TWI735951B - Preparation method of lake - Google Patents

Abstract

8的條件下發生螯合/絡合反應，得到色澱。本發明方法簡單易行，方便色澱顏色或色相差的調節，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。 The invention belongs to the technical field of lakes, and relates to a method for preparing lakes, lakes and applications thereof. The preparation method of the lake of the present invention includes the following steps: adding a solution containing at least two metal ions to an acid dye solution containing pigment raw materials to obtain solution A; adding a chelating agent to solution A, and increasing the pH value

The chelating/complexing reaction occurs under the conditions of 8, and the lake is obtained. The method of the invention is simple and easy to implement, facilitates the adjustment of the color or color difference of the lake, the prepared lake has a small particle size, high coloring power and better heat resistance, excellent acid and alkali resistance and light resistance, and widens The scope of application of the lake.

Description

Preparation method of lake

The invention belongs to the technical field of lakes, and specifically relates to a method for preparing lakes, lakes and applications thereof.

Lake generally refers to the pigment produced by the precipitation of soluble dyes in inorganic bases, and it is basically insoluble in water. Different from water-soluble pigments, lakes can remain particulate and insoluble in most solvents. Lakes are non-water-soluble colored substances precipitated by water-soluble dyes under the action of different types of precipitating agents. Generally, lakes are required to have bright shades, good hiding power, insoluble in water, stable to acid, alkali, and heat, and have good light resistance.

Most of the existing lakes are prepared using aluminum hydroxide as a substrate. Improvements in the preparation process of lakes are also mainly focused on the preparation of activated aluminum hydroxide substrates. The traditional preparation of aluminum hydroxide is prepared by the reaction of aluminum sulfate with sodium hydroxide and sodium carbonate, which has disadvantages such as affecting the adsorption of the pigment by the matrix, consuming a large amount of washing water, and poor performance and stability of the obtained product. The improved preparation methods of aluminum hydroxide, such as those prepared from aluminum trichloride and sodium bicarbonate, still have the defects of softness, easy pulverization, inconvenience, and poor water dissolution resistance.

In addition, the existing methods for preparing lakes also have the problems of large particle size of the lakes produced, which reduces the color strength and limits the application; and the light resistance, acid and alkali resistance, heat resistance, etc. are not ideal; The color adjustment method of the lake is single, and the color is single.

In view of this, the present invention is proposed.

The first object of the present invention is to provide a method for preparing a lake, which is simple and easy to implement, and facilitates the adjustment of the color or color difference of the lake. The prepared lake has a small particle size, high coloring power and better Heat resistance, acid and alkali resistance and light resistance are excellent, which broadens the application of lake Use range.

The second object of the present invention is to provide a lake. The lake prepared by the method of the present invention is rich in color, bright, small in particle size, has high coloring power, good heat resistance, acid and alkali resistance, and Excellent light resistance and broad application prospects.

The third object of the present invention is to provide an application of lake. The lake prepared by the method of the present invention has a small particle size, high coloring power and better heat resistance, and excellent acid and alkali resistance and light resistance. Therefore, it can be used in the fields of dyes, pigments, medicine, cosmetics, food, printing, coatings, inks or inks.

To achieve the above objective, the present invention adopts the following technical solutions.

8的條件下發生螯合/絡合反應，得到色澱。 According to one aspect of the present invention, the present invention provides a method for preparing a lake, including the following steps: adding a solution containing at least two metal ions to an acid dye solution containing pigment raw materials to obtain solution A; adding chelate to solution A Mixture, at pH

The chelating/complexing reaction occurs under the conditions of 8, and the lake is obtained.

As a further preferred technical solution, the pH value of the chelation/complexation reaction is 8.0-11, preferably 8.5-10.5, and more preferably 9-10.

As a further preferred technical solution, the pigment raw materials include natural pigments and/or synthetic pigments; preferably, the natural pigments include at least one of natural plant pigments, natural animal pigments and natural mineral pigments.

As a further preferred technical solution, the pH value of the acid dye solution is 0.5-2, preferably 0.9-1.8, and more preferably 1.0-1.5; and/or the mass percentage concentration of the acid dye solution is 4% ~12%, preferably 5%-10%, further preferably 6%-9%.

As a further preferred technical solution, the metal ions include at least two of alkali metal ions, alkaline earth metal ions, aluminum ions, iron ions, tin ions, chromium ions, manganese ions, copper ions, cobalt ions, nickel ions, and zinc ions. Species; and/or the mass percentage concentration of the solution containing at least two metal ions is 4%-12%, preferably 5%-10%, more preferably 6%-9%; preferably, the metal Ions include at least two of sodium ion, potassium ion, iron ion, aluminum ion, tin ion, calcium ion, magnesium ion, copper ion, chromium ion and barium ion; preferably, the metal ion includes a mass ratio of 50 ~1:1 aluminum ion and tin ion; preferably, the metal ion includes iron ion and tin ion in a mass ratio of 20 to 1:1; preferably, the metal ion includes a mass ratio of 100 to 1 :1 sodium ion and magnesium ion; preferably, the metal ion includes potassium ion, barium ion and chromium ion in a mass ratio of 50 to 1:50 to 1:1.

As a further preferred technical solution, the chelating agent includes at least one of tannic acid, gallic acid and sodium gluconate; and/or the mass percentage concentration of the chelating agent is 4%-12%, preferably 5%-10%, more preferably 6%-9%.

As a further preferred technical solution, under stirring conditions, a solution containing at least two metal ions is added dropwise to the acid dye solution containing the pigment raw materials; preferably, the dropping time is 0.5 to 3 hours, preferably 1 to 2.5 hours, more preferably 1 to 2 hours; preferably, after dripping the solution containing at least two metal ions, the temperature is raised to 50°C to 60°C, and the reaction is kept constant for 10 to 12 hours to obtain solution A.

As a further preferred technical solution, under stirring conditions, the chelating agent is added dropwise to solution A; preferably, the dropping time is 0.5 to 3 hours, preferably 1 to 2.5 hours, and more preferably It is 1~2 hours; preferably, after dripping the chelating agent, the temperature is raised to 50°C~60°C, stirred, and the chelation/complexation reaction occurs under the conditions of 1~2 hours and pH value of 9~10.

According to another aspect of the present invention, the present invention provides a lake prepared by the above-mentioned method for preparing lakes.

According to another aspect of the present invention, the present invention provides an application of the above-mentioned lake in the fields of dyes, pigments, medicine, cosmetics, food, printing, paint, ink or ink.

Compared with the prior art, the present invention has the following beneficial effects:

8的條件下發生螯合/絡合反應，得到結構、性能穩定的色澱，該色澱不僅具有優異的物理性能如著色力、粒徑、色相等，還具有優異的應用性能如耐熱性、耐光性、耐酸鹼性、耐溶劑性、耐水溶出性等。 (1) The preparation method of the lake of the present invention is to first add a solution containing at least two metal ions to the acid dye solution containing the pigment raw materials, and then add a chelating agent to the acid dye solution at the pH value.

The chelating/complexing reaction occurs under the conditions of 8, and a lake with stable structure and performance is obtained. The lake not only has excellent physical properties such as tinting power, particle size, and color, but also has excellent application properties such as heat resistance, Light resistance, acid and alkali resistance, solvent resistance, water elution resistance, etc.

(2) The present invention uses a solution containing at least two metal ions. In addition to adjusting the color of the lake by using different pigment raw materials, it can also be adjusted by different metal ions. Because different metal ions have different absorption spectra, by adding at least two different metal ions or metal ion solutions in different proportions, lakes of different colors or color differences can be produced under the same pigment raw materials, which is more convenient for color Adjustable, rich colors and better aesthetics.

(3) The lake obtained by the preparation method of the present invention has better physical properties than the lake prepared by aluminum hydroxide as the substrate in the prior art. Its particle size is small and can reach sub-micron or less. Improved color strength, better light stability, and can be completely insoluble in water, and has a wider application prospect. It can be used in dyes, pigments, medicine, cosmetics, food, printing, coatings, inks or inks and other fields. Widely used, effectively alleviating the large particle size, poor water dissolution resistance, and greatly restricted application in the preparation method of the prior art problem.

(4) The preparation method of the present invention adopts a method of reacting metal ions and chelating agents under alkaline conditions, so that the prepared product has stable structure and performance, and has excellent application properties such as heat resistance. It can exist stably at 125~150℃; acid and alkali resistance, it is stable under the condition of pH 3.5~9.5; light resistance, it will not fade or change color under long-term sunlight, maintaining excellent Color fastness.

(5) The process of the present invention is simple, easy to operate, easy to implement, easy to control the reaction process, no special requirements for equipment, low cost, and environmentally friendly raw materials are used, which reduces toxicity, improves safety, and is easy to popularize and apply .

The embodiments of the present invention will be described in detail below in conjunction with the embodiments and examples, but those skilled in the art will understand that the following embodiments and examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention. If no specific conditions are specified, the normal conditions or the conditions recommended by the manufacturer shall be followed. The reagents or instruments used without the manufacturer's indication are all conventional products that can be purchased on the market.

8的條件下發生螯合/絡合反應，得到色澱。 In the first aspect, in at least one embodiment, a method for preparing a lake is provided, which includes the following steps: adding a solution containing at least two metal ions to an acid dye solution containing pigment raw materials to obtain solution A; adding to solution A Chelating agent, at pH

The chelating/complexing reaction occurs under the conditions of 8, and the lake is obtained.

8的條件下將上述結合在一起的色素原料和金屬離子包合到螯合劑內部形成沉澱，進而形成結構、性能穩定的色澱。 In the present invention, a solution containing at least two metal ions is added to the acid dye solution containing pigment raw materials. The metal ions and the pigment raw materials are electrostatically combined in an acid environment, and then a chelating agent is added to it. PH value under alkaline conditions

Under the conditions of 8, the above-mentioned combined pigment raw materials and metal ions are included in the chelating agent to form a precipitate, and then a lake with stable structure and performance is formed.

In the present invention, a chelating agent is added during the preparation process to form a lake by chelating or complexing, which can not only avoid the unnecessary precipitation of metal ions and hydroxide radicals during the reaction process, and affect the performance of the product, but also A chelate or complex with a stable structure is obtained, so that the obtained lake has excellent physical properties such as tinting power, particle size, and color, and excellent application properties such as heat resistance, light resistance, acid and alkali resistance, Solvent resistance, water elution resistance, etc.

The present invention uses a solution containing at least two metal ions. In addition to adjusting the color of the lake by using different pigment raw materials, it can also be adjusted by different metal ions. Because different metal ions have different absorption spectra, by adding at least two different metal ions or metal ion solutions in different proportions, lakes of different colors or color differences can be produced under the same pigment raw materials, which is more convenient for color Adjustable, rich colors and better aesthetics.

The color lake prepared by the present invention has a small particle size. Compared with the prior preparation method, especially the prior art using aluminum hydroxide as a matrix to prepare the color lake, the obtained color lake has a particle size of 5-10 μm. The particle size of the prepared lake is below submicron (1μm), especially below 0.45μm, more particularly below 0.22μm, generally between 10nm and 0.5μm. Due to its finer particle size, the color strength is greatly improved, the light stability is better, the application is not restricted, and it has a wider application prospect. It is used in dyes, pigments, medicine, cosmetics, food, printing, coatings, inks or It can be widely used in ink and other fields; it effectively alleviates the problems of large particle size, easy pulverization, inconvenience in use, and great limitations in application in the preparation method of the prior art.

At the same time, the lake obtained by the preparation method of the present invention has better water dissolution resistance, Compared with the color lake of the prior art which is slightly or partly soluble in water and has poor water dissolution resistance, the color lake prepared by the present invention can be completely insoluble in water.

In addition, the preparation method of the present invention adopts a method of reacting metal ions and chelating agents under alkaline conditions, so that the prepared product has stable structure and performance, and has excellent application properties such as heat resistance. The temperature is 125~ It can exist stably at 150°C; acid and alkali resistance, which is relatively stable under the pH value of 3.5 to 9.5; light resistance, it does not fade under long-term sunlight and maintains excellent color fastness.

Furthermore, the process of the present invention is simple, easy to operate, easy to implement, easy to control the reaction process, no special requirements for equipment, low cost, and adopts environmentally friendly raw materials, reduces toxicity, improves safety, and is easy to popularize and apply.

It should be noted that the present invention has no special restrictions on the terms "chelating" and "complexing", and it can be understood in accordance with the conventional understanding in the art. The reaction can be a chelating reaction or a complexing reaction, and the chelating agent can also be Known as complexing agent.

In a preferred embodiment, the pH of the chelation/complexation reaction is 8.0-11, preferably 8.5-10.5, and more preferably 9-10. Typical but non-limiting, the pH value of the reaction may be 8.0, 8.5, 9, 9.5, 10, 10.5, or 11, for example.

The chelating agent added in the present invention needs to carry out the chelating reaction at an alkaline and suitable pH, and the pH should not be too low or too high. If the pH value is too low, the reaction time may be prolonged, and the corresponding chelate compound may not even be obtained. , The quality of the product obtained is poor; an appropriate increase in pH in the alkaline range will accelerate the reaction, but an excessively high pH will lose the reactivity, poor product stability, and is not conducive to the progress of the reaction. Therefore, in comprehensive consideration, the pH value is The chelating reaction is carried out in the range of 9-10, which is more conducive to the progress of the reaction and obtains a lake with excellent performance.

In a preferred embodiment, the pigment raw materials include natural pigments and/or synthetic pigments; preferably, the natural pigments include natural plant pigments, natural animal pigments and natural minerals. At least one of the pigments.

Preferably, the pigment raw material is a natural pigment. The pigment raw materials in the present invention are preferably natural pigments, which are environmentally friendly, do not cause harm to the human body, have better safety, and are widely sourced and easier to obtain.

It should be noted that the present invention has no special restrictions on the sources and specific types of natural pigment raw materials and synthetic pigment raw materials, and various raw materials well known to those skilled in the art can be used; for example, commercial products thereof can be used.

Natural plant pigments can be, for example, natural carotene, mixed carotenoids, corn yellow, saffron pigment, gardenia yellow pigment, gardenia green pigment, capsicum red pigment, sweet pepper red pigment, capsicum orange pigment, pumpkin yellow pigment, wolfberry pigment , Ginkgo yellow pigment, bitter gourd pigment, dandelion pigment, wild peony pigment, rhododendron pigment, mountain blue pigment, etc.

The natural animal pigments may be, for example, phycocyanin, fish scale foil, cochineal red pigment, hematoxylin pigment, shrimp shell pigment, lobster red pigment, crab shell pigment, phyco blue pigment, and the like.

The natural mineral pigment may be, for example, azurite, azurite, cinnabar, realgar, muscovite, and the like.

Synthetic pigments can be, for example, carmine, cherry red, lemon yellow, neo-red, erythrosine, allure red, sunset yellow, brilliant blue, indigo and its aluminum lake, quinoline yellow, and the like.

In practical applications, suitable pigment raw materials can be selected according to the required color of the lake, the field of application of the lake, and the like, and the present invention does not limit this too much.

In a preferred embodiment, the pH value of the acid dye solution is 0.5-2, preferably 0.9-1.8, and further preferably 1.0-1.5; typically, but not limited, the pH value of the acid dye solution For example, it can be 0.5, 0.7, 0.9, 1.0, 1.1, 1.2, 1.3, 1.5, 1.6, 1.8, or 2; and/or the mass percentage concentration of the acid dye solution is 4%-12%, preferably 5%~ 10%, more preferably 6%-9%; typical but non-limiting, the mass percentage concentration of the acid dye solution can be, for example, 4%, 5%, 6%, 7%, 8%, 9%, 10% , 11% or 12%.

It should be noted that the acid dye solution is a dye solution containing a dye raw material and an acidic aqueous solution. The present invention has no special restrictions on the acid in the acidic aqueous solution, and commonly used acids in the field can be used, such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc., as long as the concentration in the acidic aqueous solution is adjusted to be within a suitable pH range. However, it is preferable to adjust the concentration of the acidic aqueous solution so that the pH value is in the range of 0.5-2.

The appropriate pH value and concentration of the acid dye solution is more conducive to the combination of metal ions and the pigment raw materials, so that the subsequent chelation reaction proceeds smoothly; at the same time, the appropriate pH value and concentration of the acid dye solution also helps to reduce the reaction Time, improve reaction efficiency.

In a preferred embodiment, the metal ions include alkali metal ions, alkaline earth metal ions, aluminum ions, iron ions, tin ions, chromium ions, manganese ions, copper ions, cobalt ions, nickel ions, and zinc ions. At least two; and/or the mass percentage concentration of the solution containing at least two metal ions is 4%-12%, preferably 5%-10%, further preferably 6%-9%; preferably, the The metal ion includes at least two of sodium ion, potassium ion, iron ion, aluminum ion, tin ion, calcium ion, magnesium ion, copper ion, chromium ion and barium ion; preferably, the metal ion includes mass ratio Preferably, the metal ions include iron and tin ions in a mass ratio of 20 to 1:1; preferably, the metal ions include a mass ratio of 100 ~1:1 sodium ion and magnesium ion; preferably, the metal ion includes potassium ion, barium ion and chromium ion in a mass ratio of 50 to 1:50 to 1:1.

It should be noted that the present invention has no special restrictions on the metal ions contained in the metal ion solution, including but not limited to alkali metal ions, alkaline earth metal ions, aluminum ions, iron ions, tin ions, chromium ions, etc., according to actual conditions. , Choose any two or more metal ions for chelation reaction. It is better to use non-heavy metal ions, which can reduce toxicity, be safe and non-toxic, and ensure the safety of the product. It is better to use sodium ion, potassium ion, iron ion, aluminum ion, tin Any two or more of metal ions among ions, calcium ions, magnesium ions, copper ions, chromium ions, and barium ions have the characteristics of good application effect, low cost, wide sources, and easy availability.

There are no special restrictions on the metal salt containing the metal ion, and metal salts commonly used in the art can be used, for example, chlorides, sulfates, nitrates, carbonates, phosphates, etc., and further examples include potassium chloride. , Sodium chloride, magnesium chloride, calcium chloride, potassium nitrate, ferric nitrate, barium nitrate, chromium sulfate, potassium sulfate, sodium sulfate, potassium carbonate, magnesium carbonate, aluminum carbonate, potassium phosphate, sodium phosphate, iron phosphate, tin phosphate, etc. .

It is understandable that the present invention has no special restrictions on the combination of different metal ions and the ratio of different metal ions, which can be set according to the required lake color, hue, brightness, etc., including but not limited to the above-mentioned metal ions The combination and ratio of other types of metal ions can also be used according to the actual situation. For example, calcium ion: magnesium ion=20~1:1 (mass ratio, the same below), sodium ion: barium ion=50~1:1, potassium ion: sodium ion: aluminum ion=50~1:50 ~1:1, aluminum ion: sodium ion: tin ion=50~1:50~1:1 and so on.

The mass percentage concentration of the solution containing at least two metal ions may be, for example, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, or 12%.

In the above-mentioned suitable pH acid dye solution, adding a metal ion solution with a suitable concentration and a suitable metal ion can make the metal ion and the pigment raw material better combine together, and the use of multiple metal ions combined in different ratios can also help Obtain lakes of different colors, simplify the production process, reduce production costs, make the subsequent chelation reaction proceed smoothly, and also help control the size of particles, reduce the decomposition of raw materials, and improve product quality.

In a preferred embodiment, the chelating agent includes at least one of tannic acid, gallic acid, and sodium gluconate; and/or the mass percentage concentration of the chelating agent is 4%-12%, which is higher than It is preferably 5% to 10%, and more preferably 6% to 9%.

Tannic acid is also called tannic acid in the pharmacopoeia. It is a type of polyphenol compound, which is widely found in plants. It has strong biopharmacological activity, antioxidant, chelating, astringent and ultraviolet absorption properties, etc. The superior performance of other products irreplaceable.

Galllic Acid, the chemical name 3,4,5-trihydroxybenzoic acid, also known as gallic acid, is a component of hydrolyzable tannins, which is widely found in grapes, medicinal plants such as pomegranate, gall and tea Among many kinds of renewable plants, the source is wide and the price is cheap. It is reported to have various physiological and pharmacological activities such as antiviral, antitumor, antimutation and antioxidation. Combining gallic acid with the corresponding calcium, magnesium, iron and other elements has high application value.

Sodium gluconate, also known as sodium pentahydroxyhexanoate, is a deep-processed product of glucose. It is the basic raw material for the preparation of gluconolactone and gluconate (copper, zinc, and ferrous salts). Due to its excellent chelating properties, Thermal stability and non-deliquescent are widely used in food, light industry, chemical industry, medicine and other fields.

The present invention selects tannic acid, gallic acid and sodium gluconate as chelating agents through the experimental research and screening of a large number of chelating agents, which are combined with the above-mentioned metal ions under alkaline conditions, especially under the condition of pH 9~10. It reacts with pigment raw materials to form a lake with stable structure and excellent performance, which reduces the generation of other unnecessary precipitates, reduces the particle size of the product, and improves the application performance of the product, which is important for expanding the application range of the lake significance.

The mass percentage concentration of the above-mentioned chelating agent solution can be, for example, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, or 12%. The chelating agent solution is an aqueous solution containing a chelating agent. Under the appropriate concentration of the chelating agent solution, the reaction with the above-mentioned metal ions and pigment raw materials helps to improve the reaction efficiency, reduce the post-processing cost, save the production cost, and generate a lake with stable structure and excellent performance.

It should be noted that the present invention has no special restrictions on the sources of the above-mentioned tannic acid, gallic acid and sodium gluconate, and various raw materials well known to those skilled in the art can be used; if the commercially available products can also be used, Can adopt the preparation method well-known to those skilled in the art to make by oneself Prepared.

In a preferred embodiment, under stirring conditions, a solution containing at least two metal ions is added dropwise to the acid dye solution containing the pigment raw materials; preferably, the dropping time is 0.5 to 3 hours, which is more It is preferably 1 to 2.5 hours, and more preferably 1 to 2 hours; typically but not limited, the dropping time can be, for example, 0.5 hour, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours; preferably After dripping the solution containing at least two metal ions, the temperature is raised to 50°C~60°C, and the reaction is kept constant for 10~12 hours to obtain solution A; typical but non-limiting, the reaction temperature can be 50°C, 52°C, for example , 54°C, 55°C, 56°C, 58°C or 60°C, the constant temperature time can be, for example, 10 hours, 10.5 hours, 11 hours, 11.5 hours or 12 hours.

In a preferred embodiment, under stirring conditions, the chelating agent is added dropwise to solution A; preferably, the dropping time is 0.5 to 3 hours, preferably 1 to 2.5 hours, and more preferably 1~2 hours; typical but non-limiting, the dropping time can be, for example, 0.5 hour, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours; preferably, after the chelating agent is dropped, the temperature is increased to 50 ℃~60℃, stirring, the chelation/complexation reaction will occur under the conditions of 1~2 hours and pH value of 9~10; typical but non-limiting, the reaction temperature can be, for example, 50℃, 52℃, 54℃ , 55°C, 56°C, 58°C or 60°C, the reaction time can be, for example, 1 hour, 1.5 hours, or 2 hours.

Adding a metal ion solution or chelating agent under stirring can help increase the contact between the two-phase interface and increase the reaction speed. It is also conducive to the uniform dispersion of the solid phase in the liquid, making the distribution of the precipitated particles more uniform, and also helpful Eliminate local overheating and avoid material decomposition. It can be understood that the present invention has no special restrictions on the specific stirring speed. In actual operation, it can be comprehensively considered and appropriately adjusted according to the specific pigment raw materials used and other operating parameters.

The dropping time of metal ion solution or chelating agent and the reaction temperature and reaction time Time is one of the key factors affecting the particle size. It can affect the formation of crystal nuclei and the growth rate of crystal nuclei. Different addition time and different reaction temperature may cause different crystal forms of the pigment, and may also affect the pigment's crystal form. Purity, transparency, and reaction speed, etc. Therefore, the addition is completed within 1 to 2 hours, and the reaction is carried out at a temperature of 50°C to 60°C, which helps to keep the particles to a minimum, has a higher coloring strength, and the color of the synthesized pigment is more vivid.

It should be noted that in the process of chelating/complexing reaction, the way to make the pH value in the range of 9~10 can be by adding sodium hydroxide, sodium bicarbonate, etc., but it is not limited to this, and can also be used The pH value is adjusted in other ways well known to those skilled in the art, and the present invention does not limit this too much.

In a preferred embodiment, after the chelation/complexation reaction is completed, the steps of washing, filtering and drying are further included; preferably, the filtration adopts membrane filtration.

The present invention does not make too many restrictions on the specific operation methods and operating conditions of washing, filtering and drying, and those skilled in the art can appropriately adjust them according to actual conditions and process requirements.

In a preferred embodiment, the ratio of the added amount of the solution containing at least two metal ions to the added amount of the chelating agent is about 1:1.

It should be noted that the present invention has no special restrictions on the addition amount of each solution, and can be adjusted according to actual conditions.

As a preferred embodiment of the present invention, the preparation method of the lake includes the following steps: dissolving the pigment raw materials in an acidic aqueous solution with a pH of 0.5-2 to prepare acid dyes with a mass percentage concentration of 5%-10% The solution is evenly mixed; among them, the pigment raw materials include natural plant pigments, natural animal pigments, natural mineral pigments and/or synthetic pigments; under stirring, dropwise add 5% by mass to the above acid dye solution within 1 to 2 hours ~10% solution containing at least two metal ions, heated to 50 ℃ ~ 60 ℃, constant temperature reaction It should take 10-12 hours to obtain solution A; wherein, the metal ions include at least two of sodium ion, potassium ion, iron ion, aluminum ion, tin ion, calcium ion, magnesium ion, copper ion, chromium ion and barium ion; Under stirring, add dropwise a chelating agent with a mass percentage concentration of 5%~10% to the above solution A within 1~2 hours, heat up to 50℃~60℃, stir, in 1~2 hours, the pH value is 9 The chelating/complexing reaction occurs under the condition of ~10; among them, the chelating agent includes at least one of tannic acid, gallic acid and sodium gluconate; after the reaction is completed, it is eluted, membrane filtered, and dried to obtain a lake .

In a second aspect, in at least one embodiment, a lake prepared by the above-mentioned method for preparing lakes is provided.

1μm，較佳

0.45μm，更佳

0.22μm，最佳為10nm~0.5μm之間。 Preferably, the particle size of the lake

1μm, preferably

0.45μm, better

0.22μm, the best is between 10nm~0.5μm.

In a third aspect, at least one embodiment provides the application of the above-mentioned lake in the fields of dyes, pigments, medicine, cosmetics, food, printing, coatings, inks or inks.

It is understandable that the lake of the present invention and the application of the lake are based on the same inventive concept as the preparation method of the aforementioned lake, and therefore have at least the same advantages as the aforementioned preparation method of the lake. Go into details again.

The present invention will be further described below in conjunction with specific examples, comparative examples and test examples.

Example 1

A method for preparing a lake includes the following steps: dissolving natural plant pigment marigold yellow raw material in an acidic aqueous solution with a pH value of 1.0 to prepare an acid dye solution with a mass percentage concentration of 8%, and mixing uniformly; under stirring In 1.5 hours, add aluminum chloride and tin chloride solution (aluminum ion: tin ion=2:1) with a mass percentage concentration of 7% to the above acid dye solution. It should take 11 hours to obtain solution A; then, under stirring, add dropwise a tannic acid solution with a concentration of 8% by mass to the above solution A within 1.5 hours, warm up to 55°C, stir, and hold for 1.5 hours with a pH of 9.5 The chelating/complexing reaction occurs under the conditions of, and after the reaction is finished, it is eluted, filtered by membrane, and dried to obtain the lake.

Example 2

A method for preparing a lake includes the following steps: dissolving natural plant pigment grape violet and beet red in an acidic aqueous solution with a pH of 2 to prepare an acid dye solution with a concentration of 5% by mass, and mixing uniformly; Next, within 1 hour, add ferric sulfate and tin sulfate solution (iron ion: tin ion = 1:1) with a concentration of 5% by mass to the acid dye solution above, raise the temperature to 50°C, and react at a constant temperature for 12 hours to obtain a solution A; Under stirring, add dropwise a 5% mass percentage tannic acid solution to the above solution A within 1 hour, heat to 50°C, stir, and chelate under the conditions of 1 hour and pH 9 / Complexation reaction; after the reaction, elution, membrane filtration, and drying to obtain lake.

Example 3

A method for preparing a lake includes the following steps: dissolving the natural animal pigment astaxanthin (or cochineal) in an acidic aqueous solution with a pH of 0.5 to prepare an acid dye solution with a concentration of 10% by mass, and mixing Uniformity; Under stirring, add 10% by mass sodium chloride and magnesium chloride solution (sodium ion: magnesium ion=5:1) to the acid dye solution above in 2 hours, heat up to 60℃, and react at a constant temperature for 10 After 2 hours, the solution A is obtained; then, under stirring, a 10% by mass gallic acid solution is added dropwise to the above solution A within 2 hours, the temperature is raised to 60°C, and the solution is stirred. After 2 hours, the pH value is 10 Chelation Complexing/complexing reaction; after the reaction, elution, membrane filtration, and drying are carried out to obtain lake.

Example 4

A method for preparing a lake, including the following steps: dissolving natural mineral pigment cinnabar red (or azurite blue) raw materials in an acidic aqueous solution with a pH of 1.5 to prepare an acid dye solution with a concentration of 4% by mass, and mixing uniformly ; Under stirring, within 0.8 hours of the above acid dye solution was added dropwise calcium nitrate and barium nitrate solution (calcium ion: barium ion = 4: 1) with a concentration of 4% by mass to the acid dye solution, heated to 56 ℃, constant temperature reaction for 10.5 hours , To obtain solution A; and then, within 0.6 hours, add 4% by mass gallic acid solution to the above solution A within 0.6 hours, warm up to 58 ℃, stir, 1.5 hours, pH 8.5 conditions A chelating/complexing reaction occurs at the bottom; after the reaction, it is eluted, filtered through a membrane, and dried to obtain a lake.

Example 5

A method for preparing lakes includes the following steps: dissolving synthetic pigment sunset yellow (or brilliant blue) raw materials in an acidic aqueous solution with a pH of 1.5 to prepare an acid dye solution with a mass percentage concentration of 12%, and mixing uniformly; Under stirring, add potassium chloride, barium chloride and chromium chloride solutions (potassium ion: barium ion: chromium ion=6:3:1) with a concentration of 12% by mass to the acid dye solution above within 3 hours, Warm up to 52°C and react at constant temperature for 11.5 hours to obtain solution A; then, under stirring, add dropwise sodium gluconate solution with a mass percentage concentration of 11% to the above solution A within 3 hours, warm up to 56°C, stir, The chelating/complexing reaction occurs under the condition of hours and pH value of 11; after the reaction, it is eluted, filtered by membrane, and dried to obtain a lake.

Example 6-8

A method for preparing a lake, the only difference from Example 1 is that the metal ion solution is replaced with sodium sulfate, potassium sulfate and tin sulfate solutions (sodium ion: potassium ion: tin ion = 2:2:1), nitric acid Iron, aluminum nitrate and magnesium nitrate solutions (iron ion: aluminum ion: magnesium ion = 4:3:1) and potassium chloride, calcium chloride and chromium chloride solutions (potassium ion: calcium ion: chromium ion = 10:5) :1).

Examples 9-10

A method for preparing a lake is different from Example 1 only in that the pigment raw material is replaced with synthetic pigment Allure Red raw material; the chelating agent is replaced with gallic acid solution and sodium gluconate solution, respectively.

Comparative example 1

A method for preparing a lake includes the following steps: dissolving natural plant pigment marigold yellow raw material in an acidic aqueous solution with a pH of 6, to prepare an acid dye solution with a concentration of 15% by mass, and mixing uniformly; under stirring , Within 4 hours, add aluminum chloride and tin chloride solution (aluminum ion: tin ion=2:1) with a concentration of 15% by mass to the acid dye solution above, raise the temperature to 68°C, and react at a constant temperature for 9 hours to obtain Solution A; Under stirring, add dropwise a 14% tannic acid solution with a mass percentage concentration of 14% to the above solution A within 3.5 hours, raise the temperature to 65°C, stir, and chelate under the conditions of 0.5 hours and pH 7.5 Complexing/complexing reaction; after the reaction, elution, membrane filtration, and drying are carried out to obtain lake.

In this comparative example, multiple operating conditions such as pH, mass percentage concentration, dropping time, reaction temperature, and reaction pH of the solution are not within the scope provided by the present invention.

Comparative example 2

A method for preparing a lake is different from Example 1 only in that the dripping time of the metal ion solution and the chelating agent are both 20 minutes.

Comparative example 3

A method for preparing a lake is different from Example 1 only in that the reaction temperature for obtaining solution A and the chelating/complexing reaction temperature are both 40°C.

Comparative example 4

A method for preparing a lake is different from Example 1 only in that a chelating/complexing reaction occurs under the condition of a pH of 7.2.

Comparative example 5

A method for preparing a lake is different from Example 1 only in that the chelating agent tannic acid is replaced with tartaric acid.

Comparative example 6

A method for preparing a lake (previous technology), including the following steps: preparing a magnesium chloride solution with a mass percentage concentration of 5%-20%; preparing a red yeast red pigment solution with a mass percentage concentration of 10%-15%; using hydrochloric acid or sulfuric acid Acidify the red yeast red pigment solution to pH 1~2, add magnesium chloride solution and stir for 1~2 hours to produce a precipitate; then filter, dry, and package to obtain the red yeast red lake.

Test example 1

The physical properties of the lakes prepared in the respective examples and comparative examples were tested, including the particle size, water dissolution resistance, and color strength. The test results are shown in Table 1.

The test methods are: particle size test: use sieving method to measure particle size; test of water dissolution resistance: use spectrophotometry to quantitatively determine the eluted substance; test of color strength: use reflectometer to measure color strength.

It can be seen from Table 1 that the particle size of the lake prepared by the preparation method of the present invention is small, and can reach below 1μm, especially below 0.45μm, more particularly below 0.22μm, and more particularly below 10nm~ Between 0.5μm. Because of its finer particle size, the coloring strength is greatly improved; and the lake of the present invention has excellent water dissolution resistance and can be completely insoluble in water; therefore, the lake of the present invention can be used in many different fields. It has been applied, the application range is wider, and it can better meet the needs of the market.

In Comparative Examples 1-5, the operating conditions such as the type of chelating agent, reaction temperature, dropping time, reaction pH, etc. are not within the scope of the present invention, so that the lake prepared in Comparative Examples 1-5 has a relatively low particle size. It is larger than 7μm, and the color strength is also low. It is also partially soluble in water and has poor water dissolution resistance, which causes great restrictions in application and cannot meet the needs of the market. It also further illustrates that the present invention can achieve better results and obtain lakes with better performance through the coordination of various operating steps and operating parameters under the above-mentioned specific operating conditions.

Comparative Example 6 adopts the preparation method in the prior art, and the prepared lake has a larger particle size, and the color strength and water dissolution resistance are worse than those prepared in the examples of the present invention. It is explained that the lake formed by the chelating or complexing method of the present invention can effectively avoid unnecessary precipitation caused by the reaction of metal ions and hydroxide radicals during the reaction process, and obtain a lake with more excellent physical properties.

Test example 2

The application performance tests of the lakes prepared in the respective examples and comparative examples were carried out, including tests of heat stability, light resistance, and acid and alkali resistance. The test results are shown in Table 2.

The test method is: the heat stability test method is to put the lake in an oven at different temperatures for 30 minutes; the light resistance test method is to disperse the lake with a small amount of water, and then coat it on white paper to color The sample was placed under a hernia lamp for 400 hours, and then taken out to observe the degree of fading. Compared with the blue label, level 8 is the best and level 1 is the worst; the test method for acid and alkali resistance is to place the lake in acidic solutions and alkalis with different pHs. In the liquid solution, observe the degree of discoloration for 24 hours.

It can be seen from Table 2 that the lake prepared by the preparation method of the present invention has excellent application properties including heat resistance stability, which can exist stably at a temperature of 125~150℃; The value is 3.5~9.5 or the pH value is 4~9, both are more stable; the light resistance is better, can reach level 7, and the color can be maintained for a long time.

In Comparative Examples 1-5, the operating conditions such as the type of chelating agent, reaction temperature, dripping Addition time, reaction pH value, etc. are not within the scope of the present invention, so that the lake prepared in Comparative Examples 1-5 has poor heat resistance stability, and the color starts to change at 100°C; the acid and alkali resistance is poor, and the pH value is 4.5~ It cannot exist stably under the condition of 8.5 or pH value of 4~9; its light resistance is poor, and its color will start to change slightly when exposed to sunlight, and some have even lost the original color, and the color change is obvious. It also further illustrates that the present invention can achieve better results and obtain lakes with better performance through the coordination of various operating steps and operating parameters under the above-mentioned specific operating conditions.

Comparative Example 6 adopts the preparation method in the prior art, and the prepared lake is inferior to the lake prepared in the embodiment of the present invention in terms of heat resistance, acid and alkali resistance, and light resistance. It is explained that the lake formed by the chelating or complexing method of the present invention can effectively avoid unnecessary precipitation caused by the reaction of metal ions and hydroxide radicals during the reaction process, and obtain a lake with more excellent application performance.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, not to limit them; 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 recorded 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 cause the essence of the corresponding technical solutions to deviate from the technical solutions of the embodiments of the present invention. Scope.

Claims (8)

A method for preparing a lake includes the following steps: after dropping a solution containing at least two metal ions into an acid dye solution containing pigment raw materials, the temperature is raised to 50°C to 60°C for reaction to obtain solution A, wherein The dripping time is 0.5~3 hours; and after the chelating agent is dripped into the solution A, the temperature is raised to 50℃~60℃, and the pH value is

The chelating/complexing reaction occurs under the conditions of 8 to obtain a lake, wherein the dripping time is 0.5 to 3 hours, wherein the pH of the acid dye solution is 0.5 to 2, and the acid dye solution The concentration by mass percentage of the chelating agent is 4%-12%, and the chelating agent includes at least one of tannic acid, gallic acid, and sodium gluconate. The method for preparing a lake according to claim 1, wherein the pH of the chelating/complexing reaction is 8.0-11. The method for preparing a lake according to claim 1, wherein the pigment raw material includes natural pigments and/or synthetic pigments; the natural pigments include at least one of natural plant pigments, natural animal pigments and natural mineral pigments. The method for preparing a lake according to claim 1, wherein the pH value of the acid dye solution is 0.9 to 1.8; and/or the mass percentage concentration of the acid dye solution is 5% to 10%. The method for preparing a lake according to claim 1, wherein the metal ion includes alkali metal ion, alkaline earth metal ion, aluminum ion, iron ion, tin ion, chromium ion, manganese ion, copper ion, cobalt ion, nickel At least two of ions and zinc ions; and/or the mass percentage concentration of the solution containing at least two metal ions is 4%~12%. The method for preparing a lake according to claim 1, wherein the mass percentage concentration of the chelating agent is 4%-12%. The method for preparing a lake according to any one of claims 1 to 6, wherein, under stirring, a solution containing at least two metal ions is added dropwise to the acid dye solution containing pigment raw materials; The dripping time is 1 to 2.5 hours; after dripping the solution containing at least two metal ions, the temperature is raised to 50° C. to 60° C., and the reaction is kept constant for 10 to 12 hours to obtain the solution A. The method for preparing a lake according to any one of claims 1 to 6, wherein, under agitation, a chelating agent is added dropwise to the solution A; the time for the dropwise addition is 1 to 2.5 hours; After dripping the chelating agent, the temperature is raised to 50°C to 60°C, and the mixture is stirred, and a chelating/complexing reaction occurs under the conditions of 1 to 2 hours and a pH value of 9 to 10.