶性鹽類取代。 適合之單體爲丙烯酸，甲基丙烯酸，衣康酸，丁烯酸，富 11V. Description of the invention (50% by weight, preferably at least 60% by weight (based on its dry weight). Usually at that stage, it is impossible for an aqueous suspension to contain more than 80% of these particles. ^ — 装 ----B. (Please read the legal notices on the back before filling this page) This single or last-stage grinding is continued until the particle size distribution of the ground particulate matter is less than the diameter of the equivalent ball _ Particles should stop at least 65% by weight. The particulate matter treated by the method of the present invention may include one or more of carbonic acid sulfate 'barium sulfate and magnesium sulfate, all of which are balls or synthetic' such as precipitated or Primitive. The preferred material is natural calcium carbonate from ore, such as white t (chalk) or marble. This original ore contains the second most content of other ingredients (for example, up to 10% by weight). In a multi-stage grinding method, steps 0) and 0) can be combined so that the aqueous suspension is formed in a single grinding chamber or in the first grinding stage. The polycarboxylate dispersant in step (a) is preferably a polycarboxylate which is completely neutralized. Under this condition, the pH of the suspension was still maintained at ιοι or near 10.0. The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed the method according to the present invention to add polycarboxylic acid dagger powder at various addition positions, which may be the same or different substances (discussed further later). A homopolymer or a copolymer comprising one or more monomer units, wherein the monomer comprises a vinyl or fluorene hydrocarbon group, the olefin group may be substituted with at least one carboxylic acid group, or a water-soluble salt thereof Class replacement. Suitable monomers are acrylic acid, methacrylic acid, itaconic acid, butenoic acid, rich 11
經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（9 ) 馬酸，順式丁烯二酸，順式丁烯二（酸）酐，異丁烯酸，丙 烯三羧酸，甲基反式丁烯二酸，芥子酸，十一碳烯酸，當 歸酸，及經基丙稀酸。 依據本發明之方法，在每個加成位置所添加分散劑的 量爲每噸的微粒物質加入10至100莫耳的羧酸鹽。 研磨時，使處理過之懸浮液維持在一完全分散的狀況 下，其並不重要，然而在研磨期間，分散的狀況（由分散劑 的性質，所添加分散劑的量及處理過之懸浮液pH値所控 制）是如此均勻，使懸浮液爲完全流體以進行研磨，使合理 的能量進料至研磨機。在這方面，懸浮液在研磨階段所浪 費之能量總和，正常的話每噸乾燥顏料應不會超過500 KW 小時。通常最後懸浮液將完全分散，且不需要進一步加入 分散劑使之造成流體。 利用一低角度雷射光散射偵測器之凝膠滲透層析的方 法，測得聚羧酸鹽分散劑之平均分子量應不超過20,000且 較佳的範圍是從700至10,000。 更佳地，用於每個加成之聚羧酸酯分散劑爲一均聚物 或由重覆單元及下列結構所組成之共聚物：Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (9) Maleic acid, maleic acid, maleic (anhydride), methacrylic acid, propylene tricarboxylic acid, methyl trans Formulas of butenedioic acid, erucic acid, undecylenic acid, angelica acid, and trisuccinic acid. According to the method of the present invention, the amount of dispersant added at each addition site is 10 to 100 moles of carboxylate per ton of particulate matter. During grinding, it is not important to maintain the treated suspension in a completely dispersed state, but during the grinding, the state of dispersion (by the nature of the dispersant, the amount of dispersant added and the treated suspension) controlled by pH 値) is so homogeneous that the suspension is completely fluid for grinding and a reasonable amount of energy is fed to the mill. In this respect, the sum of the energy spent by the suspension during the grinding phase should normally not exceed 500 KW hours per ton of dry pigment. Usually the final suspension will be completely dispersed and no further dispersant needs to be added to make it fluid. The average molecular weight of the polycarboxylate dispersant measured by gel permeation chromatography using a low-angle laser light scattering detector should not exceed 20,000 and the preferred range is from 700 to 10,000. More preferably, the polycarboxylate dispersant used for each addition is a homopolymer or a copolymer consisting of repeating units and the following structures:
Ri RiRi Ri
I I —CH — C —I I —CH — C —
II
COOH 或當中之水溶性鹽，其中1爲-11，-Aik，—COOH或- 12 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝· " 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（10 ) COOAlk 及 R2 爲—η，—CH2，COOH 或-Aik。其中 Aik 表 示一具有1〜3個碳原子之烷基。 一共聚合物也可包含最多70%之下列結構之重覆單 元：COOH or water-soluble salts among them, 1 of which is -11, -Aik, —COOH or-12 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling in this Page) Equipment " Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (10) COOAlk and R2 are -η, -CH2, COOH or -Aik. Aik represents an alkyl group having 1 to 3 carbon atoms. A copolymer can also contain up to 70% of repeating units of the following structures:
Rs r4Rs r4
i I ~ CH ~CH - 其中 R3 爲—H，-C6H5 或-Aik.及 R4 爲一Cl，-CN，-COOAlk 或-OCOAlk，其中Aik表示一具有1~3個碳原子之烷基。 特別較佳的爲丙烯酸，甲基丙烯酸，順式丁烯二酸或 富馬酸之均聚合物的水溶性鹽類，兩個或更多單體共聚物 之水溶性鹽類，及帶有苯乙烯及醋酸乙烯酯之順式丁稀二 酸或富馬酸共聚物的水溶性鹽類。 此分散劑可以一酸或鹼的形式被加入.，且此鹼具有一 或更多個已知在分散劑習知技術中之中和陽離子，例如一 鹼金屬陽離子，銨陽離子或一燒基銨陽離子，其中此烷基 基團之碳原子數不超過7個。 如上所述，根據本發明之方法較佳地在至少三個研磨 階段中進行，且每一研磨階段與一將分散劑加入至含水懸 浮液之一個分散劑加成位置結合。每一次個別加入之分散 劑並不會超過研磨時所加入分散劑總量之50%。正常時， 分散劑加成位置的數目不會超過10個。較佳地，若有D 個加成位置，則每次加成都應該不超過製程期間之全部加 13 本紙張尺度適用中國國家標準（CMS ) A4規格（210X297公釐） ---------_ 裝— „ 一 - (請先聞讀背面之注意事項再填寫本頁) 灯 -———— 五、發明説明（11 ) 成量之(2/D X 100)%。較佳地，在每一加成位置都加入等 量之分散劑。 根據本發明之方法，此含水懸浮液在一或多個研磨階 段中研磨處理時，其pH在8.5至9.8的範圍内，更希望pH 範圍在8.5至9.5之間，特別在8.8至9.2之間。 圖式之簡單說明 圖1表示研磨過程之流程圖。 主要部分代表符號 1〜導管，2〜導管，3〜第一溼研磨機，4〜葉輪，5〜直 立轴，6〜微粒研磨介質’ 7〜筛子’ 8~出口，9〜導管，10〜 導管，11〜第二研磨機，12〜出口，13〜導管，14〜混合 槽，15~導管，16~出口。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 本發明之方法中，以各種明顯用於習知技術上處理無 機礦物懸浮液方法之一，將pH調整至所需範圍内。因此， 在實施例1的方法中，為了確認完全研磨後的pH值控制在 所需的範圍中，一種水溶性酸的分散劑加入懸浮液中，接 著並加入一鹼，如氫氧化鈉的處理。當顆粒變小時處理過 之顆粒表面上之可利用的陽離子數目增加，在許多階段中 鹼所加入的量，也可逐階段的減少，使得水相的pH值維持 在所需的範圍中。 在第二個實施例中，一種聚羧酸鹽的鹽類，例如聚羧 酸鈉，在研磨完成之後加入，且含水介質以水進行稀釋來 降低pH值，然後較佳地由一已知的脫水步驟再濃縮，如過 濾作用。稀釋方法及再濃縮的方法於本案申請人之英國專 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）i I ~ CH ~ CH-where R3 is -H, -C6H5 or -Aik. and R4 is a Cl, -CN, -COOAlk or -OCOAlk, where Aik represents an alkyl group having 1 to 3 carbon atoms. Particularly preferred are water-soluble salts of homopolymers of acrylic acid, methacrylic acid, cis-butenedioic acid or fumaric acid, water-soluble salts of two or more monomer copolymers, and benzene with benzene. Water-soluble salts of cis-succinic acid or fumaric acid copolymers of ethylene and vinyl acetate. This dispersant can be added in the form of an acid or a base, and this base has one or more neutralizing cations known in the conventional art of dispersants, such as an alkali metal cation, ammonium cation, or monoalkylammonium Cation, in which the number of carbon atoms of this alkyl group does not exceed 7. As described above, the method according to the present invention is preferably performed in at least three grinding stages, and each grinding stage is combined with a dispersant addition site where the dispersant is added to the aqueous suspension. The dispersant added individually each time will not exceed 50% of the total amount of dispersant added during milling. Normally, the number of dispersant addition sites will not exceed 10. Preferably, if there are D bonus positions, each addition to Chengdu should not exceed the total of 13 during the manufacturing process. This paper size is applicable to the Chinese National Standard (CMS) A4 specification (210X297 mm) ------- --_ 装 — „One-(Please read the precautions on the back before filling out this page) Lights ------- 5. Description of the invention (11) (2 / DX 100)% of the amount. Preferably, An equal amount of dispersant is added at each addition position. According to the method of the present invention, when the aqueous suspension is ground in one or more grinding stages, the pH is in the range of 8.5 to 9.8, and the pH range is more desirable. Between 8.5 and 9.5, especially between 8.8 and 9.2. Brief description of the drawing Figure 1 shows the flow chart of the grinding process. The main parts represent symbols 1 ~ duct, 2 ~ duct, 3 ~ first wet grinder, 4 ~ Impeller, 5 ~ Upright shaft, 6 ~ Particulate grinding medium '7 ~ Sieve' 8 ~ Outlet, 9 ~ Duct, 10 ~ Duct, 11 ~ Second grinder, 12 ~ Exit, 13 ~ Duct, 14 ~ Mixing tank, 15 ~ Duct, 16 ~ Export. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the note on the back first) (Please fill in this page again) In the method of the present invention, the pH is adjusted to the required range by one of various methods that are obviously used in conventional techniques for treating inorganic mineral suspensions. Therefore, in the method of Example 1, in order to Make sure that the pH after complete grinding is controlled in the desired range. A water-soluble acid dispersant is added to the suspension, followed by a base, such as sodium hydroxide treatment. When the particles become small, the surface of the treated particles The number of available cations is increased, and the amount of base added in many stages can also be reduced step by step, so that the pH of the aqueous phase is maintained in the desired range. In a second embodiment, a polycarboxylate Salts of acid salts, such as sodium polycarboxylate, are added after the milling is complete, and the aqueous medium is diluted with water to lower the pH, and then preferably concentrated by a known dehydration step, such as filtration. Dilution method And the method of re-concentration is applied to the applicant ’s UK-specific paper size, which applies the Chinese National Standard (CNS) A4 specification (210X297 mm)
五、發明説明$1-1) 利 PCT/GB95/00563(WO 95/25146)中有描敘。 在第三個實施例，將不同的分散劑加至不同的加成階 段。因此在研磨期間，將完全被中和的聚羧酸鹽加入以作 為分散劑，而在研磨完成之後，將一酸型式之分散劑加入。 較佳地，在每一個實施例中，不同分散劑之鹼性聚合物或 共聚物為相同的。 第四個實施例中，將不同分散劑的化合物在研磨完全 ---------.^------^-I1T------ /! , (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 14-1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（12 ) 之後加入。此不同的試劑可包含一完全被中和聚羧酸鹽類 及一酸型式之聚羧酸鹽，將之一個接著一個另一個分別加 入階段中。較佳地，在每一個實施例中不同分散劑之鹼性 聚合物或共聚物是相同的。 第五個實施例中，將一部分中和的聚羧酸鹽在研磨完 全之後加入。供顏料作研磨使用之部分中和的聚羧酸鹽在 研磨完全之後加入。供專利JP 55-40715中可知。在研磨 礦物材質時所使用的試劑，如水相介質中之CaC03，在美 國專利USA-4840985中也有描敘。然而説明書中所述之方 法是應用於單一階段且在説明書之狀況下所處理之微粒礦 物材質爲粗糙的，及在研磨之前或研磨期間，將此部分中 和試劑加入研磨介質中有助於研磨，及所加入之試劑中和 的程度在40%至96%之間。另一方面，若以本發明之方法 來進行，則我們考慮加入第五實施例之部分中和的聚羧酸 鹽分散劑，在完全研磨後，將此聚羧酸鹽加入質地細微的 材質中。而此試劑中和的程度爲30%或少於30%。在此實 施例，於研磨之前或研磨時加入的分散劑，可包令 完全 中和的聚羧酸鹽。較佳地在不同研磨階段所使用之部分或 完全中和的聚羧酸鹽，包含相同的鹼性聚合物或共聚物， 例如，一聚後酸納。 根據本發明之方法，在一多階段研磨方式中之一或多 個研磨階段中，特別是在最後一個研磨階段，此pH値也 維持在8.5至9.8的範圍中。所有階段的pH値，可由所加 入之分散劑的量/或所加之中和試劑的量（若有使用此試劑 『 「//1-響 —•—.— — —— — — —V 1 m I - n -vn —II、Trm 1 m I I- 1 - (請先閱讀背面之注意事項再填寫本頁) 15 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央標隼局員工消費合作社印製 A7 —---—__B7 五、發明説明（13 ) 的話），來調整pH値，直到pH値在所需範圍内爲止。此. 調整步驟是使用一自動機械加成裝置在緊密線圈控制下所 測得之pH値，來進行調整。 根據本發明之方法實施例一至五中之pH皆調在範 圍，當含水懸浮液一邊攪動或攪拌時，此分散劑及其他加 成物（若有的話），例實施例二中的鹼，則也一邊加入。而 此含水懸浮液的pH値將很快，幾乎是瞬間就可被調整在 調整在範圍内。 本發明之方法使用全部分散劑的量最後可提供一完全 反絮凝（defl〇cculated)之懸浮液。實際上，全部分散劑的量 至少佔重量的0.1。/。，其以微粒無機材質的乾重爲基礎，而 通常不會超過重量的L5%。更佳地，錢明所使用分散劑 的量至少佔微粒無機材質乾重之0.05%。正常的話，在每 個加成位置，分散劑的量不會超過1〇%，實際上分散劑所 使用的量是以乾燥無機微粒物質爲基準。另—種定量分散 劑的方法爲個每噸乾燥顏料中羧基之莫耳數。因此，正常 地狀況下分散劑在研磨之前或研磨時所加入的量，較佳的 範圍是每噸乾燥顏料加入10至1〇〇莫耳的羧酸鹽的量且步 驟（c)中分散劑加入的量，較佳的範圍是每噸乾顏料加入1〇 土 100莫耳的後酸鹽。在實施例中之完全中和之聚丙稀酸 納單體（CIVCH.COONa)之分子量爲94克，而聚（丙稀 酸)(CH2.CH.C00H)單體之分子量爲72克。這每一個聚合 體分散劑，每單體單位有1莫耳的羧酸鹽。在每啪的乾顏 料中有後酸鹽之聚（丙稀酸）10莫耳，其佔顏料乾重之' 本紙張尺度適用中國國家標準（CNS M4規格（210X29X^7 (請先閱讀背面之注意事項再填寫本頁) i 裝· -訂_ 齋 Μ βΑΤ ^ -a 五、發明説明（14 ) 0.079% ° 將經過研磨的無機材質之懸浮液脫水，其方法與昔知 技術相似，例如使用熱蒸發作用，過濾，或使用離心機。 若在步驟（c)中於脫水前加入分散劑，則較佳的脫水步驟是 經膜過濾進行較有效率。此懸浮液脫水至濃度至少為乾顏 料重之75%為佳。 為了使本發明更容易了解，及表示本發明如何產生作 用，依本發明之方法則晝出一圖解的流程圖，如第一圖所 示0 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 一鹼土金屬顏料的懸浮液經初步粉碎之後，經由導管1 導入第一個溼研磨機3 。一個大體上完全被中和之聚羧 酸鹽分散劑的溶液也經由導管2導入其中。此研磨機中有 一葉輪4，此葉輪藉由一合適的啟動裝置（沒有標示出）於 一直立軸5上旋轉。在研磨機進行研磨之前，此研磨機内 充滿微粒研磨介質6，其包含的顆粒範圍在0.5至1.0mm 之間。在此鹼土金屬顏料經一次研磨後，當量球體直徑小 於2μιη顆粒所佔之重量比例降低，降至一適中的值，此懸 浮液經篩子7之0.25mm小篩孔收回鹼土金屬顏料之懸浮 液而留下研磨介質，經由出口 8及導管9，導入第二研磨 機11，此研磨機與第一研磨機完全相同。而經由導管10 將大體上完全中和的聚羧酸鹽分散劑之溶液導入第二研磨 機内。在此鹼土金屬顏料經研磨達最後所需之細微程度之 後，將顏料之懸浮液拉引經出口 12，此出口有研磨材質殘 留在篩子上，並經導管13導至混合槽14。經由導管15 17 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 第85111170號說明書修正頁 A> B7 五、發明説明（15 )定量之聚鲮酸鹽分散劑導入其中 1辩f明示—正後是否變—i 經濟部中央標準局員工消費合作社印t 法調至約PH9。若需要添加其他松且將pH值*如上ϋ 藉由導管15加^於混合—段時^例如制Η，也可 酸鹽分散劑散佈在整個顏料的懸^此部分中和之聚缓 定流變性的顏料懸浮液被拉引至出口 Μ，為-流體及具穩 在其他的實施例中（沒有表 殺，軔4认μ· “ ^ 丁出來）’更多的研磨階共至少有三個研磨階段，其與研磨㈣狀況 本發明由下列實施例來作進一步的說明。實施例 天然大理石質地之粉末的樣品，其顆粒大小分布是 使传大體上全部顆粒都比53μ則、，將此樣品與含有大理 石乾重之0.2%之完全中和之平均分子量& &⑼的聚丙稀 酸納分_之核合。如麟形叙懸雜含有65%重量 比的，大理石。使用具有大體上直捏在。5 至i 〇 mm 之球狀顆粒的二氧化矽沙作為研磨介質*以將此懸浮液予 以研磨。研磨將持續進行直到大理石之顆粒分佈情況為具 當量球體直徑小於2μηΐ2顆粒佔重量之4〇%才停止。 進一步加入大理石乾重之〇.1%的相同分散劑量，並將 經研磨之大理石懸浮液通入至第二研磨階段，且使用與第 個研磨階段相同等級之二氧化發沙顆粒。此研磨作用將 持續進行直到大理石之顆粒分佈情況為當量球體直徑小於 2μΓη之顆粒佔重量之90%才停止。質地报細微之大理石懸浮液分成Α與Β兩部分。對V. Description of the invention $ 1-1) It is described in PCT / GB95 / 00563 (WO 95/25146). In a third embodiment, different dispersants are added to different addition stages. Therefore, during the grinding, a fully neutralized polycarboxylate is added as a dispersant, and after the grinding is completed, an acid type dispersant is added. Preferably, in each embodiment, the basic polymers or copolymers of different dispersants are the same. In the fourth embodiment, the compounds of different dispersants are completely ground ---------. ^ ------ ^-I1T ------ /!, (Please read the back first Please fill in this page again) Printed by the Central Consumers ’Cooperative of the Ministry of Economic Affairs 14-1 Printed on the paper standard of China National Standards (CNS) A4 (210X297 mm) A7 B7 Printed by the Consumer ’s Cooperatives of the Central Standards Bureau of Ministry of Economic Affairs 5. Invention description (12) is added after. This different reagent may comprise a polycarboxylate which is completely neutralized and a polycarboxylate of an acid form, which are added to the stage one after the other. Preferably, the basic polymers or copolymers of the different dispersants are the same in each embodiment. In a fifth embodiment, a part of the neutralized polycarboxylate was added after the grinding was completed. Partially neutralized polycarboxylates for pigments for grinding are added after grinding is complete. Available from Patent JP 55-40715. The reagents used when grinding mineral materials, such as CaC03 in aqueous media, are also described in US Patent USA-4840985. However, the method described in the instructions is applied to a single stage and the particulate mineral material processed under the conditions of the instructions is rough, and it is helpful to add this part of the neutralizing reagent to the grinding medium before or during grinding. The degree of neutralization during grinding and the added reagents is between 40% and 96%. On the other hand, if it is carried out by the method of the present invention, we consider adding a partially neutralized polycarboxylate dispersant in the fifth embodiment. After being completely ground, this polycarboxylate is added to a fine-grained material. . The degree of neutralization of this reagent is 30% or less. In this embodiment, the dispersant added before or during the milling may include a fully neutralized polycarboxylate. The partially or fully neutralized polycarboxylates preferably used in the different milling stages comprise the same basic polymer or copolymer, e.g., sodium polyacrylate after polymerization. According to the method of the present invention, the pH 多 is also maintained in the range of 8.5 to 9.8 in one or more of the grinding stages in a multi-stage grinding method, especially in the last grinding stage. The pH at all stages can be determined by the amount of dispersant added / or the amount of neutralizing reagent added (if this reagent is used "// 1- 响 — • —.— — — — — — V 1 m I-n -vn —II, Trm 1 m I I- 1-(Please read the notes on the back before filling out this page) 15 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) Central Ministry of Economic Affairs A7 is printed by the Consumers ’Cooperative of the Bureau of Standards ------__ B7 V. Inventive Note (13)), to adjust pH 直到 until pH 値 is within the required range. This adjustment step is to use an automatic mechanical processing The pH value measured by a compact device under the control of a tight coil is adjusted. The pH values in the first to fifth embodiments of the method according to the present invention are adjusted to a range. When the aqueous suspension is agitated or stirred, the dispersant and others The adduct (if any), the base in Example 2 is also added at the same time. The pH of this aqueous suspension will be very fast, and it can be adjusted within the range almost instantaneously. The present invention The method uses the total amount of dispersant to provide a complete reaction Deflocculated suspension. In fact, the total amount of dispersant is at least 0.1% by weight. It is based on the dry weight of the particulate inorganic material, and usually does not exceed L5% by weight. Better Ground, the amount of dispersant used by Qian Ming is at least 0.05% of the dry weight of the particulate inorganic material. Normally, the amount of dispersant will not exceed 10% at each addition position. In fact, the amount of dispersant used It is based on dry inorganic particulate matter. Another method of quantitative dispersant is the number of moles of carboxyl groups per ton of dry pigment. Therefore, under normal conditions, the amount of dispersant added before or during grinding is smaller than A preferred range is the amount of carboxylate added from 10 to 100 moles per ton of dry pigment and the amount of dispersant added in step (c). A preferred range is 100 moles per ton of dry pigment. The post-acid salt. The molecular weight of the completely neutralized sodium polyacrylic acid monomer (CIVCH.COONa) in the examples is 94 g, and the molecular weight of the poly (acrylic acid) (CH2.CH.C00H) monomer is 72 grams. Each polymer dispersant has 1 mole per monomer unit. The acid (polyacrylic acid) of each post-dried pigment is 10 moles, which accounts for the dry weight of the pigment. This paper size applies to Chinese national standards (CNS M4 specifications (210X29X ^ 7 (please first Read the notes on the back and fill in this page again.) I Packing · -Order _ Zhai M βΑΤ ^ -a V. Description of the invention (14) 0.079% ° Dewatering the suspension of the ground inorganic material, the method is similar to the previous technology For example, using thermal evaporation, filtration, or using a centrifuge. If a dispersant is added before dehydration in step (c), a better dehydration step is more efficient through membrane filtration. The suspension is preferably dehydrated to a concentration of at least 75% by weight of the dry pigment. In order to make the present invention easier to understand, and to show how the present invention works, according to the method of the present invention, a diagrammatic flowchart is displayed daily, as shown in the first figure. 0 (Please read the notes on the back and fill in this page again) After a preliminary pulverization of the alkaline earth metal pigment suspension, it is introduced into the first wet grinder 3 through the conduit 1. A solution of the polycarboxylate dispersant which is substantially completely neutralized is also introduced into it via the catheter 2. The grinder has an impeller 4 which is rotated on a vertical shaft 5 by a suitable starting device (not shown). Before the grinder is ground, the grinder is filled with a particulate grinding medium 6 containing particles ranging from 0.5 to 1.0 mm. After the alkaline earth metal pigment is ground once, the weight ratio of particles with an equivalent sphere diameter less than 2 μιη is reduced to a moderate value. The suspension is recovered through a small 0.25 mm sieve of the sieve 7 to recover the suspension of the alkaline earth metal pigment. The grinding medium is left, and is introduced into the second grinding machine 11 through the outlet 8 and the duct 9. This grinding machine is completely the same as the first grinding machine. A solution of the substantially completely neutralized polycarboxylate dispersant is introduced into the second mill through the conduit 10. After the alkaline earth metal pigment has been ground to the last required degree of fineness, the pigment suspension is drawn through an outlet 12 where the ground material remains on the sieve and is guided to the mixing tank 14 through a conduit 13. Via conduit 15 17 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) No. 85111170 Specification Correction Page A > B7 V. Description of the invention (15) Introduction of quantitative polyphosphonate dispersant Explicitly-whether it will change after i-i The law of the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economy is adjusted to about PH9. If you need to add other pine and add the pH value * as above, add it through the conduit 15 to the mixing stage ^ such as making Η, or the acid dispersant can be dispersed throughout the suspension of the pigment ^ this part of the neutralized polymer flow The denatured pigment suspension is drawn to the outlet M, which is-fluid and stable in other examples (no surface killing, 轫 4 认 μ · "^ Ding out) 'more grinding stages with a total of at least three grinding The present invention is further explained by the following examples. The sample of natural marble texture powder has a particle size distribution such that substantially all particles are smaller than 53 μ. Contains 0.2% of the completely neutralized average molecular weight of the dry weight of marble & & < " > Squeeze. Silica sand with spherical particles of 5 to 10 mm is used as the grinding medium * to grind this suspension. The grinding will continue until the particle distribution of the marble is equivalent to a spherical diameter of less than 2μηΐ2 particles account for the weight of 4 〇% was stopped. Further add the same dispersing amount of 0.1% of the dry weight of marble, and pass the ground marble suspension to the second grinding stage, and use the same grade of sand dioxide as the first grinding stage. Granules. This grinding will continue until the distribution of marble particles is equivalent to 90% by weight of particles with an equivalent sphere diameter less than 2μΓη. The fine marble suspension is divided into two parts, A and B.
A 請 先 閲 讀 面 之 注 項 再i% i 本 -% 訂 1 \w 18 本紙張尺度朗中H國家轉（CNS )纟4胁（2丨Gx297公着） 五、發明説明（16 ) 部分，加入早期階段所使用之相同分散劑，其量佔大理石 乾重之0·25%，對B部分則加入平均分子量為6500的聚丙 (請先閲讀背面之注意事項再填寫本頁) 稀酸（為完全中和之型式），且無其他的添加物，及對Β部 份添加平均分子量為6500的聚丙烯酸鹽分散劑並調整此 懸浮液pH值大約在pH 9，例如pH 8.8至9.2。所加入.的 量是使得，對於每單位重量之乾色素所加入的缓酸基莫耳 ¥ 數，和A部分是相同的。每一部分皆經膜過濾作用脫去水 份，使固體濃度為大理石乾重之76%，且每個懸浮液在脫 水後立即以一 Brookfield黏度計配合3號軸，速度為 lOOOrpm，進行黏稠度的偵測。再於懸浮液分別靜置1小 時及24小時後，再測量懸浮液的黏度。 為了用作比較，將大理石以研磨介質研磨至顆粒大小 分佈為使得具當量球體直徑小於2μηι之顆粒佔重量之 90%，以製備另一懸浮液。然而，在此例中，在研磨操作 開始時，加入在Α部分所使用之完全中和分散劑，其量為 乾大理石重量之0.55%重量比。 - 所得之結果詳列於下表中。 Α部分 於下列時間1 0小時 185 1所測之黏度值 1小時 330 (mPa*s) 24小時 640 B部分 150 210 350 比較組 220 600 1360 這些結果表示，對於被研磨成顆粒大小分佈為90%重 量為當量球體直徑小於2 μιη的顆粒之含有76%重量比之 大理石的懸浮液，當其在研磨後以聚羧酸鹽分散劑作處 19 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） IB7 06· — 6 芩酌无 五、發明説明（17 ) 理，並將pH調整為pH 8.8至9.2時，與當其以當量劑量之 k- 完全中後和之聚羧酸分散劑作處理，並且不控制pH時來 作比較，可發現以前者方式處理的懸浮液具有較低的初始 黏度，並且較不易凝膠，或較不易在靜置後黏度增加。而 且，對於在研磨後再以加入另外劑量之分散劑來處理的兩 懸浮液，與在研磨開始時即以單獨劑量方式加入相同總量 的分散劑所製得的研磨大理；懸浮液相比較，前者顯現出 較優異的流變性。 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）A Please read the above notes before i% i this-% order 1 \ w 18 paper size Langzhong H country transfer (CNS) 纟 4 threats (2 丨 Gx297) V. Description of the invention (16), Add the same dispersant used in the early stage, the amount of which is 0.25% of the dry weight of the marble. For Part B, add polypropylene with an average molecular weight of 6500 (please read the precautions on the back before filling this page). Dilute acid (for Completely neutralized type), without other additives, and adding a polyacrylate dispersant with an average molecular weight of 6,500 to Part B and adjusting the pH of the suspension to about pH 9, such as pH 8.8 to 9.2. The amount of. Is added so that the number of retarded mols per unit weight of dry pigment added is the same as that of Part A. Each part is dehydrated by membrane filtration, so that the solid concentration is 76% of the dry weight of the marble, and each suspension is dehydrated immediately with a Brookfield viscosity meter and a No. 3 shaft at a speed of 1000 rpm for viscosity. Detect. After the suspension was allowed to stand for 1 hour and 24 hours, the viscosity of the suspension was measured again. For comparison, the marble was ground with a grinding medium to a particle size distribution such that particles with an equivalent sphere diameter of less than 2 μm accounted for 90% by weight to prepare another suspension. However, in this example, at the beginning of the grinding operation, the completely neutralizing dispersant used in part A was added in an amount of 0.55% by weight based on the weight of the dry marble. -The results obtained are detailed in the table below. Part A is at the following time 10 hours 185 1 The measured viscosity value is 1 hour 330 (mPa * s) 24 hours 640 Part B 150 210 350 Comparative group 220 600 1360 These results indicate that the size distribution of the particles being ground is 90% A suspension containing 76% by weight of marble containing granules with an equivalent sphere diameter less than 2 μιη. After grinding, it is treated with a polycarboxylate dispersant. 19 This paper applies the Chinese National Standard (CNS) A4 specification ( 210Χ297 mm) IB7 06 · - 6 baicalensis no discretion V. Description of the invention (17) Li, and the pH was adjusted to pH 8.8 to 9.2, which is equivalent to when a dose of k- and after full dispersion of polycarboxylic acid When the agent is treated and the pH is not controlled for comparison, it can be found that the suspension treated in the former way has a lower initial viscosity, and is less prone to gelling, or less prone to increase in viscosity after standing. Moreover, for the two suspensions treated by adding another dose of dispersant after grinding, compared with the grinding liquid prepared by adding the same total amount of dispersant in a single dose at the beginning of grinding; compared with the suspension liquid phase, The former shows better rheology. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs This paper is sized for China National Standard (CNS) A4 (210X297 mm)
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9518597.1A GB9518597D0 (en) | 1995-09-12 | 1995-09-12 | Aqueous suspensions of alkaline earth metal pigments |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW394705B true TW394705B (en) | 2000-06-21 |
Family
ID=10780573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW85111170A TW394705B (en) | 1995-09-12 | 1996-09-12 | Process for preparing a concentrated aqueous suspension of a finely ground particulate material and the product thereof |
Country Status (2)
| Country | Link |
|---|---|
| GB (1) | GB9518597D0 (en) |
| TW (1) | TW394705B (en) |
-
1995
- 1995-09-12 GB GBGB9518597.1A patent/GB9518597D0/en active Pending
-
1996
- 1996-09-12 TW TW85111170A patent/TW394705B/en not_active IP Right Cessation
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| Publication number | Publication date |
|---|---|
| GB9518597D0 (en) | 1995-11-15 |
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