阅读说明：本技术 一种天然介孔矿物与动植物色素的复合颜料及制备方法 (Composite pigment of natural mesoporous mineral and animal and plant pigment and preparation method thereof ) 是由 唐颖 曹力化 张兆伦 张茜 于 2021-06-15 设计创作，主要内容包括：本发明公开天然介孔矿物与动植物色素的复合颜料及制备方法,涉及日用化学工业技术领域,复合颜料包括70％-90％百分含量的天然介孔矿物；以及10％-30％百分含量的通过物理吸附和经金属离子相配合的化学吸附到矿物上的水溶性动植物色素或10％-30％百分含量的通过物理吸附和经接枝物单体接枝的化学吸附到矿物上的油溶性动植物色素。本发明的复合颜料有较高的热稳定性、光稳定性、耐酸碱性、色牢固性,对人体无毒无害,还具有一定保健功能。制备过程中负载效率高,色素负载量大,整个过程都无需高温加热,能耗低,对于亲水亲油性不同、热不稳定色素都能有效吸附,可应用于日化产品、彩妆、油墨、涂料、儿童玩具、工艺品以及食品、医药、妇婴用品的包装材料等多种领域。(The invention discloses a composite pigment of natural mesoporous mineral and animal and plant pigment and a preparation method thereof, relating to the technical field of daily chemical industry, wherein the composite pigment comprises 70-90 percent of natural mesoporous mineral; and 10-30% of water-soluble animal and plant pigment which is chemically adsorbed on the mineral by physical adsorption and by matching with metal ions or 10-30% of oil-soluble animal and plant pigment which is chemically adsorbed on the mineral by physical adsorption and by grafting of graft monomer. The composite pigment has high heat stability, light stability, acid and alkali resistance and color fastness, is non-toxic and harmless to human bodies, and also has a certain health-care function. The preparation method has the advantages of high loading efficiency, large pigment loading capacity, no need of high-temperature heating in the whole process, low energy consumption, effective adsorption of pigments with different hydrophilicity and lipophilicity and thermal instability, and can be applied to various fields such as daily chemical products, color cosmetics, printing ink, coating, toys for children, artware, and packaging materials of foods, medicines, women and infants.)

1. The composite pigment of natural mesoporous minerals and animal and plant pigments is characterized by comprising the following components:

70-90% of natural mesoporous mineral; and

10 to 30 percent of water-soluble animal and plant pigment which is chemically adsorbed on the natural mesoporous mineral through physical adsorption and metal ion matched chemical adsorption or 10 to 30 percent of oil-soluble animal and plant pigment which is chemically adsorbed on the natural mesoporous mineral through physical adsorption and graft monomer grafting.

2. The composite pigment according to claim 1, wherein the natural mesoporous mineral comprises one or more of attapulgite, sepiolite, halloysite and diatomite.

3. The composite pigment according to claim 1 or 2, wherein the water-soluble animal and plant pigment comprises one or more of anthocyanidin, gallic acid, gardenia yellow pigment, pomegranate red pigment, tea pigment, pomegranate rind pigment, betel nut pigment, hawthorn red pigment, beet red pigment, purple sweet potato pigment, and pale butterflybush flower yellow pigment.

4. The composite pigment according to any one of claims 1 to 3, wherein the oil-soluble animal and plant pigment comprises one or more of arnebia euchroma pigment, lycopene, astaxanthin, canthaxanthin, lactoflavin, lycium barbarum pigment, zeaxanthin, curcumin, bixin, sorghum red, capsanthin, ranunculin, violaxanthin, rhodoxanthin, and zeaxanthin.

5. The composite pigment according to any one of claims 1 to 4, wherein the metal ion is Fe²⁺、Fe³⁺、Cu²⁺、Ti⁴⁺、Al³⁺、Mg²⁺Or Zn²⁺。

6. The composite pigment according to any one of claims 1 to 5, wherein the graft monomer is chitosan, a silane coupling agent, a titanate coupling agent, a quaternary ammonium cationic surfactant, octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride or hexadecyl trimethyl ammonium bromide.

7. The method for preparing the composite pigment of the natural mesoporous mineral and the animal and plant pigment according to any one of claims 1 to 6, comprising the following steps:

preparing a first pigment solution by mixing 1-20 parts of water-soluble animal and plant pigment and 80-90 parts of a first solvent according to parts by weight;

cleaning natural mesoporous minerals by using a low-temperature plasma cleaning method, wherein the weight percentage of the natural mesoporous minerals to the water-soluble animal and plant pigments is (7-9) to (1-3);

adding the cleaned natural mesoporous mineral into a metal ion solution, soaking for 24-72 hours, and centrifuging to obtain mineral solid;

adding the mineral solid into the first pigment solution, continuously stirring for a period of time, placing into a constant-temperature oscillation box, performing physical adsorption and chemical adsorption through metal ion coordination for 12-48 hours, and then performing centrifugation, cleaning, drying, grinding and sieving to obtain the composite pigment of the natural mesoporous mineral and the animal and plant pigment.

8. The preparation method according to claim 7, wherein the step of cleaning the natural mesoporous mineral by using the low-temperature plasma cleaning method comprises:

putting natural mesoporous mineral into low-temperature plasma reaction equipment, and reacting with O₂As cleaning gas, discharging and reacting for 2-15 minutes, and setting parameters as follows: o is₂The pressure is 10Pa, the power is 50-100W, the voltage is 500-800V, and the current is 40-100 mA; in the process, inorganic gas is excited to a plasma state and then is adsorbed on the surface of the solid, the inorganic gas reacts with molecules on the surface of the solid to generate by-product molecules, the by-product molecules are resolved to form a gas phase, and reaction residues are separated from the surface through vacuum pumping and discharging, so that the effect of removing impurities is achieved.

9. The method for preparing the composite pigment of the natural mesoporous mineral and the animal and plant pigment according to any one of claims 1 to 6, comprising the following steps:

preparing a second pigment solution by mixing 1-20 parts of oil-soluble animal and plant pigment and 80-90 parts of a second solvent according to parts by weight;

cleaning natural mesoporous minerals by using a low-temperature plasma cleaning method, wherein the mass ratio of the natural mesoporous minerals to the oil-soluble animal and plant pigments is (7-9) to (1-3);

carrying out low-temperature plasma modified grafting on the cleaned natural mesoporous mineral to obtain a modified and grafted mineral;

and adding the modified and grafted mineral into the second pigment solution, continuously stirring for a period of time, placing the mixture into a constant-temperature oscillation box, performing physical adsorption and chemical adsorption grafted by a graft monomer for 12 to 48 hours, and then performing centrifugation, cleaning, drying, grinding and sieving to obtain the composite pigment of the natural mesoporous mineral and the animal and plant pigment.

10. The preparation method according to claim 9, wherein the step of subjecting the cleaned natural mesoporous mineral to low-temperature plasma modified grafting to obtain a modified grafted mineral comprises:

the cleaned natural mesoporous mineral is treated by N in low-temperature plasma reaction equipment₂As initiating gas, discharging for 4-20 minutes, discharging once every 2-10 minutes for two times, and setting parameters as follows: n is a radical of₂The pressure is 10Pa, the power is 50-100W, the voltage is 500-800V, and the current is 40-100 mA;

and adding a graft monomer solution after the discharge reaction is finished, wherein the weight percentage of the mineral to the graft monomer is 1 to (0.4-5.0), reacting for 3-6 hours, washing to be neutral, filtering and drying to obtain the modified grafted mineral.

Technical Field

The invention relates to the technical field of daily chemical industry, in particular to a composite pigment of natural mesoporous mineral and animal and plant pigment and a preparation method thereof.

Background

The animal and plant pigment has rich resources and wide sources, and is an environment-friendly colorant with natural color tone and capable of being continuously produced. The animal and plant pigments from natural sources are mostly anthocyanins, carotenoids and flavonoids, are functional components in a plurality of Chinese herbal medicines and foods, have biological activity incomparable with artificially synthesized pigments or mineral pigments, and can bring health-care effects of regulating human immune function, resisting oxidation, reducing blood fat and the like in the long-term use process of contacting with human bodies. At present, natural animal and plant pigments are applied to food, textiles and cosmetics as additives for coloring, and are accepted and accepted by wide consumers. Moreover, most natural pigments have no toxic or side effect on human bodies, and the animal and plant pigments from natural sources are more favored by consumers and safer to use. However, many animal and plant pigments are not as stable as synthetic pigments or inorganic mineral pigments, and have high sensitivity to various environmental factors (such as light, pH value, high temperature, microorganisms, etc.), and are prone to oxidative discoloration, low degree of coloration, and the like, thereby limiting their wide application in industrial products.

In order to solve the problem of instability of animal and plant pigments, one of the solutions is to embed animal and plant pigments with highly stable inorganic carriers to form inorganic-organic composite pigments. At present, some researches have been made, for example, chinese patent CN111303655A discloses a method for preparing natural pigment from palygorskite hybridized Chinese herbal medicine natural pigment, the pigment is natural plant pigment, and is green and environment-friendly, the disadvantages are that the used pigments are all pigments with low molecular weight and high temperature resistance, and are not suitable for macromolecular or non-high temperature resistant pigments, the application range is limited, and high temperature activation and high temperature baking are performed in the reaction process, the energy consumption is high, and the cost is high.

Chinese patent CN107488363A discloses a method for preparing carotenoid pigment-clay composite products, which performs inorganic modification on clay to realize stable use of carotenoid pigment, but the clay-loaded pigment range after inorganic modification still has certain limitation, and can not be popularized and applied to other oil-soluble pigments.

Chinese patent CN112175414A discloses a preparation method of chlorophyll/clay mineral hybrid green pigment, which improves the heat resistance of chlorophyll, but the preparation process only comprises the steps of simply mixing raw materials, magnetically stirring, self-assembling, not cleaning clay, and the like, and has low load efficiency and low load capacity.

Chinese patent CN109651851A discloses an organic-inorganic hybrid nano pigment from natural plant sources and a preparation method and application thereof, wherein a stabilizer and a surface modifier are adopted to prepare the nano pigment, but cerium oxide and zirconium oxide in the raw materials have certain irritation to skin, eyes and mucous membranes, certain safety risks exist in the preparation process and the use process, and the pigment is only attached to the surface of nano particles, so that the loading efficiency is not high.

Disclosure of Invention

Therefore, in order to overcome the defects of low stability of natural animal and plant pigments, low loading efficiency of inorganic carrier and organic pigment composite pigments, narrow range of selectable raw materials and less application of oil-soluble and thermolabile pigments, the embodiment of the invention provides the natural mesoporous mineral and animal and plant pigment composite pigments and the preparation method thereof, which can improve the loading efficiency and can be well applied to pigments with different hydrophilicity and lipophilicity and thermal instability.

Therefore, the composite pigment of the natural mesoporous mineral and the animal and plant pigment, provided by the embodiment of the invention, comprises the following components:

70-90% of natural mesoporous mineral; and

10 to 30 percent of water-soluble animal and plant pigment which is chemically adsorbed on the natural mesoporous mineral through physical adsorption and metal ion matched chemical adsorption or 10 to 30 percent of oil-soluble animal and plant pigment which is chemically adsorbed on the natural mesoporous mineral through physical adsorption and graft monomer grafting.

Preferably, the natural mesoporous minerals comprise one or more than two of attapulgite, sepiolite, halloysite and diatomite.

Preferably, the water-soluble animal and plant pigment comprises one or more of anthocyanidin, gallic acid, gardenia yellow pigment, pomegranate red pigment, tea pigment, pomegranate peel pigment, betel nut pigment, hawthorn red pigment, beet red, purple sweet potato pigment and pale butterflybush flower yellow pigment.

Preferably, the oil-soluble animal and plant pigment comprises one or more of alkannin, lycopene, astaxanthin, canthaxanthin, lactoflavin, medlar pigment, zeaxanthin, curcumin, bixin, sorghum red, capsanthin, ranunculin, violaxanthin, rhodoxanthin and zeaxanthin.

Preferably, the metal ion is Fe²⁺、Fe³⁺、Cu²⁺、Ti⁴⁺、Al³⁺、Mg²⁺Or Zn²⁺。

Preferably, the graft monomer is chitosan, a silane coupling agent, a titanate coupling agent, a quaternary ammonium salt cationic surfactant, octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride or hexadecyl trimethyl ammonium bromide.

The preparation method of the composite pigment of the natural mesoporous mineral and the animal and plant pigment, provided by the embodiment of the invention, comprises the following steps of:

preparing a first pigment solution by mixing 1-20 parts of water-soluble animal and plant pigment and 80-90 parts of a first solvent according to parts by weight;

cleaning natural mesoporous minerals by using a low-temperature plasma cleaning method, wherein the weight percentage of the natural mesoporous minerals to the water-soluble animal and plant pigments is (7-9) to (1-3);

adding the cleaned natural mesoporous mineral into a metal ion solution, soaking for 24-72 hours, and centrifuging to obtain mineral solid;

adding the mineral solid into the first pigment solution, continuously stirring for a period of time, placing into a constant-temperature oscillation box, performing physical adsorption and chemical adsorption through metal ion coordination for 12-48 hours, and then performing centrifugation, cleaning, drying, grinding and sieving to obtain the composite pigment of the natural mesoporous mineral and the animal and plant pigment.

Preferably, the step of cleaning the natural mesoporous mineral by using the low-temperature plasma cleaning method comprises the following steps:

putting natural mesoporous mineral into low-temperature plasma reaction equipment, and reacting with O₂As cleaning gas, discharging and reacting for 2-15 minutes, and setting parameters as follows: o is₂The pressure is 10Pa, the power is 50-100W, the voltage is 500-800V, and the current is 40-100 mA; in the process, inorganic gas is excited to a plasma state and then is adsorbed on the surface of the solid, the inorganic gas reacts with molecules on the surface of the solid to generate product molecules, the product molecules are resolved to form a gas phase, and reaction residues are separated from the surface through vacuum pumping and discharging, so that the effect of removing impurities is achieved.

The preparation method of the composite pigment of the natural mesoporous mineral and the animal and plant pigment, provided by the embodiment of the invention, comprises the following steps of:

preparing a second pigment solution by mixing 1-20 parts of oil-soluble animal and plant pigment and 80-90 parts of a second solvent according to parts by weight;

cleaning natural mesoporous minerals by using a low-temperature plasma cleaning method, wherein the mass ratio of the natural mesoporous minerals to the oil-soluble animal and plant pigments is (7-9) to (1-3);

carrying out low-temperature plasma modified grafting on the cleaned natural mesoporous mineral to obtain a modified and grafted mineral;

and adding the modified and grafted mineral into the second pigment solution, continuously stirring for a period of time, placing the mixture into a constant-temperature oscillation box, performing physical adsorption and chemical adsorption grafted by a graft monomer for 12 to 48 hours, and then performing centrifugation, cleaning, drying, grinding and sieving to obtain the composite pigment of the natural mesoporous mineral and the animal and plant pigment.

Preferably, the step of performing low-temperature plasma modified grafting on the cleaned natural mesoporous mineral to obtain a modified grafted mineral comprises:

the cleaned natural mesoporous mineral is treated by N in low-temperature plasma reaction equipment₂As initiating gas, discharging for 4-20 minutes, discharging once every 2-10 minutes for two times, and setting parameters as follows: n is a radical of₂Pressure of 10Pa, 50-100W of power, 500-800V of voltage and 40-100mA of current;

and adding a graft monomer solution after the discharge reaction is finished, wherein the weight percentage of the mineral to the graft monomer is 1 to (0.4-5.0), reacting for 3-6 hours, washing to be neutral, filtering and drying to obtain the modified grafted mineral.

Preferably, the step of drying comprises:

putting the object to be dried into a decompression dryer, and setting the parameters as follows: the pressure is 0-2.67KPa, the temperature is 30-40 ℃, and the time is 2-12 hours.

The composite pigment of the natural mesoporous mineral and the animal and plant pigment and the preparation method thereof provided by the embodiment of the invention have the following advantages:

1. the composite pigment prepared from the natural mesoporous mineral and the animal and plant pigment has excellent stability, and the thermal stability, the light stability, the acid and alkali resistance and the color fastness of the pigment are improved through the physical and chemical adsorption effects. The natural mesoporous minerals such as attapulgite, sepiolite, halloysite, diatomite and the like have similar porous structures, a large number of nanoscale pore canals and higher specific surface area, and provide a large number of adsorption sites for pigment molecules. The nanometer rod-shaped crystals of attapulgite and sepiolite are arranged to form regular pore channels, dye can be adsorbed on the outer surface of the fiber clay, the grooves and the inlets of the channels, the halloysite crystals are bent to form a hollow tubular structure, adsorption balance can be achieved within a short time, and algae remains in the diatomite form an ordered microporous structure, so that the pigment dispersion performance can be enhanced. Meanwhile, the surface of the mineral crystal has hydroxyl, silanol and other groups, and the surface of the mineral crystal has negative electricity and can be combined with pigment molecules through the chemical adsorption effect: active hydroxyl groups and other groups can be complexed with pigment molecules, and Si on the surface of the crystal⁴⁺、Mg²⁺Can be coated with Fe²⁺、Al³⁺Plasma ion exchange, these metal ions act as a bridge between the mineral crystals and the pigment.

2. The pigment and the carrier of the composite pigment of the natural mesoporous mineral and the animal and plant pigment are both made of natural materials, are green and environment-friendly, have no stimulation to human bodies, and a plurality of natural animal and plant pigments have certain antibacterial, antioxidant, anti-inflammatory and other effects and biological activity incomparable with synthetic pigments. The composite pigment can be applied to various fields of daily chemical products, cosmetics, printing ink, paint, toys for children, artware, food, medicines, packaging materials of women and infants and the like. The natural mesoporous mineral and animal and plant pigment raw materials have rich resources and low price, and can be massively produced. Different mineral carriers and different pigments are selected in various ways to form different combinations, and the obtained pigment is more abundant, bright and various.

3. The low-temperature plasma cleaning technology and the low-temperature plasma surface modification technology are adopted to clean and modify the minerals, the conditions are mild, the low-temperature energy consumption is low, and the composite material can effectively compound pigments with different hydrophilicity and lipophilicity and heat resistance. Impurities in minerals can be removed through low-temperature plasma cleaning, pigments are effectively adsorbed on the surfaces of crystals, grooves and pore channels, load efficiency and load capacity are improved, only trace gas is used in work, the operation environment is a dry gas environment, additional drying is not needed, the cleaning effect is good, and the crystal structure of the minerals cannot be damaged. The low-temperature plasma surface modification technology can introduce different functional groups on the surface of the mineral by changing plasma parameters (voltage, gas, modification time, pressure and the like), change the hydrophilic or hydrophobic performance of the mineral, load pigments with different hydrophilic and lipophilic properties, and has the advantages of mild conditions and short reaction time. In the embodiment, heating is not needed in the cleaning, modification and compounding processes, the energy consumption is low, the pigment with unstable heat can be well applied, and the application range of the natural animal and plant pigment is enlarged.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a schematic structural view of one specific example of attapulgite and sepiolite;

FIG. 2 is a schematic diagram of a specific example of a halloysite;

FIG. 3 is a schematic structural view of a specific example of diatomaceous earth;

FIG. 4 is a schematic diagram showing the action of metal ions between the mineral surface and water-soluble animal and plant pigments in example 1 of the present invention;

FIG. 5 is a schematic view showing the effect of the graft between the mineral surface and the oil-soluble animal and plant pigment in example 1 of the present invention;

FIG. 6 is a schematic structural view of a composite pigment of attapulgite, sepiolite, halloysite and diatomaceous earth in example 1 of the present invention;

FIG. 7 is a flowchart showing a specific example of a method for preparing a natural mesoporous mineral/animal and plant pigment composite pigment according to example 2 of the present invention;

fig. 8 is a flowchart illustrating another specific example of the method for preparing the composite pigment of natural mesoporous minerals and animal and plant pigments in example 2 of the present invention.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In describing the present invention, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms "comprises" and/or "comprising," when used in this specification, are intended to specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The term "and/or" includes any and all combinations of one or more of the associated listed items. The terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.

In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

Example 1

The embodiment provides a composite pigment of natural mesoporous minerals and animal and plant pigments, which comprises:

70-90% of natural mesoporous mineral; and

10 to 30 percent of water-soluble animal and plant pigment which is chemically adsorbed on the natural mesoporous mineral through physical adsorption and metal ion matched chemical adsorption or 10 to 30 percent of oil-soluble animal and plant pigment which is chemically adsorbed on the natural mesoporous mineral through physical adsorption and graft monomer grafting. Preferably, the natural mesoporous minerals comprise one or more than two of attapulgite, sepiolite, halloysite and diatomite. The natural mesoporous minerals are carrier materials with excellent performance, and the attapulgite, the sepiolite, the halloysite and the diatomite have rich resources, low price and environmental protection. All of them have similar porous structures, have a large number of nanometer-scale pore channels and higher specific surface area, and provide a large number of adsorption sites for pigment molecules, as shown in fig. 1, the nanometer rod-shaped crystals of attapulgite and sepiolite are arranged to form regular pore channels, and the dye can be adsorbed on the outer surface of the fiber clay, the inlets of the grooves and the channels, as shown in fig. 2, the halloysite crystals are bent to form a hollow tubular structure, and can reach adsorption balance in a short time, as shown in fig. 3, the remains of algae in the diatomite form an ordered microporous structure, and can enhance the pigment dispersion performance. The minerals can adsorb pigment molecules to the inside, the inlet and the outer surface of the pore passage through physical adsorption. Meanwhile, the surface of the mineral crystal has hydroxyl, silanol and other groups, and the surface of the mineral crystal has negative electricity and can be combined with pigment molecules through the chemical adsorption effect: reactive hydroxyl groups and the like can be reacted withComplexation of pigment molecules, Si on crystal surface⁴⁺、Mg²⁺Can be coated with Fe²⁺、Al³⁺And (3) after metal ion exchange, the metal ions are used as mordants of some water-soluble animal and plant pigments and matched with coordination groups on mineral crystals and pigment molecules to form a complex, so that the metal ions play a role of a bridge between the mineral crystals and the pigments, as shown in figure 4, the pigments can effectively dye the minerals, the depth and the fastness of the color of the mordant-dyed composite pigment are improved, different colors can be obtained by using different metal ions, and the prepared composite pigment is rich in color. As shown in FIG. 5, the surface of the mineral crystal can be selectively modified and grafted, and the grafted group is hydrophobic so as to be capable of adsorbing and binding oil-soluble animal and plant pigments. The colored attapulgite, sepiolite, halloysite and diatomite are shown in figure 6. The pigment molecule and the mineral carrier are firmly combined under the physical and chemical adsorption effects, and the thermal stability, the light stability, the acid and alkali resistance and the color fastness of the pigment can be improved.

Preferably, the water-soluble animal and plant pigment comprises one or more of anthocyanidin, gallic acid, gardenia yellow pigment, pomegranate red pigment, tea pigment, pomegranate peel pigment, betel nut pigment, hawthorn red pigment, beet red, purple sweet potato pigment and pale butterflybush flower yellow pigment.

Preferably, the oil-soluble animal and plant pigment comprises one or more of alkannin, lycopene, astaxanthin, canthaxanthin, lactoflavin, medlar pigment, zeaxanthin, curcumin, bixin, sorghum red, capsanthin, ranunculin, violaxanthin, rhodoxanthin and zeaxanthin.

Preferably, the metal ion is Fe²⁺、Fe³⁺、Cu²⁺、Ti⁴⁺、Al³⁺、Mg²⁺Or Zn²⁺。

Preferably, the graft monomer is chitosan, a silane coupling agent, a titanate coupling agent, octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride or hexadecyl trimethyl ammonium bromide.

The composite pigment of the natural mesoporous mineral and the animal and plant pigment is prepared from the natural nano porous mineral and the animal and plant pigment, has excellent stability, and improves the thermal stability, the light stability, the acid and alkali resistance and the color fastness of the pigment through the physical and chemical adsorption. The composite pigment is green and natural, has high safety, and many natural animal and plant pigments have certain antibacterial, antioxidant and anti-inflammatory effects and biological activity incomparable with synthetic pigments. The composite pigment can be applied to various fields of daily chemical products, cosmetics, printing ink, paint, toys for children, artware, food, medicines, packaging materials of women and infants and the like. The natural mesoporous mineral and animal and plant pigment raw materials have rich resources and low price, and can be massively produced. Different mineral carriers and different pigments are selected in various ways to form different combinations, and the obtained pigment is more abundant, bright and various.

Example 2

The present embodiment provides a method for preparing the composite pigment of the natural mesoporous mineral and the animal and plant pigment in example 1, as shown in fig. 7, including the following steps:

s101, preparing a first pigment solution from 1-20 parts by weight of water-soluble animal and plant pigment and 80-90 parts by weight of a first solvent; preferably, the first solvent is distilled water or an aqueous ethanol solution. The water soluble animal and plant pigment comprises one or more of anthocyanidin, gallic acid, fructus Gardeniae yellow pigment, flos Granati red pigment, tea pigment, pericarpium Granati pigment, Arecae semen pigment, fructus crataegi red pigment, beet red, purple sweet potato pigment, and flos Buddlejae yellow pigment.

S102, cleaning natural mesoporous minerals (powder) by using a low-temperature plasma cleaning method, wherein the weight percentage of the natural mesoporous minerals to the water-soluble animal and plant pigments is (7-9) to (1-3); preferably, the method specifically comprises the following steps: putting natural mesoporous mineral into low-temperature plasma reaction equipment, and reacting with O₂As cleaning gas, discharging and reacting for 2-15 minutes, and setting parameters as follows: o is₂The pressure is 10Pa, the power is 50-100W, the voltage is 500-800V, and the current is 40-100 mA. In the process, inorganic gas is excited to plasma state and adsorbed on solidA surface; the product molecules are generated by reaction with solid surface molecules, and then the product molecules are resolved to form a gas phase, and reaction residues are separated from the surface by vacuum pumping and discharging, so that the effect of removing impurities is achieved.

S103, adding the cleaned natural mesoporous mineral into a metal ion solution, soaking for 24-72 hours, and centrifuging to obtain a mineral solid; preferably, the metal ion is Fe²⁺、Fe³⁺、Cu²⁺、Ti⁴⁺、Al³⁺、Mg²⁺Or Zn²⁺。

S104, adding the mineral solid into the first pigment solution, continuously stirring for a period of time, placing the mixture into a constant-temperature oscillation box, performing physical adsorption and chemical adsorption through metal ion coordination for 12 to 48 hours, and then performing centrifugation, cleaning (for example, cleaning the solid obtained after the centrifugation with a solvent for more than two times), drying (for example, at room temperature), grinding and sieving (for example, with a 200-mesh sieve) to obtain the composite pigment of the natural mesoporous mineral and the animal and plant pigment. The adsorption of the minerals to the pigments is saturated after the physical and chemical adsorption. The chemical adsorption process by the matching of metal ions is as follows: active hydroxyl group on the surface of mineral crystal is complexed with pigment molecule, and Si on the surface of crystal⁴⁺、Mg²⁺Can be covered by Fe²⁺、Al³⁺And after metal ion exchange, the metal ions are used as a mordant of the water-soluble animal and plant pigment and are matched with the mineral crystal and a ligand on a pigment molecule to form a complex, so that the metal ions play a role of a bridge between the mineral crystal and the pigment, the pigment can effectively dye the mineral, the color depth and the fastness of the mordant compound pigment are improved, different colors can be obtained by using different metal ions, and the prepared compound pigment is rich in color.

According to the preparation method, impurities in the minerals can be removed through low-temperature plasma cleaning, so that the pigment can be better adsorbed on the surface of the mineral crystal, in the grooves and in the pore channels, and the loading efficiency and firmness are improved. And only trace gas is used in the cleaning process, no pollutant is discharged, the operation environment is a dry gas environment, additional drying is not needed, the energy consumption is low, and the cleaning effect is good.

This example provides another preparation method of the composite pigment of the natural mesoporous mineral and the animal and plant pigment in example 1, as shown in fig. 8, including the following steps:

s201, preparing a second pigment solution from 1-20 parts by weight of oil-soluble animal and plant pigment and 80-90 parts by weight of a second solvent; preferably, the second solvent is methanol, ethanol, acetone, diethyl ether or ethyl acetate. The oil soluble animal and plant pigment comprises one or more of alkannin, lycopene, astaxanthin, canthaxanthin, lactoflavin, fructus Lycii pigment, zeaxanthin, curcumin, bixin, sorghum red, capsanthin, ranunculin, violaxanthin, rhodoxanthin, and zeaxanthin.

S202, cleaning natural mesoporous minerals by using a low-temperature plasma cleaning method, wherein the mass ratio of the natural mesoporous minerals to the oil-soluble animal and plant pigments is (7-9) to (1-3); preferably, the method specifically comprises the following steps: putting natural mesoporous mineral into low-temperature plasma reaction equipment, and reacting with O₂As cleaning gas, discharging and reacting for 2-15 minutes, and setting parameters as follows: o is₂The pressure is 10Pa, the power is 50-100W, the voltage is 500-800V, and the current is 40-100 mA. In the process, inorganic gas is excited to a plasma state and then is adsorbed on the surface of the solid, the inorganic gas reacts with molecules on the surface of the solid to generate product molecules, the product molecules are resolved to form a gas phase, and reaction residues are separated from the surface through vacuum pumping and discharging, so that the effect of removing impurities is achieved.

S203, carrying out low-temperature plasma modified grafting on the cleaned natural mesoporous mineral to obtain a modified and grafted mineral; preferably, the method specifically comprises the following steps: the cleaned natural mesoporous mineral is treated by N in low-temperature plasma reaction equipment₂As initiating gas, discharging for 4-20 minutes, discharging once every 2-10 minutes for two times, and setting parameters as follows: n is a radical of₂The pressure is 10Pa, the power is 50-100W, the voltage is 500-800V, and the current is 40-100 mA; adding graft monomer solution after the discharge reaction is finished, wherein the weight percentage of the mineral to the graft monomer is 1 to (0.4-5.0), reacting for 3-6 hours, then washing to be neutral, filtering and drying to obtain the modified grafted mineralA compound (I) is provided. Preferably, the graft monomer is chitosan, a silane coupling agent, a titanate coupling agent or a quaternary ammonium salt cationic surfactant.

S204, adding the modified and grafted mineral into the second pigment solution, continuously stirring for a period of time, placing the solution into a constant-temperature oscillation box, carrying out physical adsorption and chemical adsorption grafted by the graft monomer for 12-48 hours, then centrifuging, washing (for example, washing the solid obtained after centrifuging with a solvent for more than two times), drying (for example, in a decompression dryer, setting parameters of pressure of 0-2.67KPa, temperature of 30-40 ℃ and time of 2-12 hours), grinding and sieving (for example, 200 meshes) to obtain the composite pigment of the natural mesoporous mineral and the animal and plant pigment. The adsorption of the minerals to the pigments is saturated after the physical and chemical adsorption. As the surface of the mineral crystal contains hydroxyl, the hydrophilicity is good, and the adsorption capacity for oil-soluble animal and plant pigments is poor, the hydrophilic or hydrophobic performance of the mineral is changed by introducing organic functional groups for the oil-soluble pigments. The surface of the mineral crystal is modified and grafted, and the grafted hydrophobic group can be adsorbed and combined with oil-soluble animal and plant pigments under the chemical adsorption effect of grafting of a graft monomer.

The preparation method adopts the low-temperature plasma cleaning technology and the low-temperature plasma surface modification technology to clean and modify the minerals, has mild conditions and low-temperature energy consumption, and can effectively compound pigments with different hydrophilicity and lipophilicity and heat resistance. Impurities in minerals can be removed through low-temperature plasma cleaning, pigments are effectively adsorbed on the surfaces of crystals, grooves and pore channels, load efficiency and load capacity are improved, only trace gas is used in work, the operation environment is a dry gas environment, additional drying is not needed, the cleaning effect is good, and the crystal structure of the minerals cannot be damaged. The low-temperature plasma surface modification technology can introduce different functional groups on the surface of the mineral by changing plasma parameters (voltage, gas, modification time, pressure and the like), change the hydrophilic or hydrophobic performance of the mineral, load pigments with different hydrophilic and lipophilic properties, and has the advantages of mild conditions and short reaction time. In the embodiment, heating is not needed in the cleaning, modification and compounding processes, the energy consumption is low, the pigment with unstable heat can be well applied, and the application range of the natural animal and plant pigment is enlarged.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.