TW202010796A - Method for preparing lake pigment, lake pigment and use thereof - Google Patents

Method for preparing lake pigment, lake pigment and use thereof Download PDF

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TW202010796A
TW202010796A TW108133064A TW108133064A TW202010796A TW 202010796 A TW202010796 A TW 202010796A TW 108133064 A TW108133064 A TW 108133064A TW 108133064 A TW108133064 A TW 108133064A TW 202010796 A TW202010796 A TW 202010796A
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lake
ions
solution
ion
chelating agent
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TW108133064A
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Chinese (zh)
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謝義鴻
劉媛媛
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大陸商樂象永續科技(杭州)有限公司
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Publication of TW202010796A publication Critical patent/TW202010796A/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B63/00Lakes
    • C09B63/005Metal lakes of dyes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Cosmetics (AREA)

Abstract

Provided are a method for preparing a lake pigment, a lake pigment and the use thereof, which belong to the technical field of lake pigments. The method for preparing a lake pigment involves adding a solution containing at least two metal ions to an acidic aqueous solution containing a pigment raw material, reacting same to obtain solution A, further adding a chelating agent solution to the solution A, and carrying out a chelation reaction at a pH of 6-8 to obtain the lake pigment. The preparation method is simple in process and convenient in operation, and the prepared lake pigment has a small particle size, a high coloring property, and an excellent heat stability, acid and alkali resistance and light resistance, thereby broadening the scope of application of the lake pigment, and solving the technical problems of lake pigments prepared by using existing preparation methods having a larger particle size, a low coloring property, limited applications, and none of the light resistance, acid and alkali resistance, heat resistance, etc., thereof being ideal.

Description

色澱的製備方法、色澱及應用Preparation method, lake and application of lake

本發明關於色澱技術領域,具體而言,關於色澱的製備方法、色澱及應用。The present invention relates to the technical field of color lakes, in particular, to the preparation method, color lakes and applications of color lakes.

色澱是由水溶性染料在不同類型的沉澱劑的作用下沉澱出來的非水溶性有色物質,通常應用於染料、油墨、顏料、墨水、醫藥、化妝品或食品等領域。上述應用一般要求色澱具有鮮豔的色光,良好的遮蓋力,不溶於水,對酸、鹼、熱具有穩定性,且具有良好的耐光性等特點。Lake is a non-water-soluble colored substance precipitated by water-soluble dyes under the action of different types of precipitants. It is usually used in the fields of dyes, inks, pigments, inks, medicine, cosmetics or food. The above applications generally require the lake to have bright shades, good hiding power, insoluble in water, stability to acids, alkalis, heat, and good light resistance.

色澱的製備方法很多,但是先前技術的色澱的製備製程普遍存在著製得的色澱顆粒粒徑較大(一般大於5μm),使得著色強度降低,應用受限的問題;並且色澱的耐光性能、耐酸鹼性能、耐熱性能等均不是很理想。There are many preparation methods for lakes, but the prior art lake preparation process generally has large particle sizes (generally greater than 5 μm), which reduces the coloring strength and limits the application; and Light resistance, acid and alkali resistance, and heat resistance are not ideal.

有鑑於此,特提出本發明以解決上述技術問題中的至少一個。In view of this, the present invention is specifically proposed to solve at least one of the above technical problems.

本發明的第一個目的在於提供一種色澱的製備方法,該製備方法製程簡單、操作方便,製備得到的色澱粒徑較小,具有很高的著色力和較好的耐熱性,耐酸鹼性能和耐光性能優異,拓寬色澱的應用範圍。The first object of the present invention is to provide a method for preparing a lake, which has a simple manufacturing process and is easy to operate. The prepared lake has a small particle size, high color rendering power, good heat resistance, and acid resistance It has excellent alkali performance and light resistance, which broadens the application range of lakes.

本發明的第二個目的在於提供一種色澱,採用上述色澱的製備方法製備而成。The second object of the present invention is to provide a color lake prepared by the above-mentioned color lake preparation method.

本發明的第三個目的在於提供一種色澱的應用。The third object of the present invention is to provide a lake application.

為了實現本發明的上述目的,特採用以下技術方案。In order to achieve the above object of the present invention, the following technical solutions are specifically adopted.

本發明提供了一種色澱的製備方法,包括以下步驟: (a)向含有色素原料的酸性水溶液中加入含有至少兩種金屬離子的溶液,反應,得到溶液A; (b)向溶液A中加入螯合劑溶液,於pH 6-8中進行螯合反應,分離,得到色澱。The invention provides a method for preparing a lake, including the following steps: (a) Add a solution containing at least two metal ions to the acidic aqueous solution containing the pigment raw material, and react to obtain solution A; (b) Add a chelating agent solution to solution A, perform chelation reaction at pH 6-8, and separate to obtain a lake.

進一步的,步驟(a)中,色素原料包括天然植物色素、天然動物色素或合成色素中的一種或至少兩種的組合;及/或 步驟(a)中,色素原料在酸性水溶液的質量分數為5-10%,較佳為6-9%,進一步較佳為7-8%;及/或 步驟(a)中,酸性水溶液的pH為0.5-2。Further, in step (a), the pigment raw material includes one or a combination of at least two of natural plant pigments, natural animal pigments or synthetic pigments; and/or In step (a), the mass fraction of the pigment raw material in the acidic aqueous solution is 5-10%, preferably 6-9%, further preferably 7-8%; and/or In step (a), the pH of the acidic aqueous solution is 0.5-2.

進一步的,步驟(a)中,含有至少兩種金屬離子的溶液中的金屬離子包括鉀離子、鈉離子、鐵離子、鋁離子、錫離子、鈣離子、鎂離子、銅離子、鉻離子或鋇離子中的至少兩種的組合; 較佳地,金屬離子包括鋁離子和錫離子,進一步較佳地,鋁離子和錫離子的質量比為(1-10):1; 較佳地,金屬離子包括鐵離子和錫離子,進一步較佳地,鐵離子和錫離子的質量比為(0.5-10):1;及/或 步驟(a)中,含有至少兩種金屬離子的溶液中金屬離子的質量分數為5-10%,較佳為6-9%,進一步較佳為7-8%。Further, in step (a), the metal ions in the solution containing at least two metal ions include potassium ions, sodium ions, iron ions, aluminum ions, tin ions, calcium ions, magnesium ions, copper ions, chromium ions, or barium Combination of at least two of the ions; Preferably, the metal ions include aluminum ions and tin ions. Further preferably, the mass ratio of aluminum ions to tin ions is (1-10): 1; Preferably, the metal ions include iron ions and tin ions. Further preferably, the mass ratio of iron ions to tin ions is (0.5-10): 1; and/or In step (a), the mass fraction of metal ions in the solution containing at least two metal ions is 5-10%, preferably 6-9%, and more preferably 7-8%.

進一步的,步驟(a)中,含有色素原料的酸性水溶液與含有至少兩種金屬離子的溶液的質量比為(3-5):1;及/或 步驟(a)中,反應溫度為50-60℃,反應時間為10-12h。Further, in step (a), the mass ratio of the acidic aqueous solution containing the pigment raw material to the solution containing at least two metal ions is (3-5): 1; and/or In step (a), the reaction temperature is 50-60°C and the reaction time is 10-12h.

進一步的,步驟(b)中,螯合劑溶液中的螯合劑包括草酸、檸檬酸、葡萄糖酸鈉、酒石酸或內酯中的一種;及/或 步驟(b)中,螯合劑溶液中的螯合劑的質量分數為5-10%,較佳為6-9%,進一步較佳為7-8%。Further, in step (b), the chelating agent in the chelating agent solution includes one of oxalic acid, citric acid, sodium gluconate, tartaric acid, or lactone; and/or In step (b), the mass fraction of the chelating agent in the chelating agent solution is 5-10%, preferably 6-9%, and more preferably 7-8%.

進一步的,溶液A與螯合劑的質量比為(0.5-1.5): 1;及/或 螯合溫度為50-60℃,螯合時間為1-2h。Further, the mass ratio of solution A to chelating agent is (0.5-1.5): 1; and/or The chelating temperature is 50-60℃, and the chelating time is 1-2h.

進一步的,色澱的製備方法,包括如下步驟: (a)向含有質量分數為5-10%色素原料的酸性水溶液中滴加含有至少兩種金屬離子的溶液,反應,反應溫度為50-60℃,反應時間為10-12h,得到溶液A;其中,金屬離子包括鉀離子、鈉離子、鐵離子、鋁離子、錫離子、鈣離子、鎂離子、銅離子、鉻離子或鋇離子中的至少兩種的組合; (b)向溶液A中加入螯合劑溶液,升溫至50-60℃,於pH 6-8中進行螯合反應,反應結束後,洗脫,分離,乾燥,得到色澱; 其中,螯合劑溶液中的螯合劑包括草酸、檸檬酸、葡萄糖酸鈉、酒石酸或內酯中的一種。Further, the preparation method of the lake includes the following steps: (a) Add a solution containing at least two metal ions dropwise to an acidic aqueous solution containing 5-10% pigment raw material, and react. The reaction temperature is 50-60°C and the reaction time is 10-12h to obtain solution A; Wherein, the metal ion includes a combination of at least two of potassium ion, sodium ion, iron ion, aluminum ion, tin ion, calcium ion, magnesium ion, copper ion, chromium ion or barium ion; (b) Add a chelating agent solution to solution A, raise the temperature to 50-60°C, and perform a chelating reaction at pH 6-8. After the reaction, elute, separate, and dry to obtain a lake; The chelating agent in the chelating agent solution includes one of oxalic acid, citric acid, sodium gluconate, tartaric acid, or lactone.

進一步的,色澱的粒徑不大於1μm;較佳地,色澱的粒徑不大於0.22μm。Further, the particle size of the lake is not greater than 1 μm; preferably, the particle size of the lake is not greater than 0.22 μm.

本發明還提供了一種色澱,採用上述色澱的製備方法製得。The invention also provides a color lake, which is prepared by the above-mentioned color lake preparation method.

較佳地,色澱的粒徑不大於1μm,進一步較佳地,色澱的粒徑不大於0.22μm。Preferably, the particle size of the lake is not greater than 1 μm, further preferably, the particle size of the lake is not greater than 0.22 μm.

本發明還提供了一種色澱在染料、油墨、顏料、墨水、製備藥物、化妝品或食品中的應用。The invention also provides an application of the lake in dyes, inks, pigments, inks, preparation of medicines, cosmetics or food.

與先前技術相比,本發明提供的色澱的製備方法和色澱具有以下優勢: (1)本發明提供了一種色澱的製備方法,該製備方法主要是向含有色素原料的酸性水溶液中加入含有至少兩種金屬離子的溶液,反應,得到溶液A,再向溶液A中加入螯合劑溶液,於pH 6-8中進行螯合反應,得到色澱。該製備方法製程簡單、操作方便,製備得到的色澱粒徑較小,具有很高的著色力,且耐熱穩定性,耐酸鹼性能和耐光性能優異,拓寬了色澱的應用範圍,改善了採用先前技術製備方法製得的色澱存在的顆粒粒徑較大,著色強度低,應用受限,且耐光性能、耐酸鹼性能、耐熱性能等均不是很理想的技術問題。Compared with the prior art, the preparation method and lake of the lake provided by the present invention have the following advantages: (1) The present invention provides a method for preparing a lake. The preparation method is mainly to add a solution containing at least two metal ions to an acidic aqueous solution containing a pigment raw material, react to obtain a solution A, and then add a chelate to the solution A. The mixture solution is chelated at pH 6-8 to obtain a lake. The preparation method has simple process and convenient operation, the prepared lake particle size is small, has high color rendering power, and has high heat stability, excellent acid and alkali resistance and light resistance, which broadens the application range of the lake and improves The lake prepared by the prior art preparation method has large particle size, low coloring strength, limited application, and light resistance, acid and alkali resistance, heat resistance, etc. are not ideal technical problems.

另外,螯合劑與金屬離子在偏中性條件下發生螯合反應,可以避免過多的金屬離子進入產品而導致污染,保證了產品的安全性。In addition, the chelating agent and the metal ion undergo a chelating reaction under partial neutral conditions, which can prevent excessive metal ions from entering the product and causing pollution, thereby ensuring the safety of the product.

(2)本發明提供了一種色澱,採用上述製備方法製得,與傳統製備方法相比,所得到的色澱粒徑較小,可達1μm以下,顆粒較為細膩,著色效果好,且色澱還具有優異的應用性能如耐熱穩定性,其在溫度為125~150℃下均可穩定存在;耐酸鹼性,其在pH值為3.5~9.5條件下均較穩定;耐光性,其在長時間的日光照射下,仍不掉色、不變色,保持優異的色牢度。(2) The present invention provides a lake prepared by the above-mentioned preparation method. Compared with the traditional preparation method, the obtained lake has a smaller particle size, which can be less than 1 μm, the particles are finer, the coloring effect is good, and the color Dian also has excellent application properties such as heat resistance and stability, which can be stable at a temperature of 125 to 150 ℃; acid and alkali resistance, which is relatively stable at a pH value of 3.5 to 9.5; light resistance, which is It will not fade or change color under long-term sunlight, and maintain excellent color fastness.

由於採用螯合劑對金屬離子進行螯合的特定的製備方法,使得色澱中金屬離子含量較低,從而使得色澱不含重金屬,安全無毒,保證了產品的安全性。Due to the specific preparation method of chelating metal ions with a chelating agent, the content of metal ions in the lake is low, so that the lake does not contain heavy metals, is safe and non-toxic, and ensures the safety of the product.

(3)本發明提供了色澱的應用,鑒於上述色澱所具有的優勢,使得其在染料、油墨、顏料、墨水、醫藥、化妝品或食品等領域具有良好的應用。(3) The present invention provides the application of the lake. In view of the advantages of the above lake, it has good applications in the fields of dyes, inks, pigments, inks, medicine, cosmetics or food.

下面將結合實施例對本發明的實施方案進行詳細描述,但是本領域技術人員將會理解,下列實施例僅用於說明本發明,而不應視為限制本發明的範圍。實施例中未注明具體條件者,按照常規條件或製造商建議的條件進行。所用試劑或儀器未註明生產廠商者,均為可以通過市售購買獲得的常規產品。The embodiments of the present invention will be described in detail below in conjunction with examples, but those skilled in the art will understand that the following examples are only for illustrating the present invention and should not be considered as limiting the scope of the present invention. If no specific conditions are indicated in the examples, the conventional conditions or the conditions recommended by the manufacturer shall be followed. The reagents or instruments used do not indicate the manufacturer, are all conventional products that can be obtained through commercial purchase.

根據本發明第一個方面,提供了一種色澱的製備方法,包括以下步驟: (a)向含有色素原料的酸性水溶液中加入含有至少兩種金屬離子的溶液,反應,得到溶液A; (b)向溶液A中加入螯合劑溶液,於pH 6-8中進行螯合反應,分離,得到色澱。According to the first aspect of the present invention, a method for preparing a lake is provided, including the following steps: (a) Add a solution containing at least two metal ions to the acidic aqueous solution containing the pigment raw material, and react to obtain solution A; (b) Add a chelating agent solution to solution A, perform chelation reaction at pH 6-8, and separate to obtain a lake.

本發明先向含有色素原料的酸性水溶液中加入含有至少兩種金屬離子的溶液,形成溶液A,其中金屬離子與色素原料在酸性條件下靜電結合在一起,然後再向溶液A中加入螯合劑溶液,該螯合劑溶液在偏中性條件下(即在pH 6-8的條件下)與金屬離子發生螯合反應,並包覆在金屬離子外側形成螯合物沉澱,分離,即可得到結構、性能穩定的色澱。In the present invention, a solution containing at least two metal ions is added to an acid aqueous solution containing a pigment raw material to form a solution A, wherein the metal ion and the pigment raw material are electrostatically combined together under acidic conditions, and then a chelating agent solution is added to the solution A The chelating agent solution undergoes a chelating reaction with metal ions under partially neutral conditions (that is, at a pH of 6-8), and is coated on the outside of the metal ions to form a chelate precipitate, which can be separated to obtain the structure, The lake with stable performance.

需要說明的是,步驟(b)中,進行螯合反應時的pH在6-8之間,典型但非限制性的pH值為6、7或8。螯合體系中pH值不宜過低或過高,若pH值過低或過高,則可能會延長反應時間,甚至得不到相應的穩定的螯合物,嚴重影響色澱的產品品質。It should be noted that in step (b), the pH during the chelation reaction is between 6-8, and a typical but non-limiting pH value is 6, 7 or 8. The pH value in the chelating system should not be too low or too high. If the pH value is too low or too high, the reaction time may be prolonged, and even the corresponding stable chelate may not be obtained, which seriously affects the product quality of the lake.

對於步驟(b)中pH的調節,可採用添加氫氧化鈉或者碳酸氫鈉的方式,實現對溶液pH的調節。而且在逐步調高pH 於6-8之間時,會有部分金屬離子與氫氧根發生反應生成不必要的沉澱,而加入螯合劑正是利用螯合劑與金屬離子的強結合作用,將金屬離子包合到螯合劑內部生成螯合物沉澱,從而避免上述不必要的沉澱的產生,進一步提高產品的純度。同時,將金屬離子包合到螯合劑內部生成螯合物沉澱,使得色澱中金屬離子含量較低,從而使得色澱不含重金屬,安全無毒,保證了色澱的安全性。For the pH adjustment in step (b), the method of adding sodium hydroxide or sodium bicarbonate can be used to adjust the pH of the solution. And when the pH is gradually adjusted to between 6-8, some metal ions will react with hydroxide to generate unnecessary precipitation, and the addition of chelating agent is to use the strong binding effect of chelating agent and metal ion to remove the metal The inclusion of ions into the chelating agent generates a chelate precipitate, thereby avoiding the occurrence of the above-mentioned unnecessary precipitation and further improving the purity of the product. At the same time, the inclusion of metal ions into the chelating agent generates a chelate precipitate, which makes the content of metal ions in the lake low, thus making the lake free of heavy metals, safe and non-toxic, and ensuring the safety of the lake.

該製備方法製程簡單、操作方便,適合於大規模工業化推廣應用。The preparation method has simple process and convenient operation, and is suitable for large-scale industrialization and application.

與傳統製備方法相比,通過上述製備方法製得的色澱粒徑較小,可達1μm以下,著色效果好,且具有優異的應用性能如耐熱穩定性,其在溫度為125~150℃下均可穩定存在;耐酸鹼性,其在pH值為3.5~9.5條件下均較穩定;耐光性,其在長時間的日光照射下,仍不掉色、不變色,保持優異的色牢度。Compared with the traditional preparation method, the particle size of the lake prepared by the above preparation method is smaller, up to 1 μm or less, the coloring effect is good, and it has excellent application properties such as heat resistance and stability at a temperature of 125 to 150 ℃ They can all exist stably; acid and alkali resistance, which is relatively stable under the pH value of 3.5 to 9.5; light resistance, which does not fade or change color under long-term sunlight exposure, and maintains excellent color fastness.

作為本發明的一種較佳實施方式,步驟(a)中,色素原料包括天然植物色素、天然動物色素或合成色素中的一種或至少兩種的組合。As a preferred embodiment of the present invention, in step (a), the pigment raw material includes one or a combination of at least two of natural plant pigments, natural animal pigments, or synthetic pigments.

對於天然植物色素、天然動物色素或合成色素的具體種類不作特殊限定,採用本領域技術人員所熟知的原料即可。The specific types of natural plant pigments, natural animal pigments or synthetic pigments are not particularly limited, and raw materials well known to those skilled in the art may be used.

其中,典型但非限制性的天然植物色素例如為花青素、類胡蘿蔔素、葉黃素、番茄紅素、藏紅花色素、梔子黃色素、梔子綠色素、辣椒紅色素、甜椒紅色素、辣椒橙色素、南瓜黃色素、沙棘黃、密蒙黃色素、柑橘披黃色素、苜蓿色素、枸杞色素、銀杏黃色素、苦瓜色素或蒲公英色素。Among them, typical but non-limiting natural plant pigments are, for example, anthocyanins, carotenoids, lutein, lycopene, saffron pigments, gardenia yellow pigments, gardenia green pigments, capsicum red pigments, bell pepper red pigments , Capsicum orange pigment, pumpkin yellow pigment, sea buckthorn yellow, dense yellow pigment, citrus yellow pigment, alfalfa pigment, wolfberry pigment, ginkgo yellow pigment, bitter gourd pigment or dandelion pigment.

典型但非限制性的天然動物色素例如為胭脂蟲紅、紫膠紅、藻青素、魚鱗箔、蘇木藻色素、蝦殼色素、龍蝦紅色素、蟹殼色素、藻藍色素或念珠藻藍色色素。Typical but non-limiting natural animal pigments are for example cochineal red, shellac red, phycocyanin, fish scale foil, hematoxylin pigment, shrimp shell pigment, lobster red pigment, crab shell pigment, algal blue pigment or Candida blue pigment .

典型但非限制性的合成色素例如為莧菜紅、胭脂紅、檸檬黃、新紅、赤蘚紅、誘惑紅、日落黃、亮藍、靛藍或喹啉黃。Typical but non-limiting synthetic pigments are, for example, amaranth, carmine, lemon yellow, neo-red, erythrosine, alluring red, sunset yellow, brilliant blue, indigo, or quinoline yellow.

作為本發明的一種較佳實施方式,步驟(a)中,色素原料在酸性水溶液的質量分數為5-10%,較佳為6-9%,進一步較佳為7-8%;色素原料在酸性水溶液中典型但非限制性的質量分數為5%、6%、7%、8%、9%或10%。As a preferred embodiment of the present invention, in step (a), the mass fraction of the pigment raw material in the acidic aqueous solution is 5-10%, preferably 6-9%, further preferably 7-8%; Typical but non-limiting mass fractions in acidic aqueous solutions are 5%, 6%, 7%, 8%, 9% or 10%.

作為本發明的一種較佳實施方式,步驟(a)中,酸性水溶液的pH為0.5-2,酸性水溶液典型但非限制性的酸性水溶液的pH值為0.5、1、1.5或2。As a preferred embodiment of the present invention, in step (a), the pH of the acidic aqueous solution is 0.5-2, and the pH value of a typical but non-limiting acidic aqueous solution is 0.5, 1, 1.5, or 2.

通過對色素原料在酸性水溶液的質量分數以及酸性水溶液的pH值的限定,使得色素原料陰離子與金屬離子更易形成靜電吸附。By limiting the mass fraction of the pigment raw material in the acidic aqueous solution and the pH value of the acidic aqueous solution, the anion of the pigment raw material and metal ion are more likely to form electrostatic adsorption.

作為本發明的一種較佳實施方式,步驟(a)中,含有至少兩種金屬離子的溶液中金屬離子包括鉀離子、鈉離子、鐵離子、鋁離子、錫離子、鈣離子、鎂離子、銅離子、鉻離子或鋇離子中的至少兩種的組合。As a preferred embodiment of the present invention, in step (a), the metal ions in the solution containing at least two metal ions include potassium ions, sodium ions, iron ions, aluminum ions, tin ions, calcium ions, magnesium ions, copper A combination of at least two of ions, chromium ions, or barium ions.

對於具體金屬離子的種類以及配比不作具體限定,可以是兩種金屬離子的組合,例如鉀離子和鈉離子的組合、鐵離子和鋁離子的組合、鋁離子和錫離子的組合、錫離子和鈣離子的組合、鈣離子和鎂離子的組合、鉻離子和鋇離子的組合;也可以是三種金屬離子的組合,例如鉀離子、鈉離子和鉻離子的組合、鐵離子、鎂離子和鋁離子的組合、錫離子、鋁離子和鈣離子的組合等等。The type and ratio of specific metal ions are not specifically limited, and may be a combination of two metal ions, such as a combination of potassium ions and sodium ions, a combination of iron ions and aluminum ions, a combination of aluminum ions and tin ions, tin ions and Combination of calcium ions, combination of calcium ions and magnesium ions, combination of chromium ions and barium ions; can also be a combination of three metal ions, such as potassium ions, sodium ions and chromium ions, iron ions, magnesium ions and aluminum ions Combination, tin ion, aluminum ion and calcium ion, etc.

較佳地,金屬離子包括鋁離子和錫離子,進一步較佳地,鋁離子和錫離子的質量比為(1-10):1,典型但非限制性的鋁離子和錫離子的質量比為1 :1、2 :1、4 :1、5 :1、6 :1、8 :1或10 :1更較佳地,鋁離子和錫離子的質量比為2 :1。Preferably, the metal ions include aluminum ions and tin ions. Further preferably, the mass ratio of aluminum ions to tin ions is (1-10): 1, and the typical but non-limiting mass ratio of aluminum ions to tin ions is 1:1, 2:1, 4:1, 5:1, 6:1, 8:1 or 10:1 More preferably, the mass ratio of aluminum ions to tin ions is 2:1.

較佳地,金屬離子包括鐵離子和錫離子,進一步較佳地,鐵離子和錫離子的質量比為(0.5-10):1,典型但非限制性的鋁離子和錫離子的質量比為0.5 :1、1 :1、2 :1、4 :1、5 :1、6 :1、8 :1或10 :1;更佳地,鐵離子和錫離子的質量比為1 :1。Preferably, the metal ions include iron ions and tin ions. Further preferably, the mass ratio of iron ions to tin ions is (0.5-10): 1, and the typical but non-limiting mass ratio of aluminum ions to tin ions is 0.5: 1, 1: 1: 2, 2: 1, 4: 1, 5: 1, 6: 1, 8: 1 or 10: 1; more preferably, the mass ratio of iron ions and tin ions is 1:1.

較佳地,金屬離子包括鉀離子、鈉離子和鉻離子,進一步較佳地,鉀離子、鈉離子和鉻離子的質量比為(0.5-10):(0.5-10):1,典型但非限制性的鉀離子、鈉離子和鉻離子的質量比為0.5 :1 :1、2 :1 :1、4 :2 :1、5 :2 :1、10 :2 :1、10 :5 :1或10 :8 :1;更佳地,鉀離子、鈉離子和鉻離子的質量比為5 :2 :1。Preferably, the metal ions include potassium ions, sodium ions and chromium ions. Further preferably, the mass ratio of potassium ions, sodium ions and chromium ions is (0.5-10): (0.5-10): 1, typical but not The restrictive mass ratio of potassium ion, sodium ion and chromium ion is 0.5:1:1:1,2:1:1:1,4:2:1,5:2:1,10:2:1,10:5:1 Or 10:8:1; more preferably, the mass ratio of potassium ion, sodium ion and chromium ion is 5:2:1.

因為不同的金屬離子吸收光譜不同,加以不同金屬離子之間的比例不同,所以相同的染料原料,可以產生各種不同顏色或色偏的色澱,從而增大色澱的應用範圍。Because different metal ions have different absorption spectra and different ratios of different metal ions, the same dye raw material can produce lakes of various colors or color casts, thereby increasing the application range of lakes.

作為本發明的一種較佳實施方式,步驟(a)中,含有至少兩種金屬離子的溶液中金屬離子的質量分數為5-10%,較佳為6-9%,進一步較佳為7-8%。As a preferred embodiment of the present invention, in step (a), the mass fraction of metal ions in the solution containing at least two metal ions is 5-10%, preferably 6-9%, and more preferably 7- 8%.

典型但非限制性的金屬離子的質量分數為5%、6%、7%、8%、9%或10%。Typical but non-limiting mass fractions of metal ions are 5%, 6%, 7%, 8%, 9% or 10%.

通過對上述金屬離子種類、不同金屬離子之間的配比以及金屬離子質量分數的限定,使得螯合劑可以與金屬離子發生強結合作用,將金屬離子包合到螯合劑內部,更易形成穩定的、分子量更大的色澱產品。By restricting the types of metal ions, the ratio between different metal ions and the mass fraction of metal ions, the chelating agent can have a strong binding effect with the metal ions, and the metal ions can be included in the chelating agent, making it easier to form stable, Lake products with higher molecular weight.

作為本發明的一種較佳實施方式,步驟(a)中,含有色素原料的酸性水溶液與含有至少兩種金屬離子的質量比為(3-5):1;As a preferred embodiment of the present invention, in step (a), the mass ratio of the acidic aqueous solution containing the pigment raw material to the at least two metal ions is (3-5): 1;

含有色素原料的酸性水溶液與含有一種金屬離子的質量比典型但非限制性的例如為3 : 1、3.5 : 1、4 : 1、4.5 : 1或5 : 1。The mass ratio of the acidic aqueous solution containing the pigment raw material to that containing a metal ion is typically, but not limited to, for example, 3:1, 3.5:1, 4:1, 4.5:1, or 5:1.

作為本發明的一種較佳實施方式,步驟(a)中,反應溫度為50-60℃,反應時間為10-12h。As a preferred embodiment of the present invention, in step (a), the reaction temperature is 50-60° C., and the reaction time is 10-12 h.

色素原料與金屬離子典型但非限制性的反應溫度為50℃、52℃、54℃、55℃、56℃、58℃或60℃,典型但非限制性的反應時間為10h、11h或12h。The typical but non-limiting reaction temperature of the pigment raw material and the metal ion is 50°C, 52°C, 54°C, 55°C, 56°C, 58°C or 60°C, and the typical but non-limiting reaction time is 10h, 11h or 12h.

通過對含有至少兩種金屬離子的溶液中金屬離子的種類和質量分數的限定,使得色素原料的陰離子與金屬陽離子能更好的實現靜電結合。By defining the type and mass fraction of metal ions in a solution containing at least two metal ions, the anion of the pigment raw material and the metal cation can better achieve electrostatic bonding.

選用對上述金屬離子敏感的螯合劑,可使得螯合反應進行的更為順利。作為本發明的一種較佳實施方式,步驟(b)中,螯合劑溶液中的螯合劑包括草酸、檸檬酸、葡萄糖酸鈉、酒石酸或內酯中的一種。Selecting a chelating agent that is sensitive to the above metal ions can make the chelating reaction proceed more smoothly. As a preferred embodiment of the present invention, in step (b), the chelating agent in the chelating agent solution includes one of oxalic acid, citric acid, sodium gluconate, tartaric acid, or lactone.

草酸、檸檬酸、葡萄糖酸鈉、酒石酸或內酯均為羥基羧酸類螯合劑,能夠螯合大多數二價和三價金屬離子。其中草酸和檸檬酸能夠與金屬離子空軌道相結合形成配位化合物。葡萄糖酸鈉是一種良好的全能螯合劑,對多種金屬離子都有很好的螯合能力。Oxalic acid, citric acid, sodium gluconate, tartaric acid or lactone are all hydroxycarboxylic acid chelating agents, which can chelate most divalent and trivalent metal ions. Among them, oxalic acid and citric acid can combine with metal ion empty orbits to form coordination compounds. Sodium gluconate is a good all-round chelating agent, and it has a good chelating ability to various metal ions.

作為本發明的一種較佳實施方式,步驟(b)中,螯合劑溶液中的螯合劑的質量分數為5-10%,較佳為6-9%,進一步較佳為7-8%。典型但非限制性的螯合劑的質量分數為5%、6%、7%、8%、9%或10%。As a preferred embodiment of the present invention, in step (b), the mass fraction of the chelating agent in the chelating agent solution is 5-10%, preferably 6-9%, further preferably 7-8%. The mass fraction of a typical but non-limiting chelating agent is 5%, 6%, 7%, 8%, 9% or 10%.

作為本發明的一種較佳實施方式,溶液A與螯合劑的質量比為1:1;As a preferred embodiment of the present invention, the mass ratio of solution A to chelating agent is 1:1;

作為本發明的一種較佳實施方式,螯合溫度為50-60℃,螯合時間為1-2h。As a preferred embodiment of the present invention, the chelating temperature is 50-60°C, and the chelating time is 1-2h.

典型但非限制性的螯合溫度為50℃、52℃、54℃、55℃、56℃、58℃或60℃,典型但非限制性的螯合時間為1h、1.5h或2h。Typical but non-limiting chelation temperatures are 50°C, 52°C, 54°C, 55°C, 56°C, 58°C or 60°C, and typical but non-limiting chelation times are 1h, 1.5h or 2h.

通過螯合劑種類、螯合劑質量分數以及螯合溫度與時間的限定,使得螯合反應進行更為充分,所形成的螯合物具有較高的穩定性。The limitation of the type of chelating agent, the mass fraction of the chelating agent and the chelating temperature and time makes the chelation reaction proceed more fully, and the formed chelate compound has higher stability.

作為本發明的一種較佳實施方式,該色澱的製備方法,包括如下步驟: (a)向含有質量分數為5-10%色素原料的酸性水溶液中滴加含有至少兩種金屬離子的溶液,反應,反應溫度為50-60℃,反應時間為10-12h,得到溶液A;其中,金屬離子包括鉀離子、鈉離子、鐵離子、鋁離子、錫離子、鈣離子、鎂離子、銅離子、鉻離子或鋇離子中的至少兩種的組合; (b)向溶液A中加入螯合劑溶液,升溫至50-60℃,於pH 6-8中進行螯合反應,反應結束後,洗脫,分離,乾燥,得到色澱; 其中,螯合劑溶液中的螯合劑包括草酸、檸檬酸、葡萄糖酸鈉、酒石酸或內酯中的一種。As a preferred embodiment of the present invention, the preparation method of the lake includes the following steps: (a) Add a solution containing at least two metal ions dropwise to an acidic aqueous solution containing 5-10% pigment raw material, and react. The reaction temperature is 50-60°C and the reaction time is 10-12h to obtain solution A; Wherein, the metal ion includes a combination of at least two of potassium ion, sodium ion, iron ion, aluminum ion, tin ion, calcium ion, magnesium ion, copper ion, chromium ion or barium ion; (b) Add a chelating agent solution to solution A, raise the temperature to 50-60°C, and perform a chelating reaction at pH 6-8. After the reaction, elute, separate, and dry to obtain a lake; The chelating agent in the chelating agent solution includes one of oxalic acid, citric acid, sodium gluconate, tartaric acid, or lactone.

步驟(b)中,分離通常採用濾膜或者濾網,即採用一定目數的濾膜或者濾網濾出沉澱物,並於真空下去除游離水;將去除游離水後的沉澱物置於乾燥設備中乾燥至含水率符合要求,即得到色澱。In step (b), the separation usually uses a filter membrane or a filter screen, that is, a certain mesh filter membrane or filter screen is used to filter out the precipitate, and the free water is removed under vacuum; the precipitate after removing the free water is placed in a drying device Medium drying until the moisture content meets the requirements, that is, the lake.

通過對色澱的製備方法中具體步驟以及製程參數的限定,使得所製得的色澱具有良好的性能和品質。By defining the specific steps in the preparation method of the lake and the parameters of the process, the resulting lake has good performance and quality.

作為本發明的一種較佳實施方式,色澱的粒徑不大於1μm,特別是在0.45μm以下,更特別是在0.22μm以下,一般在10nm~0.5μm之間。由於其粒徑較細,進而極大的提高了著色強度,光穩定性更好,應用不受限制。As a preferred embodiment of the present invention, the particle size of the lake is not more than 1 μm, especially below 0.45 μm, more particularly below 0.22 μm, generally between 10 nm and 0.5 μm. Because of its finer particle size, the coloring strength is greatly improved, the light stability is better, and the application is not limited.

根據本發明的第二個方面,還提供了一種色澱,採用上述色澱的製備方法製得; 較佳地,色澱的粒徑不大於1μm,特別是在0.45μm以下,更特別是在0.22μm以下。According to the second aspect of the present invention, a color lake is also provided, which is prepared by the above-mentioned color lake preparation method; Preferably, the particle size of the lake is not more than 1 μm, especially below 0.45 μm, more particularly below 0.22 μm.

本發明提供的一種色澱,採用上述製備方法製得,與傳統製備方法相比,所得到的色澱粒徑較小,可達1μm以下,且具有優異的應用性能如耐熱性,其在溫度為125~150℃下均可穩定存在;耐酸鹼性,其在pH值為3.5~9.5條件下均較穩定;耐光性,其在長時間的日光照射下,仍不掉色、不變色,保持優異的色牢度。The lake provided by the present invention is prepared by the above-mentioned preparation method. Compared with the traditional preparation method, the particle size of the obtained lake is smaller, which can be less than 1 μm, and has excellent application properties such as heat resistance. It can be stable at 125~150℃; it is acid and alkali resistant, it is more stable under the pH value of 3.5~9.5; light resistance, it will not fade or change color under long-term sunlight Excellent color fastness.

由於所採用的特定的製備方法,使得色澱中金屬離子含量較低,從而使得色澱不含重金屬,安全無毒,保證了產品的安全性。Due to the specific preparation method adopted, the content of metal ions in the lake is low, so that the lake does not contain heavy metals, is safe and non-toxic, and ensures the safety of the product.

根據本發明的第三個方面,還提供了一種色澱的應用。According to the third aspect of the present invention, an application of a lake is also provided.

鑒於上述色澱所具有的優勢,使得其在染料、油墨、顏料、墨水、製備藥物、化妝品或食品等領域具有良好的應用。In view of the advantages of the above lake, it has good applications in the fields of dyes, inks, pigments, inks, preparation of medicines, cosmetics or food.

下面結合具體實施例和對比例,對本發明作進一步說明。The present invention will be further described below with reference to specific examples and comparative examples.

實施例1Example 1

本實施例提供的一種色澱的製備方法,包括如下步驟: (a)將梔子黃色素溶於pH為 2的酸性水溶液中,製成質量分數為5%的染料溶液,混合均勻; 在攪拌下,1h內滴加質量分數為5%的含有兩種金屬離子(鋁離子和錫離子,質量比為2 :1)的溶液,升溫至50℃,恆溫反應10h,得到溶液A; 其中,染料溶液與含有兩種金屬離子的溶液的質量比為5:1; (b)於攪拌下,1h內向溶液A中滴加質量分數為5%的草酸溶液,升溫至50℃,再於攪拌下,1h內逐漸調高溶液pH值為6的條件中螯合,反應結束後,洗脫,膜過濾,乾燥,得到色澱; 其中,溶液A與草酸溶液的質量比為5:1。The method for preparing a lake provided by this embodiment includes the following steps: (a) Dissolve the gardenia yellow pigment in an acidic aqueous solution with a pH of 2 to prepare a dye solution with a mass fraction of 5% and mix it uniformly; Under stirring, a solution containing two kinds of metal ions (aluminum ions and tin ions, with a mass ratio of 2:1) of 5% by mass was added dropwise within 1 hour, and the temperature was raised to 50°C, and the reaction was carried out at a constant temperature for 10 hours to obtain solution A; Among them, the mass ratio of the dye solution to the solution containing two metal ions is 5:1; (b) Under stirring, add 5% oxalic acid solution to solution A dropwise within 1h, warm to 50°C, then under stirring, gradually increase the pH value of the solution to 6 within 1h to chelate and react After the end, elution, membrane filtration and drying to obtain lake; Among them, the mass ratio of solution A to oxalic acid solution is 5:1.

實施例2Example 2

本實施例提供的一種色澱的製備方法,包括如下步驟: (a)將藻青素溶於pH為1的酸性水溶液中,製成質量分數為10%的染料溶液,混合均勻; 在攪拌下,2h內滴加質量分數為8%的含有兩種金屬離子(鐵離子和錫離子,質量比為1 :1)的溶液,升溫至55℃,恆溫反應12h,得到溶液A; 其中,染料溶液與含有兩種金屬離子的溶液的質量比為3:1; (b)於攪拌下,2h內向溶液A中滴加質量分數為8%的檸檬酸溶液,升溫至55℃,再於攪拌下,2h內逐漸調高溶液pH值為7的條件中螯合,反應結束後,洗脫,膜過濾,乾燥,得到色澱; 其中,溶液A與檸檬酸溶液的質量比為4:1。The method for preparing a lake provided by this embodiment includes the following steps: (a) Dissolve phycocyanin in an acidic aqueous solution with a pH of 1 to prepare a dye solution with a mass fraction of 10%, and mix evenly; Under stirring, a solution containing two kinds of metal ions (iron ions and tin ions, mass ratio of 1:1) with a mass fraction of 8% was added dropwise within 2 hours. The solution was heated to 55°C and reacted at a constant temperature for 12 hours to obtain solution A; Among them, the mass ratio of the dye solution to the solution containing two metal ions is 3:1; (b) Under stirring, add a citric acid solution with a mass fraction of 8% to solution A within 2 hours, warm to 55°C, and then under stirring, gradually increase the pH of the solution to 7 within 2 hours. After the reaction, elute, filter the membrane, and dry to obtain lake; Among them, the mass ratio of solution A to citric acid solution is 4:1.

實施例3Example 3

本實施例提供的一種色澱的製備方法,包括如下步驟: (a)將日落黃溶於pH為0.5的酸性水溶液中,製成質量分數為7%的染料溶液,混合均勻; 在攪拌下,1.5h內向染料溶液中滴加質量分數為10%的含有至少兩種金屬離子(鈉離子和鉻離子,質量比為5 :1)的溶液,升溫至60℃,恆溫反應11h,得到溶液A; 其中,染料溶液與含有至少兩種金屬離子的溶液的質量比為5:1; (b)於攪拌下,1.5h內向溶液A中滴加質量分數為10%的內酯溶液,升溫至60℃,再於攪拌下,2h內逐漸調高溶液pH值為8的條件中螯合,反應結束後,洗脫,膜過濾,乾燥,得到色澱; 其中,溶液A與內酯溶液的質量比為5:1。The method for preparing a lake provided by this embodiment includes the following steps: (a) Dissolve sunset yellow in an acidic aqueous solution with a pH of 0.5 to make a dye solution with a mass fraction of 7%, and mix evenly; Under stirring, a solution containing at least two kinds of metal ions (sodium ions and chromium ions, mass ratio of 5:1) with a mass fraction of 10% is added dropwise to the dye solution within 1.5 hours. The temperature is raised to 60°C and the reaction is carried out at a constant temperature for 11 hours. Get solution A; Among them, the mass ratio of the dye solution to the solution containing at least two metal ions is 5:1; (b) Under stirring, add a lactone solution with a mass fraction of 10% to solution A within 1.5h, and warm up to 60°C. Then, under stirring, gradually increase the pH of the solution to 8 under 2h. After the reaction, elute, filter the membrane, and dry to obtain the lake; Among them, the mass ratio of solution A to lactone solution is 5:1.

實施例4Example 4

本實施例提供的一種色澱的製備方法,除了步驟(b)中,溶液pH調至8,其餘步驟以及製程參數與實施例1相同。This embodiment provides a method for preparing a lake, except that in step (b), the pH of the solution is adjusted to 8, the remaining steps and process parameters are the same as in Example 1.

實施例5Example 5

本實施例提供的一種色澱的製備方法,除了步驟(b)中螯合劑溶液採用羥乙基乙二胺三乙酸(HEDTA),其餘步驟以及製程參數與實施例1相同。This embodiment provides a method for preparing a lake, except that the chelating agent solution in step (b) uses hydroxyethylethylenediamine triacetic acid (HEDTA), and the remaining steps and process parameters are the same as those in Example 1.

實施例6Example 6

本實施例提供的一種色澱的製備方法,除了步驟(b)中螯合劑溶液採用二羥乙基甘氨酸(DEG),其餘步驟以及製程參數與實施例2相同。This embodiment provides a method for preparing a lake, except that the chelating agent solution in step (b) uses dihydroxyethylglycine (DEG), and the remaining steps and process parameters are the same as in Example 2.

實施例7Example 7

本實施例提供的一種色澱的製備方法,除了步驟(b)中螯合劑溶液中螯合劑的質量分數為3%,其餘步驟以及製程參數與實施例2相同。This embodiment provides a method for preparing a lake, except that the mass fraction of the chelating agent in the chelating agent solution in step (b) is 3%, and the remaining steps and process parameters are the same as in Example 2.

實施例8Example 8

本實施例提供的一種色澱的製備方法,除了步驟(b)中螯合劑溶液為葡萄糖酸鈉溶液,其餘步驟以及製程參數與實施例3相同。This embodiment provides a method for preparing a lake, except that the chelating agent solution in step (b) is a sodium gluconate solution, and the remaining steps and process parameters are the same as in Example 3.

實施例9Example 9

本實施例提供的一種色澱的製備方法,除了步驟(b)中螯合劑溶液為酒石酸溶液,其餘步驟以及製程參數與實施例3相同。This embodiment provides a method for preparing a lake, except that the chelating agent solution in step (b) is a tartaric acid solution, and the remaining steps and process parameters are the same as in Example 3.

實施例10Example 10

本實施例提供的一種色澱的製備方法,除了步驟(b)中螯合溫度為40℃,其餘步驟以及製程參數與實施例3相同。This embodiment provides a method for preparing a lake, except that the chelating temperature in step (b) is 40° C. The remaining steps and process parameters are the same as in Example 3.

實施例11Example 11

本實施例提供的一種色澱的製備方法,除了步驟(b)中螯合溫度為70℃,其餘步驟以及製程參數與實施例3相同。This embodiment provides a method for preparing a lake, except that the chelating temperature in step (b) is 70° C. The remaining steps and process parameters are the same as in Example 3.

實施例12Example 12

本實施例提供的一種色澱的製備方法,除了步驟(b)中螯合時間為0.5h,其餘步驟以及製程參數與實施例3相同。This embodiment provides a method for preparing a lake, except that the chelating time in step (b) is 0.5 h, and the remaining steps and process parameters are the same as in Example 3.

實施例13Example 13

本實施例提供的一種色澱的製備方法,包括如下步驟: (a)將亮藍溶於pH為 3.5的酸性水溶液中,製成質量分數為8%的染料溶液,混合均勻; 在攪拌下,1h內向染料溶液中滴加質量分數為6%的含有至少兩種金屬離子(鉀離子、鈉離子和鉻離子,質量比為5 :2 :1)的溶液,升溫至56℃,恆溫反應10h,得到溶液A; 其中,染料溶液與含有至少兩種金屬離子的溶液的質量比為5:1; (b)於攪拌下,1.5h內向溶液A中滴加質量分數為10%的內酯溶液,升溫至60℃,再於攪拌下,1h內逐漸調高溶液pH值為7的條件中螯合,反應結束後,洗脫,膜過濾,乾燥,得到色澱; 其中,溶液A與內酯溶液的質量比為5:1。The method for preparing a lake provided by this embodiment includes the following steps: (a) Dissolve Brilliant Blue in an acidic aqueous solution with a pH of 3.5 to make a dye solution with a mass fraction of 8%, and mix evenly; Under stirring, a solution containing at least two kinds of metal ions (potassium ions, sodium ions and chromium ions, with a mass ratio of 5:2:1) of 6% by mass was added dropwise to the dye solution within 1 hour, and the temperature was raised to 56°C. Constant temperature reaction for 10h to obtain solution A; Among them, the mass ratio of the dye solution to the solution containing at least two metal ions is 5:1; (b) Under stirring, add a lactone solution with a mass fraction of 10% to solution A within 1.5 hours, and warm up to 60°C. Then, under stirring, gradually increase the pH of the solution to 7 within 1 hour. After the reaction, elute, filter the membrane, and dry to obtain the lake; Among them, the mass ratio of solution A to lactone solution is 5:1.

對比例1Comparative Example 1

本對比例提供的一種色澱的製備方法,除了步驟(b)中,溶液pH調至4,其餘步驟以及製程參數與實施例1相同。A method for preparing a lake provided in this comparative example, except that in step (b), the pH of the solution is adjusted to 4, the remaining steps and process parameters are the same as in Example 1.

對比例2Comparative Example 2

本對比例提供的一種色澱的製備方法,除了步驟(b)中,溶液pH調至10,其餘步驟以及製程參數與實施例1相同。The method for preparing a lake provided in this comparative example, except that in step (b), the pH of the solution is adjusted to 10, the remaining steps and process parameters are the same as in Example 1.

對比例3Comparative Example 3

本對比例提供的一種色澱的製備方法,除了步驟(b)中未添加螯合劑溶液,其餘步驟以及製程參數與實施例1相同。The preparation method of the lake provided in this comparative example is the same as that in Example 1 except that the chelating agent solution is not added in step (b).

為了驗證實施例1-13以及對比例1-3的效果,特設以下實驗例。In order to verify the effects of Examples 1-13 and Comparative Examples 1-3, the following experimental examples were set up.

實驗例1Experimental Example 1

對實施例1-13和對比例1-3所製得的色澱的性能進行測試,具體結果見表1。The properties of the lakes prepared in Examples 1-13 and Comparative Examples 1-3 were tested. The specific results are shown in Table 1.

其中,採用篩分法測定色澱的顆粒度大小; 耐水溶出性是利用分光光度法對溶出物質進行定量測量; 著色強度是採用分光光度法對水溶出物質進行定量測定的結果,上色後溶出物質越少代表著色強度越高,其中,著色強度優異是指1-999μg/mL;著色強度極佳是指1000-4999μg/mL;著色強度高是指5000-15000μg/mL; 耐熱穩定性測試方法為:將色澱放在烘箱中,在不同的溫度下恆溫30min; 耐光性的測試方式為:將色澱用少量水分散,然後塗裝在白紙上,將著色樣品置於疝氣燈下照400小時,取出觀察褪色程度,對照藍標,8級最佳,1級最差; 耐酸鹼性的測試方式為:將色澱放在不同pH的酸性溶液和鹼液溶液中,保持24小時觀察變色程度。Among them, the sieving method is used to determine the particle size of the lake; Water dissolution resistance is the quantitative measurement of the dissolved substances by spectrophotometry; Coloring strength is the result of quantitative determination of water-dissolved substances by spectrophotometry. Less coloring after coloring means higher coloring strength. Among them, excellent coloring strength means 1-999 μg/mL; excellent coloring strength means 1000 -4999μg/mL; high color strength means 5000-15000μg/mL; The heat resistance stability test method is: place the lake in an oven and keep it at a constant temperature for 30 minutes at different temperatures; The light resistance test method is: disperse the lake with a small amount of water, then coat it on white paper, place the colored sample under a hernia lamp and illuminate it for 400 hours, take out and observe the degree of discoloration, control blue label, grade 8 is best, grade 1 Worst The test method for acid and alkali resistance is: place the lake in acid solution and lye solution of different pH, and keep it for 24 hours to observe the degree of discoloration.

表1 各實施例和對比例色澱物理性能測試結果。

Figure 02_image001
Table 1 Test results of physical properties of lakes of the examples and comparative examples.
Figure 02_image001

表2 各實施例和對比例色澱應用性能測試結果。

Figure 02_image003
Table 2 Application performance test results of various examples and comparative lakes.
Figure 02_image003

由表1可以看出,通過本發明的製備製程製備得到的色澱,整體上粒徑小,可以達到在1μm以下,且具有較好的耐熱穩定性、耐酸鹼性能和耐光性能。It can be seen from Table 1 that the lake prepared by the preparation process of the present invention has a small particle size as a whole, can reach less than 1 μm, and has good heat stability, acid and alkali resistance and light resistance.

其中,實施例5為實施例1的對照實驗,實施例6為實施例2的對照實驗,實施例5和實施例6均採用不同於本發明限定的螯合劑種類。由表1和2中資料可以看出,相比實施例1和實施例2,實施例5和實施例6製備得到的色澱,耐光性較差,且著色強度也較低,還部分溶於水,耐水溶出性較差,導致應用時受到很大的限制,不能滿足市場的需求。Among them, Example 5 is a control experiment of Example 1, Example 6 is a control experiment of Example 2, and Examples 5 and 6 use different types of chelating agents defined in the present invention. As can be seen from the data in Tables 1 and 2, compared to Example 1 and Example 2, the lakes prepared in Example 5 and Example 6 have poor light resistance and low color strength, and are partially soluble in water. , Poor water dissolution resistance, resulting in great restrictions in application, can not meet market demand.

實施例7為實施例2的對照實驗,兩者不同之處在於螯合劑溶液中螯合劑的質量分數不同。當螯合劑溶液中螯合劑的質量分數低於本發明限定的數值範圍時,體系中螯合劑的用量太少,螯合能力有限,故色澱產率較低,且有部分金屬離子螯合不完全,從而進入到色澱產品中,造成色澱中金屬離子含量較高,影響色澱的使用安全性。Example 7 is a control experiment of Example 2. The difference between the two is that the mass fraction of the chelating agent in the chelating agent solution is different. When the mass fraction of the chelating agent in the chelating agent solution is lower than the numerical range defined by the present invention, the amount of the chelating agent in the system is too small, the chelating ability is limited, so the yield of the lake is low, and some metal ions do not chelate. Completely, so as to enter the lake product, resulting in a higher content of metal ions in the lake, affecting the safety of the lake.

實施例10-12均為實施例3的對照實驗,四者不同之處在於螯合反應時螯合溫度或螯合時間不同。由表1和2中資料可以看出,螯合溫度過低時,活化能不足,而螯合溫度過高時,螯合劑的螯合能力下降,即當螯合溫度超出本發明限定的數值範圍時,螯合劑與金屬離子均不能很好的形成穩定的螯合物。當螯合時間過短時,螯合劑與金屬離子發生螯合反應不充分,色澱的產率較低,且純度不高。Examples 10-12 are the control experiments of Example 3, the difference between the four is that the chelation temperature or time during the chelation reaction is different. It can be seen from the data in Tables 1 and 2 that when the chelating temperature is too low, the activation energy is insufficient, and when the chelating temperature is too high, the chelating ability of the chelating agent decreases, that is, when the chelating temperature exceeds the numerical range defined by the present invention At this time, neither the chelating agent nor the metal ion can form a stable chelate well. When the chelating time is too short, the chelating agent and metal ions have insufficient chelation reaction, the yield of lake is low, and the purity is not high.

對比例1和對比例2均為實施例1的對比實驗,三者不同之處在於螯合反應時體系pH值不同。不同pH值條件下,螯合劑對於金屬離子的螯合能力不同。由表1和2中資料可以看出,當體系pH值在本發明限定的數值範圍內時,螯合劑對於金屬離子才具有較強的螯合能力,從而使得得到的色澱具有較為優異的性能。Comparative Example 1 and Comparative Example 2 are comparative experiments of Example 1. The difference between the three is that the pH value of the system during the chelation reaction is different. Under different pH conditions, the chelating ability of the chelating agent to metal ions is different. It can be seen from the data in Tables 1 and 2 that when the pH value of the system is within the numerical range defined by the present invention, the chelating agent has a strong chelating ability for metal ions, thereby making the resulting lake have superior performance .

對比例3為實施例1的對比實驗,兩者不同之處在於是否添加螯合劑溶液。體系中未添加螯合劑溶液時,不能產生色澱。Comparative Example 3 is a comparative experiment of Example 1. The difference between the two is whether a chelating agent solution is added. When no chelating agent solution is added to the system, no lake can be produced.

綜上所述,本發明提供的色澱的製備方法製程簡單、操作方便,製備得到的色澱粒徑較小,具有很高的著色力和較好的耐熱性,耐酸鹼性能和耐光性能優異,拓寬了色澱的應用範圍,為色澱的工業化生產提供依據。In summary, the preparation method of the lake provided by the present invention is simple in process and convenient in operation, the prepared lake has a small particle size, high color rendering power and good heat resistance, acid and alkali resistance and light resistance Excellent, widen the application range of color lake, and provide a basis for the industrial production of color lake.

最後應說明的是:以上各實施例僅用以說明本發明的技術方案,而非對其限制;儘管參照前述各實施例對本發明進行了詳細的說明,本領域的普通技術人員應當理解:其依然可以對前述各實施例所記載的技術方案進行修改,或者對其中部分或者全部技術特徵進行等同替換;而這些修改或者替換,並不使相應技術方案的本質脫離本發明各實施例技術方案的範圍。Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, rather than limiting it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features can be equivalently replaced; and these modifications or replacements do not deviate from the essence of the corresponding technical solutions of the technical solutions of the embodiments of the present invention. range.

無。no.

無。no.

無。no.

Claims (10)

一種色澱的製備方法,包括以下步驟: (a)向含有色素原料的酸性水溶液中加入含有至少兩種金屬離子的溶液,反應,得到溶液A;以及 (b)向所述溶液A中加入螯合劑溶液,於pH 6-8中進行螯合反應,分離,得到色澱。A method for preparing a lake includes the following steps: (a) Adding a solution containing at least two metal ions to an acidic aqueous solution containing pigment raw materials, and reacting to obtain a solution A; and (b) Add a chelating agent solution to the solution A, perform a chelating reaction at pH 6-8, and separate to obtain a lake. 如請求項1所述之製備方法,其中,步驟(a)中,所述色素原料包括天然植物色素、天然動物色素或合成色素中的一種或至少兩種的組合;及/或 步驟(a)中,所述色素原料在所述酸性水溶液的質量分數為5-10%,較佳為6-9%,進一步較佳為7-8%;及/或 步驟(a)中,所述酸性水溶液的pH為0.5-2。The preparation method according to claim 1, wherein in step (a), the pigment raw material includes one or a combination of at least two of natural plant pigments, natural animal pigments or synthetic pigments; and/or In step (a), the mass fraction of the pigment raw material in the acidic aqueous solution is 5-10%, preferably 6-9%, further preferably 7-8%; and/or In step (a), the pH of the acidic aqueous solution is 0.5-2. 如請求項1所述之製備方法,其中,步驟(a)中,所述含有至少兩種金屬離子的溶液中的金屬離子包括鉀離子、鈉離子、鐵離子、鋁離子、錫離子、鈣離子、鎂離子、銅離子、鉻離子或鋇離子中的至少兩種的組合; 較佳地,所述金屬離子包括鋁離子和錫離子,進一步較佳地,鋁離子和錫離子的質量比為(1-10):1; 較佳地,所述金屬離子包括鐵離子和錫離子,進一步較佳地,鐵離子和錫離子的質量比為(0.5-10):1;及/或 步驟(a)中,所述含有至少兩種金屬離子的溶液中金屬離子的質量分數為5-10%,較佳為6-9%,進一步較佳為7-8%。The preparation method according to claim 1, wherein in step (a), the metal ions in the solution containing at least two metal ions include potassium ions, sodium ions, iron ions, aluminum ions, tin ions, calcium ions , Magnesium ion, copper ion, chromium ion or barium ion at least two combinations; Preferably, the metal ions include aluminum ions and tin ions. Further preferably, the mass ratio of aluminum ions to tin ions is (1-10): 1; Preferably, the metal ions include iron ions and tin ions. Further preferably, the mass ratio of iron ions to tin ions is (0.5-10): 1; and/or In step (a), the mass fraction of metal ions in the solution containing at least two metal ions is 5-10%, preferably 6-9%, and more preferably 7-8%. 如請求項1所述之製備方法,其中,步驟(a)中,所述含有色素原料的酸性水溶液與所述含有至少兩種金屬離子的溶液的質量比為(3-5):1;及/或 步驟(a)中,反應溫度為50-60℃,反應時間為10-12h。The preparation method according to claim 1, wherein in step (a), the mass ratio of the acidic aqueous solution containing the pigment raw material to the solution containing at least two metal ions is (3-5): 1; and /or In step (a), the reaction temperature is 50-60°C and the reaction time is 10-12h. 如請求項1所述之製備方法,其中,步驟(b)中,所述螯合劑溶液中的螯合劑包括草酸、檸檬酸、葡萄糖酸鈉、酒石酸或內酯中的一種;及/或 步驟(b)中,所述螯合劑溶液中的螯合劑的質量分數為5-10%,較佳為6-9%,進一步較佳為7-8%。The preparation method according to claim 1, wherein in step (b), the chelating agent in the chelating agent solution includes one of oxalic acid, citric acid, sodium gluconate, tartaric acid, or lactone; and/or In step (b), the mass fraction of the chelating agent in the chelating agent solution is 5-10%, preferably 6-9%, and more preferably 7-8%. 如請求項1所述之製備方法,其中,所述溶液A與所述螯合劑溶液的質量比為(0.5-1.5): 1;及/或 螯合溫度為50-60℃,螯合時間為1-2h。The preparation method according to claim 1, wherein the mass ratio of the solution A to the chelating agent solution is (0.5-1.5): 1; and/or The chelating temperature is 50-60℃, and the chelating time is 1-2h. 如請求項1所述之製備方法,其中,包括如下步驟: (a)向含有質量分數為5-10%色素原料的酸性水溶液中滴加含有至少兩種金屬離子的溶液,反應,反應溫度為50-60℃,反應時間為10-12h,得到溶液A;其中,所述金屬離子包括鉀離子、鈉離子、鐵離子、鋁離子、錫離子、鈣離子、鎂離子、銅離子、鉻離子或鋇離子中的至少兩種的組合; (b)向所述溶液A中加入螯合劑溶液,升溫至50-60℃,於pH 6-8中進行螯合反應,反應結束後,洗脫,分離,乾燥,得到色澱; 其中,所述螯合劑溶液中的螯合劑包括草酸、檸檬酸、葡萄糖酸鈉、酒石酸或內酯中的一種。The preparation method according to claim 1, which includes the following steps: (a) Add a solution containing at least two metal ions dropwise to an acidic aqueous solution containing 5-10% pigment raw material, and react. The reaction temperature is 50-60°C and the reaction time is 10-12h to obtain solution A; Wherein, the metal ion includes a combination of at least two of potassium ion, sodium ion, iron ion, aluminum ion, tin ion, calcium ion, magnesium ion, copper ion, chromium ion or barium ion; (b) Add a chelating agent solution to the solution A, raise the temperature to 50-60°C, and perform a chelating reaction at pH 6-8. After the reaction, elute, separate, and dry to obtain a lake; Wherein, the chelating agent in the chelating agent solution includes one of oxalic acid, citric acid, sodium gluconate, tartaric acid or lactone. 如請求項1至7中任一項所述之製備方法,其中,所述色澱的粒徑不大於1μm; 較佳地,所述色澱的粒徑不大於0.22μm。The preparation method according to any one of claims 1 to 7, wherein the particle size of the lake is not more than 1 μm; Preferably, the particle size of the lake is not greater than 0.22 μm. 一種色澱,其採用請求項1至8中任一項所述之色澱的製備方法製得; 較佳地,所述色澱的粒徑不大於1μm,進一步較佳地,色澱的粒徑不大於0.22μm。A color lake prepared by the method for preparing a color lake described in any one of claims 1 to 8; Preferably, the particle size of the lake is not greater than 1 μm, further preferably, the particle size of the lake is not greater than 0.22 μm. 一種色澱的應用,其係請求項1至8中任一項所述之色澱的製備方法製得的色澱或請求項9所述之色澱在染料、油墨、顏料、墨水、製備藥物、化妝品或食品中的應用。An application of a lake, which is a lake prepared by the method for preparing a lake described in any one of claims 1 to 8 or a lake described in claim 9 in dyes, inks, pigments, inks, and pharmaceutical preparations , Cosmetics or food applications.
TW108133064A 2018-09-12 2019-09-12 Method for preparing lake pigment, lake pigment and use thereof TW202010796A (en)

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