508249 A7 B7 五、發明説明（1 ) 本發明之背景 本發明係關於製造粒狀淸潔劑之方法，其帶有鬆密度 高達至少0 · 7g/cm3,尤其是0 · 7至0 · 9 g / c m 3，且廣泛地用於，例如，衣物用淸潔劑組成物。 已有各種製造帶高鬆密度粒狀淸潔劑而不須使用噴霧 乾燥塔之方法被提出。在大部分已提出方法中，係將粒狀 鹼送入附有攪拌器之切變成粒器，之後將陰離子界面活性 劑之液體酸前驅物緩緩地滴入或噴入，此時由攪動而保持 粒狀鹼流動，並保持在流動狀態以執行粒化〔例如見 Japanese Patent Unexamined Published Application (以下弓| 用作”J· P. ΚΟΚΑΓ ) No· Hei 4 - 3 6 3 3 9 8 及爲相相目 的的 Japanese Patent Publication (以下引用作"J. P. KOKOKU" ) No. Hei 6 - 7 8 6 5 8 )。 經濟部中央標隼局員工消費合作社印製 在這些方法中，由於粒化尙不充分而須要黏結劑，此 外，將難以得到鬆密度高達至少0 · 7 g / c m 3之產物， 尤其是至少0 · 8 g / c m 3。此外，也須使用滴液設備或 噴霧設備以將陰離子界面活性劑之液體酸前驅物加入，也 須複雜操作以控制這些材料之進料量。 本發明槪要 本發明目標係爲提供製造高鬆密度粒狀淸潔劑之方法 ，由使用攪動/粒化方法能簡易地增加鬆密度。 本發明之此項及其它目標可由下列敘述及實施例明顯 看出。 -4- (請先閱讀背面之注意事項再填寫本頁} 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 508249 A7 B7 經濟部中央標隼局員工消費合作社印製 五、發明説明（2 ) 本發明係基於下列發現而完成：當一種液體酸前驅物 層與粉末層接觸，該粉末層中粒狀鹼組份含量大於中和液 體酸前驅物所須，以大團形式形成一層，且於使用至少一 份的液體酸前驅物含浸粉末層後，以帶有攪動及切變功能 之粒化器將生成物攬動並混合，此方法造成之優點在於， 可作粒化，可在短於先前技藝所須之時間內完成中和，可 在單一步驟中製造高鬆密度粒狀淸潔劑，並可有效地解決 前述問題。 也就是，本發明提供製造高鬆密度粒狀淸潔劑之方法 ，其中包含以粒狀鹼組份中和陰離子界面活性劑之液體酸 前驅物，並粒化此中和產物，且其特色在將一層液體酸前 驅物與粉末層接觸，該粉末層中粒狀鹼組份含量大於中和 液體酸前驅物所須，以至少一份的液體酸前驅物含浸粉末 層，之後攪動並混合生成物以同時執行中和與粒化。 較佳的體系之敘述 本發明之陰離子界面活性劑之液體酸前驅物可用任何 的衣物用淸潔劑組成物。其中較佳者爲線性的或分支的烷 基（平均碳鏈長：8至1 8 )苯磺酸，長鏈烷基（平均碳 鏈長1 0至2 0 )磺酸，長鏈烯烴（平均碳鏈長：1 0 至2 0 )磺酸，長鏈單烷基（平均碳鏈長：1 0至2 0 ) 醚硫酯，聚伸氧基乙烯（平均聚合度：1至1 0 )鏈烷基 (平均碳鏈長：1 0至2 0 )醚硫酯，聚伸氧基乙烯（平 均聚合度：3至30)烷基（平均碳鏈長：6至12)苯 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CMS ) A4規格（210X297公釐） -5 - 508249 A7 B7 經濟部中央標拿·局員工消費合作社印製 五、發明説明（3 ) 基醚硫酯，^ -硫脂肪酸（平均碳鏈長：8至2 2 )，長鏈 單烷基，二烷基或倍半烷基磷酸，聚伸氧基乙烯單烷基， 二烷基及倍半烷基磷酸。它們宜單獨或以其二或更多個混 合物形式使用。其中，尤其較佳的是一個，或二或更多個 之混合物的，線性的或分支的烷基（平均碳鏈長·· 8至 18)苯擴酸’長鏈院基（平均碳鏈長：10至20)磺 酸，長鏈烯烴（平均碳鏈長：1 〇至2 0 )磺酸，長鏈單 烷基（平均碳鏈長：1 0至2 0 )硫酯，聚伸氧基乙烯（ 平均聚合度：1至10)鏈烷基（平均碳鏈長：10至 2 0 )醚硫酯及α -硫脂肪酸（平均碳鏈長：8至2 2 ) 〇 本發明所使用陰離子界面活性劑之酸前驅物爲水溶液 漿液。此水溶液漿液含有7 0至1 0 0 %重量（以下引用 作”％ ”），更佳爲9 0至1 0 0 %的酸前驅物。此外，水溶液漿液黏度較佳爲0 · 1至5 0 p ( 1 0至8 0 °C ) 〇 可用於本發明之水溶液漿液在陰離子界面活性劑之酸 前驅物之外，可包含非離子界面活性劑。在此所用非離子 界面活性劑包括，例如，（1 ) E〇加合型非離子界面活 性劑，其係得自在帶有8至1 8碳原子的一級或二級醇中 ，加入平均4至5 0莫耳的環氧乙烷，（2 ) E〇-P〇加 合型非離子界面活性劑，其係得自在帶有8至1 8碳原子 的一級或二級醇中，加入平均4至5 0莫耳的環氧乙烷及 平均3至1 5莫耳的環氧丙烷，（3 )糖類/脂肪酸酯型 (請先閲讀背面之注意事項再填寫本頁) 本纸張尺度適用中國國家標準（CNS )八4規格（210X297公釐） -6 - 經濟部中央標隼局員工消費合作杜印製 508249 A7 _ B7 五、發明説明（4 ) 非離子界面活性劑，其係得自帶有6至1 6碳原子之脂肪 酸與糖類如葡萄糖，及（4 )糖類/醇醚型非離子界面活 性劑，其係得自帶有6至1 6碳原子之醇與糖類如葡萄糖 。這些界面活性劑可單獨或以其二或更多個混合物形式使 用。非離子界面活性劑使用量較佳爲〇至1 5重量部分， 更佳爲0至8重量部分，就1 0 0重量部分的陰離子界面 活性劑前驅物而言。 · 用於本發明鹼性組份之較佳實施例爲鈉與鉀進料源， 如鈉與鉀的碳酸鹽，碳酸氫鹽，矽酸鹽，多磷酸鹽及焦磷 酸鹽。其中，碳酸鈉，碳酸鈉鉀，碳酸鉀，碳酸氫鈉及碳 酸氫鉀爲較佳。碳酸鈉及碳酸鉀尤其是較佳的。本發明中 此鹼性組份係以粒狀形式使用。即使顆粒直徑未特別限定 ，平均粒徑較佳爲1 0至3 0 0 // m，更佳爲1 0至 1 5 0 m 〇 即使粒狀鹼組份本身可作爲含粒狀鹼組份粉末層，也 可以其與無機鹽混合物形式使用，該無機鹽如硫酸鹽，亞 硫酸鹽或鋁矽酸鹽（尤其是沸石）。此無機鹽平均粒徑較 佳爲1至3 0 0 // m。 無機鹽用量較佳爲0至2 0 0重量部分，更佳爲0至 1 0 0重量部分，就1 0 0重量部分的粒狀鹼組份而言。 本發明中粒狀鹼組份使用量大於須中和液體酸前驅物 之量。粒狀鹼組份所用之莫耳數較佳爲至少須中和液體酸 前驅物，且更佳爲2至8倍。 含有粒狀鹼組份之粉末層可進一步包含乙烯二胺四醋 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ~ ΙΊΙ.Ί--.--豐II (請先閱讀背面之注意事項再填寫本頁) 、1Τ 508249 經濟部中夬標隼局員工消費合作社印製 A7 B7 i、發明説明（5 ) 酸酯，二乙烯三胺五醋酸酯，氮基三醋酸酯，由1 -羥基乙 烷-1，1 -二磷酸酯所代表之磷化合物，多磷酸，由瀉藥酸 所代表之有機磷酸，及（甲基）丙烯酸聚合物。 本發明中，將一層液體酸性前驅物與粉末層接觸之步 驟，該粉末層含有粒狀鹼組份其含量大於中和陰離子界面 活性劑液體酸性前驅物之所須。將兩者相互接觸之模式如 下： 模式1 將含有粒狀驗組份之粉末送入帶有攪動與切變功能之 粒化機器而形成沉降粉末層。之後將液體酸前驅物送入機 器而在粉末層表面形成液體酸前驅物層。靜置一會兒待使 至少一部份的液體酸前驅物含浸粉末層後，經由攬動混合 而同時執行中和與粒化。 模式2 將一部分的含有粒狀鹼組份之粉末送入帶有攪動與切 變功能之粒化機器而形成沉降的第一粉末層。之後將一部 分的液體酸前驅物送入機器而在粉末層表面形成第一液體 酸前驅物層。將一部分的含有粒狀鹼組份之粉末送入而形 成沉降的第二粉末層。將一部分的液體酸前驅物層送入而 在粉末層表面形成第二液體酸前驅物層。如此，此兩種層 交互排列。靜置一會兒待使至少一部份的液體酸前驅物含 浸粉末層後，經由攪動混合而同時執行中和與粒化。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） Ί:--ϊ------- (請先閱讀背面之注意事項再填寫本頁)508249 A7 B7 V. Description of the invention (1) Background of the present invention The present invention relates to a method for manufacturing granular detergents with a bulk density of at least 0 · 7 g / cm3, especially 0 · 7 to 0 · 9 g / cm 3 and is widely used, for example, in laundry detergent compositions. Various methods have been proposed for manufacturing granular detergents with a high bulk density without using a spray drying tower. In most of the proposed methods, the granular alkali is sent into a granulator with a stirrer, and then the liquid acid precursor of the anionic surfactant is slowly dropped or sprayed. At this time, the Keep the granular base flowing and keep flowing to perform granulation [see Japanese Patent Unexamined Published Application (see below | for "J · P. ΚΟΚΑΓ") No · Hei 4-3 6 3 3 9 8 and phase The relevant Japanese Patent Publication (hereinafter referred to as " JP KOKOKU ") No. Hei 6-7 8 6 5 8) Printed in these methods by the Consumers' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs due to insufficient granulation Adhesives are required. In addition, it is difficult to obtain products with a bulk density of at least 0.7 g / cm3, especially at least 0.8 g / cm3. In addition, dripping equipment or spray equipment must be used to interface the anions. The addition of liquid acid precursors of active agents also requires complicated operations to control the amount of feed of these materials. The present invention aims to provide a method for manufacturing high-density granular detergents by using agitation The / granulation method can easily increase the bulk density. This and other objectives of the present invention can be clearly seen from the following description and examples. -4- (Please read the precautions on the back before filling this page} This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 508249 A7 B7 Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs. 5. Description of the invention (2) The present invention is based on the following findings: When a liquid acid precursor The powder layer is in contact with a powder layer. The content of the granular alkali component in the powder layer is greater than that required to neutralize the liquid acid precursor, and a layer is formed in the form of a large mass. The granulator with agitating and shearing functions agitates and mixes the products. The advantage of this method is that it can be granulated, can be neutralized in a shorter time than required by previous techniques, and can be performed in a single step. The invention provides a method for manufacturing a high-density granular detergent, which can effectively solve the aforementioned problems. That is, the present invention provides a method for manufacturing a high-density granular detergent, which comprises neutralizing with a granular alkali component. The liquid acid precursor of the ionic surfactant and granulates the neutralized product, and is characterized by contacting a layer of the liquid acid precursor with a powder layer, the content of the granular alkali component in the powder layer is greater than the neutralized liquid acid precursor It is necessary to impregnate the powder layer with at least one portion of the liquid acid precursor, and then agitate and mix the product to perform the neutralization and granulation at the same time. Any laundry detergent composition. Preferred among them are linear or branched alkyl (average carbon chain length: 8 to 18) benzenesulfonic acid, long chain alkyl (average carbon chain length 10 to 20) sulfonic acid, long chain olefin (average Carbon chain length: 10 to 20) sulfonic acid, long-chain monoalkyl (average carbon chain length: 10 to 20) ether thioester, polyoxyethylene (average degree of polymerization: 1 to 10) chain Alkyl (average carbon chain length: 10 to 20) ether thioester, polyoxyethylene (average degree of polymerization: 3 to 30) alkyl (average carbon chain length: 6 to 12) benzene (please read the back first) Note: Please fill in this page again.) This paper size applies the Chinese National Standard (CMS) A4 specification (210X297mm) -5-508249 A7 B7 Printed by the Central Consumers' Bureau of the Ministry of Economic Affairs and Consumer Cooperatives. V. Invention Description (3) Ether thioester, ^ -thio fatty acid (average carbon chain length: 8 to 2 2), long-chain monoalkyl, dialkyl or sesquialkyl phosphate, polyoxyethylene monoalkyl, dialkyl and Sesquialkyl phosphate. They are preferably used alone or in the form of a mixture of two or more thereof. Among them, particularly preferred is one, or a mixture of two or more, linear or branched alkyl groups (average carbon chain length · 8 to 18) benzoic acid 'long chain courtyard group (average carbon chain length) : 10 to 20) sulfonic acid, long-chain olefin (average carbon chain length: 10 to 20) sulfonic acid, long-chain monoalkyl (average carbon chain length: 10 to 20) thioester, polyoxyl group Ethylene (average degree of polymerization: 1 to 10) alkyl (average carbon chain length: 10 to 20) ether thioester and α-thio fatty acid (average carbon chain length: 8 to 2 2) 〇 Anionic interface used in the present invention The acid precursor of the active agent is an aqueous slurry. This aqueous slurry contains 70 to 100% by weight (hereinafter referred to as "%"), more preferably 90 to 100% of the acid precursor. In addition, the viscosity of the aqueous solution slurry is preferably from 0.1 to 50 p (10 to 80 ° C). The aqueous solution slurry that can be used in the present invention may contain nonionic interface activity in addition to the acid precursor of the anionic surfactant. Agent. The non-ionic surfactants used herein include, for example, (1) E0 adduct type non-ionic surfactants, which are derived from a primary or secondary alcohol having 8 to 18 carbon atoms, added on average 4 to 50 moles of ethylene oxide, (2) E0-P0 addition type non-ionic surfactant, which is obtained from a primary or secondary alcohol having 8 to 18 carbon atoms, added on average 4 To 50 moles of ethylene oxide and 3 to 15 moles of propylene oxide on average, (3) sugar / fatty acid ester type (please read the precautions on the back before filling this page) This paper size applies China National Standard (CNS) 8-4 specification (210X297 mm) -6-Consumption Cooperation by Employees of the Central Bureau of Standards, Ministry of Economic Affairs, Du Printing 508249 A7 _ B7 V. Description of the Invention (4) Non-ionic surfactant, which is obtained from Fatty acids and sugars with 6 to 16 carbon atoms, such as glucose, and (4) sugars / alcohol ether type nonionic surfactants, which are derived from alcohols and sugars with 6 to 16 carbon atoms, such as glucose. These surfactants may be used alone or in the form of a mixture of two or more thereof. The non-ionic surfactant is preferably used in an amount of 0 to 15 parts by weight, more preferably 0 to 8 parts by weight, as far as 100 parts by weight of anionic surfactant precursor is concerned. · Preferred embodiments for the alkaline components of the present invention are sodium and potassium feed sources, such as sodium and potassium carbonates, bicarbonates, silicates, polyphosphates, and pyrophosphates. Of these, sodium carbonate, potassium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate are preferred. Sodium carbonate and potassium carbonate are particularly preferred. In the present invention, this basic component is used in a granular form. Even if the particle diameter is not particularly limited, the average particle diameter is preferably 10 to 3 0 0 // m, and more preferably 10 to 150 m. Even if the granular alkali component itself can be used as a powder containing the granular alkali component The layer can also be used in the form of a mixture with inorganic salts, such as sulfates, sulfites or aluminosilicates (especially zeolites). The average particle diameter of this inorganic salt is preferably 1 to 3 0 0 // m. The amount of the inorganic salt is preferably from 0 to 200 parts by weight, more preferably from 0 to 100 parts by weight, in terms of 100 parts by weight of the granular alkali component. The amount of the granular alkali component used in the present invention is greater than the amount of the liquid acid precursor to be neutralized. The number of moles used for the granular alkali component is preferably at least to neutralize the liquid acid precursor, and more preferably 2 to 8 times. The powder layer containing granular alkali component can further contain ethylene diamine tetraacetate. The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) ~ ΙΊΙ.Ί --.-- Feng II (Please read the back first (Notes on this page, please fill in this page), 1T 508249 A7 B7 printed by the Consumers' Cooperative of the Ministry of Economic Affairs, China Standards Bureau, the invention description (5) Ester, diethylene triamine pentaacetate, nitrogen triacetate, by Phosphorus compounds represented by 1-hydroxyethane-1,1-diphosphate, polyphosphoric acids, organic phosphoric acids represented by cathartic acid, and (meth) acrylic polymers. In the present invention, the step of contacting a layer of a liquid acidic precursor with a powder layer, the powder layer containing a granular alkali component having a content greater than that required to neutralize the liquid acidic precursor of the anionic surfactant. The mode of contacting the two with each other is as follows: Mode 1 The powder containing the granular test component is sent to a granulating machine with agitating and shearing functions to form a settled powder layer. The liquid acid precursor is then fed into the machine to form a liquid acid precursor layer on the surface of the powder layer. After leaving it for a while to impregnate at least a part of the liquid acid precursor with the powder layer, it is simultaneously neutralized and granulated by dynamic mixing. Mode 2 A part of the powder containing the granular alkali component is fed into a granulating machine with agitating and shearing functions to form a first powder layer that is settled. A portion of the liquid acid precursor is then fed into the machine to form a first liquid acid precursor layer on the surface of the powder layer. A part of the powder containing the granular alkali component is fed in to form a second powder layer which is settled. A part of the liquid acid precursor layer is fed in to form a second liquid acid precursor layer on the surface of the powder layer. As such, the two layers are arranged alternately. After being left for a while to impregnate at least a part of the liquid acid precursor with the powder layer, neutralization and granulation were performed simultaneously by stirring and mixing. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm)
、1T 508249 A7 B7 _五、發明説明（6 ) 模式3 . 將一部分的含有粒狀鹼組份之粉末送入帶有攪動與切 變功能之粒化機器而形成沉降的第一粉末層。之後將一部 分的液體酸前驅物送入機器而在粉末層表面形成第一液體 酸前驅物層。靜置一會兒待使至少一部份的液體酸前驅 物含浸粉末層後，經由攪動而將其混合。將餘下的含有粒 狀鹼組份之粉末送入而在其上形成沉降的第二粉末層。將 餘下的液體酸前驅物送入在其中而在粉末層表面形成第二 液體酸前驅物層。靜置一會兒待使至少一部份的液體酸前 驅物含浸粉末層後，經由攪動混合而同時執行中和與粒化 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央樣準局員工消費合作社印製 模式4 . 將含有粒狀鹼組份之粉末送入移動中的傳輸帶而在傳 輸帶上形成連續的粉末層。連續地將液體酸前驅物送入此 層，而在連續的粉末層上形成連續的液體酸前驅物層。如 此此二層保持在移動傳輸帶上，而以至少一部分的液體酸 前驅物使粉末層含浸。將此二層在傳輸帶上送入帶有攪動 與切變功能之粒化機器以同時執行中和與粒化。 爲了以至少一部分的液體酸前驅物將粉末層含浸’宜 在粉末層上形成液體酸前驅物層之後，在進行攪動與混合 之前使其靜置，例如至少二秒。本發明中，也可在攪動並 混合之前以全部液體酸前驅物將粉末層加以含浸。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -9 - 508249 A7 B7 五、發明説明（7 ) 可用於本發明之帶有攪動與切變功能的粒化機器有， 例如，敘述於：L P. KOKAI No. He! 2 - 4 1 3 9 9帶有攪 動功能與裁切功能，其中攪拌器與裁切器係相互獨立操作 ’各有其可變速率。其較佳的實施例包括Lodige混合機 F KM-5 0 D 及 KM-3 0 0 D (由Matsubo Corporation供 應），及 PLOUGH SHARE 混合機 W B 7 5 ，W B 3 0 0 及 W A 3 0 0 (由 Taiheiyo KIK〇 Corporation供應），。由攬 動並混合而中和與粒化宜在3 0至6 0 °C執行約3至6分 鐘。攪動並混合之執行宜使弗洛數（F r 〇 u d e數）爲〇 . 5 至3 · 5，其計算係由公式·· U/〔 （gxR)之平方根 〕（其中R代表攪動粒化機器之攪動葉片的半徑，且U代 表周圍速率），且送料程度爲1〇至60%體積。在攪動 /粒化之中，宜將冷空氣導入攪動粒化機器以同時執行冷 卻及粒化。 本發明中冋時執f了中和與粒化後，可加入塗覆劑如沸 石以塗覆顆粒表面。塗覆之用量較佳爲0 · 5至8重量部 分，就1 0 0重量部分的顆粒而言。 經濟部中央標準局員工消費合作社印製 本發明中顆粒尺寸之調整，可以使用粉碎機/壓碎機 /尺寸調整機，在粒化後立即執行或在塗覆後執行。 在前述成分（原料）之外，本發明之淸潔劑組成物可 包含各種成分（原料）。包括例如，酵素，抗再沉澱劑， 香料，著色劑及螢光劑。這些成分可在粒化完成後塗覆過 程中加入或在塗覆後加入。 阮酶包括，例如，色賓酶（S a b i n a s e )及都洛酶（ -10- (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 508249 _120106號專利申靈案 公告 _說明書修正頁 B7 馬_89伟5月修正 (請先閱讀背面之注意事項再填寫本頁)1T 508249 A7 B7 _V. Description of the invention (6) Mode 3. A part of the powder containing the granular alkali component is fed into a granulating machine with agitating and shearing functions to form a first powder layer that is settled. A portion of the liquid acid precursor is then fed into the machine to form a first liquid acid precursor layer on the surface of the powder layer. After standing for a while to impregnate at least a portion of the liquid acid precursor with the powder layer, they are mixed by stirring. The remaining powder containing the granular alkali component is fed in to form a second powder layer which is settled thereon. The remaining liquid acid precursor is fed thereinto to form a second liquid acid precursor layer on the surface of the powder layer. Let it stand for a while to impregnate at least part of the liquid acid precursor with the powder layer, and then perform the neutralization and granulation at the same time by stirring and mixing (please read the precautions on the back before filling this page). Consumption cooperative printing mode 4. The powder containing granular alkali component is fed into a moving conveyor belt to form a continuous powder layer on the conveyor belt. A liquid acid precursor is continuously fed into this layer, and a continuous liquid acid precursor layer is formed on a continuous powder layer. The two layers are thus held on a moving conveyor, and the powder layer is impregnated with at least a portion of the liquid acid precursor. The two layers are sent on a conveyor belt to a granulating machine with agitating and shearing functions to perform neutralization and granulation at the same time. In order to impregnate the powder layer with at least a portion of the liquid acid precursor ', it is preferable to allow the liquid acid precursor layer to form on the powder layer, and then allow it to stand for at least two seconds before performing agitation and mixing. In the present invention, the powder layer may be impregnated with all the liquid acid precursors before being stirred and mixed. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -9-508249 A7 B7 V. Description of the invention (7) Granulation machines with agitating and shearing functions that can be used in the present invention are, for example, Described in: L P. KOKAI No. He! 2-4 1 3 9 9 with agitating function and cutting function, where the mixer and cutter are operated independently of each other 'each has its variable rate. Preferred examples thereof include the Lodige mixers F KM-5 0 D and KM-3 0 0 D (supplied by Matsubo Corporation), and the PLOUGH SHARE mixers WB 7 5, WB 3 0 0 and WA 3 0 0 (by (Supplied by Taiheiyo KIK〇 Corporation). Neutralization and granulation by stirring and mixing should be performed at 30 to 60 ° C for about 3 to 6 minutes. The stirring and mixing should be performed such that the Flo number (F r 〇ude number) is 0.5 to 3.5. The calculation is based on the formula: U / [(square root of (gxR)]] (where R represents the stirring granulation machine) It stirs the radius of the blade, and U represents the surrounding speed), and the feeding degree is 10 to 60% by volume. During agitation / granulation, cold air should be directed to the agitation granulation machine to perform cooling and granulation simultaneously. In the present invention, after neutralization and granulation, a coating agent such as zeolite can be added to coat the surface of the particles. The coating is preferably used in an amount of 0.5 to 8 parts by weight, with respect to 100 parts by weight of particles. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The particle size adjustment in the present invention can be performed using a shredder / crusher / size adjuster immediately after granulation or after coating. In addition to the aforementioned ingredients (raw materials), the detergent composition of the present invention may contain various ingredients (raw materials). These include, for example, enzymes, anti-reprecipitation agents, fragrances, colorants and fluorescent agents. These ingredients can be added during the coating after granulation or after coating. Nguyen enzymes include, for example, Sabinase and Dulozyme (-10- (Please read the notes on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) ） 508249 _120106 Patent Application Case Announcement _ Manual Correction Page B7 Ma _89 Wei May Revision (Please read the precautions on the back before filling this page)
Durazyme)(由N〇V〇供應）及麥色酶（Maxapem)(由 Genencor International，Inc.供應）；且脂肪分解酵素包括 ，例如，利波酶（Lipolase )(由N〇V〇供應）。此外， 也可使用賽路酶（Celluzyme )(由N〇V〇供應）或其類 似物。它們可單獨使用或以其二或更多個混合物形式使用 。即使此酵素用量未特別限定，較佳爲〇 · 〇 5至2 %， 基於全體淸潔劑組成物。 香料用量較佳爲至少0 · 01%’更佳爲〇 · 03至 1 · 5 %，及最特別是0 · 0 5至〇 · 3 0 %，基於淸潔 劑組成物。 由本發明之方法，可簡易地得到粒狀淸潔劑其鬆密度 高達至少0 . 8 g / c m 3。尤其是可以短時間執行中和（ 在實施例中，約五分鐘）以減少生產所須時間。無須特別 設備如噴霧裝置以加入粉末狀或液體酸前驅物（在實施例 中，前驅物可由手工加入），且高密度粒狀淸潔劑可以簡 單裝置製造。雖然使用黏結劑對於達成粒化係有用的’但 不用黏結劑亦可得到絕佳高鬆密度粒狀淸潔劑。 經濟部智慧財產局員工消費合作社印製 下列實施例將進一步說明本發明。 實施例1 將3 0重量部分的碳酸鈉（平均粒徑：8 0 V m )， 2 7 重量部分的A -型沸石（平均粒徑：1 // m )及5重 量部分的三多磷酸鈉（平均粒徑：5 0 // m )，作爲粉末 狀起始材料，送入Lodige混合機F K Μ - 5 0 D (由 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -11- 508249 A7 _ B7_ 五、發明説明（9 ) M atsubo Corporation供應），以主軸旋轉速率1 5 0 r pm 將其攪動一分鐘。之後停止粒化器。將粉末混合物靜置後 ，將3 0重量部分的烷基苯磺酸水溶液漿液（在烷基基團 之碳原子數：8至18，烷基苯磺酸含量：96%)送入 粉末層上。靜置2 0秒後，水溶液漿液局部滲入粉末層， 在下列條件下將其攪動以執行中和/粒化： 中和/粒化條件： 進料速率：3 0 %，軸旋轉速率：1 5 0 r p m，切 碎機旋轉速率：3，OOOrpm，Fr數：2 · 2 ,護 套進口溫度：1 5 °C，護套中流速：6 0 0 1 / h，中和 /粒化時間：5分鐘。 完成中和/粒化後，於L 〇 d i g e混合機 F K Μ - 5 ◦ D 中加入塗覆劑（3重量部分的如上相同沸石），並將所得 到混合物在如前所述相同條件下流動化三分鐘，之後自粒 化機器排出而得到高鬆密度粒狀淸潔劑。 經濟部中央標準局員工消費合作社印裝 (請先閲讀背面之注意事項再填寫本頁) 所得到高鬆密度粒狀淸潔劑，其可使用性與性質總結 如表1 〇 實施例2 將如同用於實施例1之相同粉末狀起始材料連續地送 入傳輸帶，其移動速率0 · 2m/s e e，而在傳輸帶上 形成粉末層（厚度··約5至1 5 m m )。將3 0重量部分 的如同用於實施例1相同之烷基苯磺酸水溶液漿液送入粉 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _12. 508249 A 7 — B7 __ 五、發明説明（1〇 ) 末層，並將它們保持在傳輸帶上二秒。之後將其送入如用 於實施例1相同之攬動/粒化機器中，並在如實施例1之 相同條件下執行中和/粒化。完成中和/粒化後，以如實 施例1相同方式得到高鬆密度粒狀淸潔劑。 所得到高鬆密度粒狀淸潔劑，其可使用性與性質總結 如表1。 實施例3 取如同用於實施例1的1 / 3全體量之相同粉末狀起 始材料，送入如用於實施例1相同之攪動/粒化機器。取 如用於實施例1的1 / 2的全體量的相同烷基苯磺酸水溶 液漿液，送入如此形成的粉末狀層。將另1 / 3的粉末狀 起始材料加入，並將餘下的水溶液漿液加入。將餘下的粉 末狀起始材料送入其上。靜置1 0秒後，水溶液漿液局部 滲入粉末層，如實施例1相同條件下將其攬動以執行中和 /粒化。以如實施例1相同方式完成執行中和/粒化後， 得到高鬆密度粒狀淸潔劑。 經濟部中央標隼局員工消費合作社印製 所得到高鬆密度粒狀淸潔劑，其可使用性與性質總結 如表1。 實施例4 取如同用於實施例1的1 / 3全體量之相同粉末狀起 始材料，送入如用於實施例1相同之攪動/粒化機器。取 如用於實施例1的1 / 3的全體量的相同烷基苯磺酸水溶 -13- (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 508249 A7 _ B7___五、發明説明（11 ) 液漿液，送入如此靜置之粉末狀層。靜置1 0秒後，水溶 液漿液局部滲入粉末層，如實施例1相同條件下將其攪動 二分鐘，以執行中和/粒化。重覆此操作二次（共操作三 次）以執行中和/粒化（總中和/粒化時間·· 6分鐘）。 完成中和/粒化後，以如實施例1相同方式得到高鬆密度 粒狀淸潔劑。 所得到高鬆密度粒狀淸潔劑，其可使用性與性質總結 如表1。 比較實施例1 取如用於實施例1相同粉末狀起始材料送入如用於實 施例1相同攪動/粒化機器。使用如實施例1相同條件將 粒化機器中內容物流動化。之後取如用於實施例1相同烷 基苯磺酸水溶液漿液加入其中，保持流動化狀態以執行中 和/粒化1 0分鐘。完成中和/粒化後，以如實施例1相 同方式得到高鬆密度粒狀淸潔劑。 所得到高鬆密度粒狀淸潔劑，其可使用性與性質總結 如表1。 ΙΊΊ ^---.--^^衣------1T------ (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 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -14- 508249 Α7 __—_Β7_.__ 五、發明説明（12 ) 表 1 實施例1實施例2實施例3實施例4 比較 實施例1 黏附於機器 無 少許 少許 少許 無 中和/粒化產物之性質： . B. D.(g/cc) 0.85 0.87 0.86 0.84 0.74 粉末溫度（°C ) 48 40 38 38 38 (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裝 實施例5至1 1 將3 2 重量部分的碳酸鈉（平均粒徑：8 0 // m ) 與3 0重量部分的A -型沸石（平均粒徑：1 // m )作爲粉 末狀起始材料，送入Lodige混合機F K Μ _ 5 0 D (由 Matsubo Corporation供應），以主軸旋轉速率1 5 0 r pm 將其攪動一分鐘◦之後將粒化器停止。將粉末混合物靜置 後’取3 0重量部分的烷基苯磺酸水溶液漿液（烷基基團 上的碳原子數：8至1 8，烷基苯磺酸含量：9 7 % )送 入粉末層上。靜置後2 0秒，水溶液漿液局部滲入粉末層 ’以展示如表2之條件將其攬動而執行中和/粒化。 完成中和/粒化後，塗覆劑（3重量部分如上相同的 沸石）加入Lodige混合機 F K Μ - 5 0 D，並將所得到的 混合物在如前所述相同條件下流動化三分鐘，之後自粒化 機器排出，而得到粒狀的高鬆密度粒狀淸潔劑。 -15- 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 508249 A7 B7 五、發明説明（13) 所得到高鬆密度粒狀淸潔劑，其可使用性與性質總結 如表2。 表 2 中和/粒化條件： 實施例5 實施例6 實施例7 實施例丨 進料速率（％) 15 2 0- 30 50 軸旋轉速率（rpm) 150 同前 同前 同前 切碎機旋轉速率（rpm) 3000 同前 同前 同前 Fi*數 2.2 同前 同前 .同前 護套溫度（°C ) 15 同前 35 15 護套中流速（1/h) 600 同前 同前 同前 中和/粒化時間（min) 5 同前 同前 同前 黏附於機器 Μ j\\\ 並 j \ w Μ j\w Μ j\\\ 中和/粒化產物性質 B. D. (g/cc) 0.76 0.8 0.86 0.88 粉末溫度（°C ) 38 41 60 58 (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 -16- 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 508249 A7 B7 -、發明説明（14) 表 2(繼續） 實施例( ) 實施例1 〇 實施例1 1 中和/粒化條件： 進料速率（％) 50 同前 同前 軸旋轉速率（rpm) 116 178 240 切碎機旋轉速率（rpm) 3000 .同前 同前 Fr數 1.7 2.6 3.5 護套溫度（°C ) 15 同前 同前 護套中流速（1/h) 600 同前 同前 中和/粒化時間（min) 5 同前 同前 黏附於機器 少許 無 Μ j\ w 中和/粒化產物性質 B . D.(g/cc) 0. 84 0.89 0.87 粉末溫度（°C ) 46 49 56 (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裝 實施例1 2 取如同用於實施例6相同粉末狀起始材料連續地以 0 · 2m/s e c速率送入移動中的傳輸帶’而在傳輸帶 上形成粉末層（厚度：約5至1 5 m m )。取3 0重量部 分的如同用於實施例6相同水溶液烷基苯磺酸漿液送入粉 末層，且在其上保持二秒。之後以下列條件連續操作 Lodige混合機（K Μ - 3 0〇D )，包含軸旋轉速率1 2 0 r p m，切碎機旋轉速率3，0 0 0 r p m，護套進口溫 ) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -17- 508249 Μ _Β7_ 五、發明説明（15 ) 度在3 5 °C及護套中流速1 2 0 e / h。在此步驟中，駐 留時間約Θ〇秒。 將如此連續排出的中和產物送入旋轉圓柱型連續翻滾 粒化器。取如實施例6相同塗覆沸石加入，並將所得到混 合物連續地粒化而得到中和的顆粒。 此顆粒帶有0 · 8 4 g/m 1之B.D.，且粉末溫度在 3 8。。。 實施例1 3 經濟部中央標隼局員工消費合作社印製 取如同用於實施例6的1 / 2全體量之相同粉末狀起 始材料，以0 · 2 m / s e c的速率連續地送入移動中的 傳輸帶，而在傳輸帶上形成粉末層（厚度：約5至1 5 mm)。取如同用於實施例6的1 / 2全體量之相同水溶 液烷基苯磺酸漿液送入粉末層，並在其上保持二秒。之後 將其送入連續的Lodige混合機（K Μ - 3 0〇D )。將餘下 的粉末狀材料與酸前驅物由進口，連續地且同時地送入攪 動/粒化機器經以執行中和/粒化。在此步驟中，以下列 條件操作攪動/粒化機器，包含軸旋轉速率1 2 0 r p m ，切碎機旋轉速率3，000 r pm，護套進口溫度在 3 5 t及護套中流速1. 2 0 1 / h。駐留時間約6 0秒。 將如此連續排出的中和產物送入旋轉圓柱型連續翻滾 粒化器。取如實施例6相同塗覆沸石加入，並將所得到混 合物連續地粒化而得到中和的顆粒。 此顆粒帶有0 . 8 2 g / m 1之B. D.,且粉末溫度在 -18- (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 508249 A7 ___B7 五、發明説明（16 ) 3 9 °C。 ’ 11~ 1--*---I--- (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 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -19-Durazyme) (supplied by NOV0) and wheat enzyme (Maxapem) (supplied by Genencor International, Inc.); and lipolytic enzymes include, for example, Lipolase (supplied by NOV0). In addition, Celluzyme (supplied by NOVO) or an analogue thereof can also be used. They can be used alone or as a mixture of two or more of them. Although the amount of this enzyme is not particularly limited, it is preferably from 0.5 to 2% based on the entire detergent composition. The amount of the perfume is preferably at least 0.01%, more preferably 0.03 to 1.5%, and most particularly 0.05 to 0.30%, based on the detergent composition. By the method of the present invention, a granular detergent can be easily obtained with a bulk density of at least 0.8 g / cm3. In particular, neutralization can be performed in a short time (about five minutes in the embodiment) to reduce the time required for production. No special equipment such as a spraying device is required to add the powder or liquid acid precursor (in the embodiment, the precursor can be added by hand), and the high-density granular detergent can be manufactured in a simple device. Although the use of a binder is useful for achieving a granulation system, an excellent high-density granular detergent can be obtained without a binder. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The following examples will further illustrate the present invention. Example 1 30 parts by weight of sodium carbonate (average particle size: 80 V m), 2 7 parts by weight of A-type zeolite (average particle size: 1 // m), and 5 parts by weight of sodium tripolyphosphate (Average particle size: 5 0 // m), as a powdery starting material, sent to Lodige mixer FK Μ-50 0 D (Chinese paper standard (CNS) A4 size (210 X 297 mm) applies to this paper size) -11- 508249 A7 _ B7_ 5. Description of the invention (9) (Supplied by Matsubo Corporation), agitate it at a spindle rotation rate of 150 pm for one minute. The granulator was stopped after that. After the powder mixture was left to stand, 30 parts by weight of an alkylbenzenesulfonic acid aqueous solution slurry (carbon atoms in the alkyl group: 8 to 18, alkylbenzenesulfonic acid content: 96%) was sent onto the powder layer . After standing for 20 seconds, the aqueous solution slurry partially penetrated into the powder layer, and was agitated under the following conditions to perform neutralization / granulation: Neutralization / granulation conditions: Feed rate: 30%, shaft rotation rate: 1 5 0 rpm, shredder rotation rate: 3,000 rpm, Fr number: 2 · 2, inlet temperature of sheath: 15 ° C, flow rate in sheath: 6 0 0 1 / h, neutralization / granulation time: 5 minute. After the neutralization / granulation is completed, a coating agent (3 parts by weight of the same zeolite as above) is added to the Lodige mixer FK Μ-5 ◦ D, and the resulting mixture is fluidized under the same conditions as previously described After three minutes, it was discharged from the granulating machine to obtain a high-density granular detergent. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). The obtained high-density granular detergents are summarized in Table 1. Example 2 will be the same as The same powdery starting material used in Example 1 was continuously fed into the conveyor belt at a moving speed of 0 · 2m / see, and a powder layer (thickness ·· about 5 to 15 mm) was formed on the conveyor belt. 30 parts by weight of the same alkylbenzenesulfonic acid aqueous solution slurry as used in Example 1 was fed into the paper. The paper size was applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _12.508249 A 7 — B7 __ 5 2. Description of the invention (10) The last layer and keep them on the conveyor for two seconds. It was then fed to the same moving / granulating machine as used in Example 1, and neutralization / granulating was performed under the same conditions as in Example 1. After the neutralization / granulation was completed, a high bulk granular detergent was obtained in the same manner as in Example 1. The usability and properties of the obtained high-density granular detergents are summarized in Table 1. Example 3 The same powdery starting material as in 1/3 of the entire amount used in Example 1 was taken and fed to the same agitation / granulation machine as used in Example 1. The same amount of the same alkylbenzenesulfonic acid aqueous solution slurry as used for 1/2 of the amount in Example 1 was taken and fed to the powdery layer thus formed. Add another 1/3 of the powdery starting material and add the remaining aqueous slurry. The remaining powdery starting material is fed onto it. After standing for 10 seconds, the aqueous solution slurry partially penetrated into the powder layer, and was stirred under the same conditions as in Example 1 to perform neutralization / granulation. After performing the neutralization / granulation in the same manner as in Example 1, a high bulk density granular detergent was obtained. Printed by the Consumers' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs, and obtained the high-density granular detergents. The usability and properties are summarized in Table 1. Example 4 The same powdery starting material was taken as 1/3 of the entire amount used in Example 1, and fed to the same agitation / granulation machine as used in Example 1. Take 1/3 of the same amount of the same alkylbenzenesulfonic acid water-soluble as used in Example 1-13 (Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 508249 A7 _ B7___ V. Description of the invention (11) The liquid slurry is sent to the powdery layer thus left to stand. After standing for 10 seconds, the aqueous solution slurry partially penetrated into the powder layer, and was agitated for two minutes under the same conditions as in Example 1 to perform neutralization / granulation. Repeat this operation twice (three operations in total) to perform neutralization / granulation (total neutralization / granulation time · 6 minutes). After the neutralization / granulation was completed, a high bulk granular detergent was obtained in the same manner as in Example 1. The usability and properties of the obtained high-density granular detergents are summarized in Table 1. Comparative Example 1 The same powdery starting material as used in Example 1 was taken and fed into the same agitation / granulation machine as used in Example 1. The contents in the granulator were fluidized using the same conditions as in Example 1. Thereafter, the same alkylbenzenesulfonic acid aqueous solution slurry as used in Example 1 was added thereto and maintained in a fluidized state to perform neutralization / granulation for 10 minutes. After the neutralization / granulation was completed, a high bulk granular detergent was obtained in the same manner as in Example 1. The usability and properties of the obtained high-density granular detergents are summarized in Table 1. ΙΊΊ ^ ---.-- ^^ 衣 ------ 1T ------ (Please read the precautions on the back before filling out this page) Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Applicable to China National Standard (CNS) A4 specification (210X297 mm) -14- 508249 A7 ____ Β7 _.__ V. Description of the invention (12) Table 1 Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Adhesion The properties of the product are not neutralized / granulated in the machine: BD (g / cc) 0.85 0.87 0.86 0.84 0.74 Powder temperature (° C) 48 40 38 38 38 (Please read the precautions on the back before filling in this Page) Examples 5 to 1 printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 3 2 parts by weight of sodium carbonate (average particle size: 8 0 // m) and 30 parts by weight of A-type zeolite (average particles Diameter: 1 // m) As a powdery starting material, it is fed into a Lodige mixer FK Μ _ 5 0 D (supplied by Matsubo Corporation), and it is agitated at a spindle rotation rate of 1 50 r pm for one minute. The carburetor stops. After the powder mixture was left to stand, 30 parts by weight of an alkylbenzenesulfonic acid aqueous solution slurry (the number of carbon atoms on the alkyl group: 8 to 18, and the content of the alkylbenzenesulfonic acid: 97%) were sent to the powder. On the floor. 20 seconds after standing, the aqueous solution slurry partially penetrated into the powder layer ′ to demonstrate the conditions shown in Table 2 to perform neutralization / granulation. After the neutralization / granulation is completed, the coating agent (3 parts by weight of the same zeolite as above) is added to the Lodige mixer FK Μ-50 D, and the resulting mixture is fluidized for three minutes under the same conditions as previously described, It is then discharged from the granulating machine to obtain a granular high-density granular detergent. -15- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 508249 A7 B7 V. Description of the invention (13) Summary of usability and properties of the obtained high-density granular detergent As shown in Table 2. Table 2 Neutralization / granulation conditions: Example 5 Example 6 Example 7 Example 丨 Feed rate (%) 15 2 0- 30 50 Shaft rotation rate (rpm) 150 Same as before Same as before Shredder rotation Speed (rpm) 3000 Same as before Fi * Number 2.2 Same as before. Same as jacket temperature (° C) 15 Same as 35 15 Velocity (1 / h) in jacket 600 Same as before Neutralization / granulation time (min) 5 Same as before Adhesion to the machine Μ j \\\ and j \ w Μ j \ w Μ j \\\ Properties of neutralization / granulation product BD (g / cc) 0.76 0.8 0.86 0.88 Powder temperature (° C) 38 41 60 58 (Please read the notes on the back before filling this page) Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -16- This paper size applies to Chinese national standards (CNS ) A4 specification (210X297 mm) 508249 A7 B7-, Description of the invention (14) Table 2 (continued) Example () Example 1 〇 Example 1 1 Neutralization / granulation conditions: Feed rate (%) 50 Same Rotating speed of front and front axle (rpm) 116 178 240 Rotating speed of shredder (rpm) 3000. Same as previous Fr number 1.7 2.6 3.5 Sheath Degree (° C) 15 Flow rate (1 / h) in the same sheath as before 600 Neutralization / granulation time (min) 5 Same as before Adhered to the machine a little without Μ j \ w Neutralization / Granulated product properties B. D. (g / cc) 0. 84 0.89 0.87 Powder temperature (° C) 46 49 56 (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Example 1 2 The same powdery starting material as that used in Example 6 was continuously fed to a moving conveyor belt at a rate of 0 · 2m / sec to form a powder layer on the conveyor belt (thickness: about 5 to 1 5 mm). 30 parts by weight of the same aqueous alkylbenzenesulfonic acid slurry as used in Example 6 was fed into the powder layer and held there for two seconds. After that, the Lodige mixer (K Μ-300) was continuously operated under the following conditions, including the shaft rotation rate of 120 rpm, the shredder rotation rate of 3,000 rpm, and the sheath inlet temperature.) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -17- 508249 M _B7_ V. Description of the invention (15) The temperature is at 3 5 ° C and the flow rate in the sheath is 120 e / h. In this step, the dwell time is about Θ0 seconds. The neutralized product thus continuously discharged is sent to a rotating cylindrical type continuous tumble granulator. The same coated zeolite as in Example 6 was added, and the obtained mixture was continuously granulated to obtain neutralized particles. This granule has a B.D. of 0 · 8 4 g / m 1 and a powder temperature of 38. . . Example 1 3 The Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs printed the same powdery starting material as 1/2 of the total amount used in Example 6, and fed it continuously at a rate of 0 · 2 m / sec. Medium conveyor belt while forming a powder layer on the conveyor belt (thickness: about 5 to 15 mm). The same aqueous solution alkylbenzenesulfonic acid slurry as 1/2 of the total amount used in Example 6 was taken into the powder layer and held there for two seconds. It was then fed into a continuous Lodige mixer (KM-300D). The remaining powdery material and acid precursor are continuously and simultaneously fed from the inlet to an agitation / granulation machine to perform neutralization / granulation. In this step, the agitation / granulation machine is operated under the following conditions, including a shaft rotation rate of 120 rpm, a shredder rotation rate of 3,000 r pm, a sheath inlet temperature of 3 5 t and a flow rate of 1. 2 0 1 / h. The dwell time is about 60 seconds. The neutralized product thus continuously discharged is sent to a rotating cylindrical type continuous tumble granulator. The same coated zeolite as in Example 6 was added, and the obtained mixture was continuously granulated to obtain neutralized particles. This granule has a BD of 0.8 2 g / m 1 and the powder temperature is -18- (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 508249 A7 ___B7 5. Description of the invention (16) 3 9 ° C. '11 ~ 1-* --- I --- (Please read the notes on the back before filling out this page) The paper size printed by the Staff Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification ( 210X297 mm) -19-