CN117326597B - Method for regulating and controlling size of nano iron oxide yellow, nano iron oxide yellow and application thereof - Google Patents

Abstract

The application relates to the technical field of ferric oxide pigments, and particularly discloses a method for regulating and controlling the size of nano-iron oxide yellow, the nano-iron oxide yellow and application thereof. A nanometer iron oxide yellow comprises iron oxide yellow, and nitrogen positive ion type protective agent layer coated on the surface of the iron oxide yellow; the nano iron oxide yellow is also subjected to chemical acid etching treatment; the grain diameter of the nano iron oxide yellow after chemical acid etching treatment is 200-600 nm; the preparation method comprises the following steps: mixing iron oxide yellow, a nitrogen positive ion type protective agent and acid to obtain a mixed solution; stirring and mixing the mixed solution at 50-150 ℃ for 1-10 h to obtain a reaction solution; cooling the reaction liquid to 20-25 ℃, filtering, collecting solid, washing and drying the solid to obtain nano iron oxide yellow. The method for regulating and controlling the size of the nano iron oxide yellow can be used for preparing the nano iron oxide yellow with small particle size and uniform particle size distribution, and has good dispersibility, color spreading and stability when applied to cosmetics.

Description

Method for regulating and controlling size of nano iron oxide yellow, nano iron oxide yellow and application thereof

Technical Field

The application relates to the technical field of ferric oxide pigments, in particular to a method for regulating and controlling the size of nano-iron oxide yellow, the nano-iron oxide yellow and application thereof.

Background

The iron oxide pigment is widely applied in practical production and life, and is widely applied to industries of building materials, coatings, printing ink, rubber, plastics, ceramics, glass products, hardware glass polishing, dramatic oil colors, painting, cosmetics, medicine coloring, catalysts, electronic industry and the like. In particular, in the cosmetic industry, iron oxide is the most widely used inorganic color pigment other than titanium white. Because the ferric oxide is relatively easy to disperse, is insoluble in water, alkali and organic solvents, and has the color from yellow, red to black and brown, and has rich hue. In addition, the ferric oxide has stable performance, no toxicity, no smell, no absorption by human body, no side effect, no dosage limitation, no oil permeability, no damage to skin, no color change after long exposure and long preservation, and has high tinting strength, hiding power, chemical resistance and light fastness. Therefore, iron oxide plays an indispensable role in the cosmetic field.

Currently, iron oxide is used in the cosmetic industry, mainly as a colorant for soaps, nail varnishes, facial oils, skin creams, cosmetic pens, lipsticks, and the like. Iron oxide as a colorant pigment has a particle size that affects the development of cosmetic color. The finer the particle size of the ferric oxide, the more complete the color development, the smaller the apparent color and the coating color difference, and the finer the skin feel.

The particle size may be classified into three classes of primary particle size, aggregates and agglomerates. The primary particle size is the crystal obtained in the production process of the primary particles, the aggregate is the secondary particles formed by the high surface energy of the primary particles, and the aggregate is the tertiary particles formed by loosely combining the aggregate. However, since the surface energy of the iron oxide pigment is high, in the iron oxide pigment actually used, aggregates and agglomerates are generally seen, and thus the iron oxide pigment has a large and nonuniform particle size, thereby affecting its color development in cosmetics.

Disclosure of Invention

In order to reduce the particle size of the iron oxide pigment and improve the uniformity of the particle size of the iron oxide pigment, the application provides a method for regulating and controlling the size of nano iron oxide yellow, the nano iron oxide yellow and application thereof.

In a first aspect, the present application provides a nano iron oxide yellow, which adopts the following technical scheme:

A nanometer iron oxide yellow comprises iron oxide yellow, wherein the surface of the iron oxide yellow is coated with a nitrogen positive ion type protective agent layer;

The nano iron oxide yellow is also subjected to chemical acid etching treatment;

The particle size of the nano iron oxide yellow after chemical acid etching treatment is 200-600 nm.

The protective agent is a liquid substance for protecting the surface of metal, nonmetal or composite material, so that the surface of the material has certain special functions such as acid and alkali resistance, salt spray resistance, water resistance, wear resistance, solvent resistance or special gas resistance, aging resistance, ultraviolet resistance, high temperature resistance, low temperature resistance, vibration resistance, skid resistance, antifriction, static resistance, moisture resistance, pollution resistance, insulation, electric conduction, heat insulation, flame retardance and the like.

By adopting the technical scheme, the nitrogen positive ion protective agent is coated on the surface of the iron oxide yellow, so that the chemical activity of the iron oxide yellow can be passivated, and the nano iron oxide yellow with small particle size is protected from being etched by acid and has too small particle size. Then, the nano iron oxide yellow with large particle size is subjected to chemical acid etching treatment, so that the particle size of the nano iron oxide yellow can be reduced, the nano iron oxide yellow with the particle size uniformly distributed in the range of 200-600 nm is obtained, the specific surface area is high, the tinting strength is high, and the nano iron oxide yellow has higher surface affinity with a dispersing auxiliary agent when in use, so that the nano iron oxide yellow has good dispersibility and color spreading property. Meanwhile, the nano iron oxide yellow with the particle size distribution within the range of 200-600 nm has lower specific gravity, so that the nano iron oxide yellow is easier to stabilize after being dispersed, and the stability of the nano iron oxide yellow after being used is improved.

In a second aspect, the application provides a method for regulating and controlling the size of nano iron oxide yellow, which adopts the following technical scheme: a method for regulating and controlling the size of nano iron oxide yellow, which comprises the following steps:

s1: mixing iron oxide yellow, a nitrogen positive ion type protective agent and acid to obtain a mixed solution;

s2: stirring and mixing the mixed solution for 1-10 hours at the temperature of 40-80 kHz and the temperature of 50-150 ℃ to obtain a reaction solution;

s3: cooling the reaction liquid to 20-25 ℃, filtering, collecting solid, washing and drying the solid to obtain nano iron oxide yellow.

The original size distribution of the iron oxide yellow is uneven, and the particle size is different from hundreds of nanometers to microns.

By adopting the technical scheme, after the iron oxide yellow, the nitrogen positive ion type protective agent and the acid are mixed, on one hand, the surface energy of the iron oxide yellow is higher, and the iron oxide yellow has an adsorption effect with the nitrogen positive ion type protective agent, so that the nitrogen positive ion type protective agent can be coated on the surface of the iron oxide yellow, the chemical activity of the iron oxide yellow is passivated, and the iron oxide yellow with small particle size is not etched by the acid but has too small particle size; on the other hand, for the iron oxide yellow with a large particle size, the particle size thereof can be reduced by etching it with an acid solution. Meanwhile, by controlling the temperature and time of the acid etching process, the nano iron oxide yellow with the particle size distribution within the range of 200-600 nm can be obtained, so that the particle size of the iron oxide yellow is reduced, the uniformity of the particle size distribution is improved, and the dispersibility and color spreading performance of the nano iron oxide yellow in use are improved.

Preferably, the nitrogen positive ion type protective agent is one or more of hexadecyl trimethyl ammonium bromide, 1-ethyl-3-methylimidazole tetrafluoroborate, tetrabutylammonium bromide, phenyl tripropyl ammonium bromide, tetraoctyl ammonium tetrafluoroborate, tetra (4-chlorophenyl) ammonium borate and diethyl ethanol ammonium chloride.

By adopting the technical scheme, the nitrogen positive ion type protective agent has good coating property on the iron oxide yellow, is beneficial to passivating the chemical activity of the iron oxide yellow, and is beneficial to improving the uniformity of the particle size of the obtained nano iron oxide yellow after acid etching.

Preferably, the molar ratio of the iron oxide yellow to the azotic positive ion protective agent to the acid is 1 (0.114-0.771) (3.554-35.542).

By adopting the technical scheme, the iron oxide yellow, the nitrogen positive ion protective agent and the acid are added according to the molar ratio, and the nitrogen positive ion protective agent is coated on the surface of the iron oxide yellow, so that a good passivation protection effect is achieved on the iron oxide yellow, and the nano iron oxide yellow with uniform particle size can be obtained after acid etching.

Preferably, the molar ratio of the iron oxide yellow to the azotic positive ion protective agent to the acid is 1 (0.114-0.771) (7.108-28.434).

By adopting the technical scheme, the addition amount of the iron oxide yellow, the nitrogen positive ion type protective agent and the acid is further optimized, so that the particle size of the iron oxide yellow can be reduced, the uniformity of the particle size of the iron oxide yellow can be improved, and the dispersibility and color spreading property of the nano iron oxide yellow in application can be improved.

Preferably, the mixed solution is stirred and mixed for 2 to 4 hours at the temperature of 80 to 150 ℃ to obtain the reaction solution.

By adopting the technical scheme, the reaction temperature and the reaction time during acid etching are optimized, the particle size of the iron oxide yellow can be effectively regulated and controlled, and the nano iron oxide yellow with small particle size and uniform particle size is obtained.

Preferably, the method for regulating and controlling the size of the nano iron oxide yellow comprises the following steps:

s1: mixing iron oxide yellow, a nitrogen positive ion type protective agent and acid to obtain a mixed solution;

s2: stirring and mixing the mixed solution for 2-4 hours at the temperature of 40-60 kHz and the temperature of 80-150 ℃ to obtain a reaction solution;

s3: cooling the reaction liquid to 20-25 ℃, filtering, collecting solids, washing and drying the solids to obtain nano iron oxide yellow;

the molar ratio of the iron oxide yellow, the nitrogen positive ion type protective agent and the acid is 1 (0.321-0.771) (21.325-28.434).

Preferably, the concentration of the acid is 1 to 5mol/L.

By adopting the technical scheme, the addition amount of the iron oxide yellow, the nitrogen positive ion type protective agent and the acid, and the reaction temperature and time of the mixed solution during acid etching are optimized, so that the nano iron oxide yellow with the particle size distribution of 200-500 nm can be obtained, and the nano iron oxide yellow has good dispersibility and color development during application.

Preferably, the acid is sulfuric acid or hydrochloric acid.

By adopting the technical scheme, the particle size of the iron oxide yellow coated with the nitrogen positive ion protective agent can be reduced rapidly and effectively without using the inorganic acid, and the iron oxide yellow is easy to wash and remove, so that the preparation efficiency of the nano iron oxide yellow is improved.

In a third aspect, the application provides an application of nano iron oxide yellow, which adopts the following technical scheme:

An application of nano iron oxide yellow in preparing liquid eyeliner is disclosed.

The liquid eyeliner consists of the following components in percentage by weight:

8-10% of humectant;

0.7 to 0.9 percent of bactericide;

9.5 to 10.5 percent of nano iron oxide yellow;

21-25% of film forming agent;

suspending agent 0.5-1.0%

55.45 To 57.45 percent of water.

By adopting the technical scheme, the nano iron oxide yellow is used as the colorant, the finally prepared liquid eyeliner has smooth liquid outlet, high color rendering, good water resistance, oil resistance and friction resistance, the liquid eyeliner is not easy to coarsen, the liquid eyeliner is placed in a high-temperature environment at 60 ℃ for seven days, the particle size change rate is as low as 0.32-10.45%, and the liquid eyeliner has good high-temperature storage stability.

In summary, the application has the following beneficial effects:

1. The application adopts the nitrogen positive ion protective agent to coat the surface of the iron oxide yellow, and then carries out acid etching treatment to obtain the nano iron oxide yellow with the grain size distribution within the range of 200-600 nm, and has good dispersibility and color development when the nano iron oxide yellow is used; 2. the method for regulating and controlling the particle size of the iron oxide yellow pigment by adopting the chemical acid etching method is simple to operate, the required material cost is low, the loss rate of the iron oxide yellow after chemical acid etching is small, and the method is suitable for large-scale production;

3. when the nano iron oxide yellow is applied to liquid eyeliner, the nano iron oxide yellow has good dispersibility and color development, and has high-temperature storage stability and difficult coarsening.

Drawings

FIG. 1 is a scanning electron microscope image of a nano-iron oxide pigment obtained by the reaction of example 1 of the present application;

FIG. 2 is a scanning electron microscope image of a nano-iron oxide pigment obtained by the reaction of example 2 of the present application;

FIG. 3 is a scanning electron microscope image of a nano-iron oxide pigment obtained by the reaction of example 3 of the present application;

FIG. 4 is a scanning electron microscope image of a nano-iron oxide pigment obtained by the reaction of example 4 of the present application;

FIG. 5 is a scanning electron microscope image of the nano-iron oxide pigment obtained by the reaction of example 5 of the present application;

FIG. 6 is a scanning electron microscope image of the reaction of example 6 of the present application to produce nano-sized iron oxide pigments;

FIG. 7 is a scanning electron microscope image of the reaction of example 7 of the present application to obtain nano-sized iron oxide pigments.

Detailed Description

The application is described in further detail below with reference to the drawings and examples.

The materials used in the examples of the present application are commercially available except for the following specific descriptions.

Iron oxide yellow with particle size of 600-900 nm purchased from Senxin company

Examples

Example 1

The nano iron oxide yellow comprises the following raw materials and the corresponding feeding amounts.

The method for regulating and controlling the size of the nano iron oxide yellow comprises the following steps:

s1: adding tetraoctyl ammonium tetrafluoroborate into iron oxide yellow, adding sulfuric acid solution, and mixing to obtain a mixed solution;

s2: stirring and mixing the mixed solution for 4 hours at the temperature of 40kHz and 120 ℃ to obtain a reaction solution;

s3: naturally cooling the reaction solution to 20-25 ℃, filtering, collecting solids, washing the solids with water and ethanol for three times respectively, and drying the solids at 60 ℃ for 10 hours to obtain nano iron oxide yellow.

FIG. 1 is a scanning electron microscope image of a nano iron oxide yellow pigment obtained by the reaction of example 1, and it can be seen from the image that the product has a closely connected rod-like structure, and the whole particle size range is 200-300 nm.

Example 2

The nano iron oxide yellow comprises the following raw materials and the corresponding feeding amounts.

The method for regulating and controlling the size of the nano iron oxide yellow comprises the following steps:

S1: adding diethyl ethanol-based ammonium chloride into iron oxide yellow, adding hydrochloric acid solution, and mixing to obtain a mixed solution;

s2: stirring and mixing the mixed solution for 2 hours at 50kHz and 80 ℃ to obtain a reaction solution;

s3: cooling the reaction liquid to 20-25 ℃, filtering, collecting solids, washing the solids with water and ethanol for three times respectively, and drying the solids at 60 ℃ for 10 hours to obtain nano iron oxide yellow.

FIG. 2 is a scanning electron microscope image of the nano-iron oxide yellow pigment obtained by the reaction of example 2, and it can be seen from the image that the product has a closely connected rod-like structure, and the whole particle size range is 200-400 nm.

Example 3

The nano iron oxide yellow comprises the following raw materials and the corresponding feeding amounts.

The method for regulating and controlling the size of the nano iron oxide yellow comprises the following steps:

s1: adding 1-ethyl-3-methylimidazole tetrafluoroborate into iron oxide yellow, adding sulfuric acid solution, and mixing to obtain a mixed solution;

s2: stirring and mixing the mixed solution for 3 hours at 60kHz and 150 ℃ to obtain a reaction solution;

s3: cooling the reaction liquid to 20-25 ℃, filtering, collecting solids, washing the solids with water and ethanol for three times respectively, and drying the solids at 60 ℃ for 10 hours to obtain nano iron oxide yellow.

FIG. 3 is a scanning electron microscope image of the nano-iron oxide yellow pigment obtained by the reaction of example 3, and it can be seen from the image that the product has a closely connected rod-like structure, and the whole particle size ranges from 200 nm to 500nm.

Example 4

The nano iron oxide yellow comprises the following raw materials and the corresponding feeding amounts.

The method for regulating and controlling the size of the nano iron oxide yellow comprises the following steps:

s1: adding cetyltrimethylammonium bromide into iron oxide yellow, and then adding sulfuric acid solution for mixing to obtain mixed solution;

s2: stirring and mixing the mixed solution for 1h at the temperature of 80kHz and 100 ℃ to obtain a reaction solution;

s3: cooling the reaction liquid to 20-25 ℃, filtering, collecting solids, washing the solids with water and ethanol for three times respectively, and drying the solids at 60 ℃ for 10 hours to obtain nano iron oxide yellow.

FIG. 4 is a scanning electron microscope image of the nano-iron oxide yellow pigment obtained by the reaction of example 4, and it can be seen from the image that the product has a closely connected rod-like structure, and the whole particle size ranges from 200 nm to 500nm.

Example 5

The nano iron oxide yellow comprises the following raw materials and the corresponding feeding amounts.

The method for regulating and controlling the size of the nano iron oxide yellow comprises the following steps:

s1: adding tetrabutylammonium bromide into iron oxide yellow, and then adding hydrochloric acid solution for mixing to obtain mixed solution;

S2: stirring and mixing the mixed solution for 10 hours at 70kHz and 80 ℃ to obtain a reaction solution;

s3: cooling the reaction liquid to 20-25 ℃, filtering, collecting solids, washing the solids with water and ethanol for three times respectively, and drying the solids at 60 ℃ for 10 hours to obtain nano iron oxide yellow.

FIG. 5 is a scanning electron microscope image of the nano-iron oxide yellow pigment obtained by the reaction of example 5, and it can be seen from the image that the product has a closely connected rod-like structure, and the whole particle size ranges from 200 nm to 500nm.

Example 6

The nano iron oxide yellow comprises the following raw materials and the corresponding feeding amounts.

The method for regulating and controlling the size of the nano iron oxide yellow comprises the following steps:

s1: adding phenyl tripropyl ammonium bromide into iron oxide yellow, and then adding hydrochloric acid solution for mixing to obtain mixed solution;

s2: stirring and mixing the mixed solution for 6 hours at 60kHz and 50 ℃ to obtain a reaction solution;

s3: cooling the reaction liquid to 20-25 ℃, filtering, collecting solids, washing the solids with water and ethanol for three times respectively, and drying the solids at 60 ℃ for 10 hours to obtain nano iron oxide yellow.

FIG. 6 is a scanning electron microscope image of the nano-iron oxide yellow pigment obtained by the reaction of example 6, and it can be seen from the image that the product has a closely connected rod-like structure, and the whole particle size ranges from 200 nm to 500nm.

Example 7

The nano iron oxide yellow comprises the following raw materials and the corresponding feeding amounts.

The method for regulating and controlling the size of the nano iron oxide yellow comprises the following steps:

S1: adding ammonium tetra (4-chlorophenyl) borate into iron oxide yellow, and then adding sulfuric acid solution for mixing to obtain a mixed solution;

S2: stirring and mixing the mixed solution for 8 hours at 50kHz and 100 ℃ to obtain a reaction solution;

s3: cooling the reaction liquid to 20-25 ℃, filtering, collecting solids, washing the solids with water and ethanol for three times respectively, and drying the solids at 60 ℃ for 10 hours to obtain nano iron oxide yellow.

FIG. 7 is a scanning electron microscope image of the nano-iron oxide yellow pigment obtained by the reaction of example 7, and it can be seen from the image that the product has a closely connected rod-like structure, and the whole particle size ranges from 400 nm to 600nm.

The particle diameters of the nano-iron oxide yellow obtained in the above examples 1 to 7 are shown in the following table.

As is clear from the data analysis of the above table, the nano-iron oxide yellow obtained in examples 1 to 7 has a particle size ranging as low as 200 to 600nm. Therefore, the nano iron oxide yellow prepared by the method for regulating and controlling the size of the nano iron oxide yellow has a lower particle size range.

Comparing examples 1 to 2 with examples 4 to 7, examples 1 to 2 have lower particle diameters and more uniform particle diameter distribution than examples 4 to 7. Therefore, in the method for regulating the size of the nano iron oxide yellow, in the step 1, the molar ratio of the iron oxide yellow, the nitrogen positive ion protective agent and the acid is 1 (0.321-0.771): (21.325-28.434); in the step S2, the mixed solution is stirred and mixed for 2 to 4 hours at the temperature of 80 to 150 ℃, so that the particle size of the finally obtained nano iron oxide yellow can be reduced, and the uniformity of the particle size can be improved.

Comparative example

Comparative example 1

The difference from example 1 is that the nano-iron oxide yellow is not treated by a method of controlling the size of the nano-iron oxide yellow.

The detection shows that the particle size of the nano iron oxide yellow is 600-900 nm.

Comparative example 2

A nano iron oxide yellow is different from example 1 in that an equal amount of a polyvinyl alcohol protecting agent is used instead of a nitrogen cation protecting agent, wherein polyvinyl alcohol, 1799 type, is purchased from Allatin.

The detection shows that the particle size of the nano iron oxide yellow is 700-900 nm.

Comparative example 3

A nano iron oxide yellow differs from example 1 in that an aqueous solution of potassium hydroxide in an amount of the same substance is used instead of the acid.

The detection shows that the particle size of the nano iron oxide yellow is 800-900 nm.

Comparative example 4

The difference from example 1 is that the addition amount of the nitrogen cation protecting agent is 0.

The detection shows that the particle size of the nano iron oxide yellow is 400-800 nm.

Comparing example 1 with comparative examples 1 to 3, it is seen that example 1 has a lower particle size and a more uniform particle size range than comparative examples 1 to 3. Therefore, the application adopts the nitrogen positive ion protective agent to coat the iron oxide yellow and then carries out chemical acid etching, thus reducing the particle size of the finally obtained nano iron oxide yellow and improving the uniformity of particle size distribution.

Although the particle size of the iron oxide yellow in comparative example 4 was reduced, the particle size range was large, and it was possible that the iron oxide yellow having different particle sizes was directly acid etched because the iron oxide yellow was not protected with the nitrogen cation protecting agent, and the iron oxide yellow having a large particle size was smaller and the iron oxide yellow having a small particle size was smaller, so that the particle size range of the iron oxide yellow after acid etching was large.

Application example

Application example 1

Liquid eyeliner, each component and its corresponding weight (kg) are shown in the following table.

The preparation method of the liquid eyeliner comprises the following steps:

Stirring and mixing a humectant, a bactericide and a suspending agent at 10-30 ℃ (25 ℃ in the application example of the application) for 5min at 600r/min, then adding water, stirring and mixing for 5min, adding ferric oxide yellow, stirring and mixing for 30min, finally adding a film forming agent, and continuing stirring and mixing for 20min to obtain a semi-finished liquid eyeliner; and filling the semi-finished liquid eyeliner into a commercially available eyeliner packaging material to obtain the liquid eyeliner.

In the application example of the application, the nano iron oxide yellow prepared in the example 1 is adopted.

Application examples 2 to 11

The liquid eyeliner is different from application example 1 in that iron oxide yellow is different.

In application examples 2 to 11, the nano-iron oxide yellow prepared by examples or comparative examples shown in the following table was used.

Application example 1	Example 1
		Application example 2	Example 2
Application example 3	Example 3
		Application example 4	Example 4
Application example 5	Example 5
		Application example 6	Example 6
Application example 7	Example 7
		Application example 8	Comparative example 1
Application example 9	Comparative example 2
		Application example 10	Comparative example 3
Application example 11	Comparative example 4

The liquid eyeliners obtained in application examples 1 to 11 of the present application were tested for water repellency, oil resistance, abrasion resistance, liquid discharge smoothness, color rendering index, and makeup removal, as follows:

Waterproof performance detection: drawing two lines with the same thickness and adjacent positions on the skin by adopting the liquid eyeliner obtained in the application example, washing the skin for 10S by using water flow after 30S, rubbing the skin with the hand to the same side of the two lines for 3 times, observing the rubbing phenomenon of the two lines on the skin, scoring according to 1-5 points, wherein 1 point represents complete rubbing and 5 points represent no rubbing and removing; the detection is performed in three times, and the scoring result is averaged.

Oil resistance detection: drawing two lines with the same thickness and adjacent positions on the skin by adopting the liquid eyeliner obtained in the application example, soaking for 10S by using artificial sebum after 30S, rubbing the same side of the two lines for 3 times by hands, observing the rubbing phenomenon of the two lines on the skin, scoring according to 1-5 points, wherein 1 point represents complete rubbing and 5 points represent no rubbing and removing; the detection is performed in three times, and the scoring result is averaged.

And (3) antifriction degree detection: drawing two lines with the same thickness and adjacent positions on the skin by adopting the liquid eyeliner obtained in the application example, rubbing the two lines on the skin for 3 times by pointing to the same side of the two lines by hands after 30 seconds, observing the rubbing phenomenon of the two lines on the skin, scoring according to 1-5 points, wherein 1 point represents complete rubbing and 5 points represent no rubbing and removing; the detection is performed in three times, and the scoring result is averaged.

Detecting the fluency and color rendering degree of liquid: selecting female volunteers with the ages of 18-35 years and the same skin quality, drawing an eye line at the eyelid of the volunteer by using the liquid eye line pen obtained in the application example, observing the color development depth of the eye line, grading according to 1-5 points, wherein 1 point represents no color development, and 5 points represent color development depth; the detection is performed in three times, and the scoring result is averaged. Meanwhile, when the eyeliner is drawn, the fluency of liquid discharged by the eyeliner is scored according to 1-5 points, wherein 1 point represents liquid discharge blocking and 5 points represent liquid discharge fluency; the detection is performed in three times, and the scoring result is averaged.

And (3) makeup removal detection: drawing two lines with the same thickness and adjacent positions on the skin by adopting the liquid eyeliner obtained in the application example, wiping the same side of the two lines for 1 time by adopting makeup removing cotton containing makeup removing water after 30 seconds, observing the bottom leaving condition of the two lines on the skin, scoring according to 1-5 points, wherein 1 point represents that the bottom leaving condition is serious, and 5 points represent that the bottom leaving condition is not present; the detection is performed in three times, and the scoring result is averaged.

The water repellency, oil resistance, abrasion resistance, liquid discharge smoothness, color development and makeup removal test results of the liquid eyeliners obtained in application examples 1 to 7 are shown in the following table.

From the analysis of the performance data of the table, the liquid eyeliner prepared from the nano iron oxide yellow obtained in the application examples 1 to 7 is high in waterproofness of 4.6 to 4.8 minutes, oil resistance of 4.8 to 5.0 minutes, friction resistance of 4.7 to 4.9 minutes, liquid outflow smoothness of 4.9 to 5.0 minutes, color rendering of 4.5 to 4.6 minutes and bottom retention of 4.8 to 5.0 minutes when the makeup is removed and checked. Therefore, the nano iron oxide yellow prepared by the method for regulating and controlling the size of the iron oxide yellow pigment has the advantages of good water resistance, oil resistance, friction resistance and smoothness in liquid discharge, and good makeup holding effect.

The water repellency, oil resistance, abrasion resistance, liquid discharge smoothness, color development and makeup removal test results of the liquid eyeliners obtained in application examples 8 to 11 are shown in the following table.

Comparing application examples 1 to 7 with application example 8, it is known that the liquid eyeliner made of nano iron oxide yellow of application examples 1 to 7 is improved by 6.98 to 11.63% in water resistance, 9.09 to 13.64% in oil resistance, 6.82 to 11.36% in friction resistance and 32.43 to 35.14% in liquid smoothness, compared with the liquid eyeliner made of untreated iron oxide yellow of application example 8, the nano iron oxide yellow prepared by the method for regulating and controlling the size of iron oxide yellow pigment of the application can improve the water resistance, oil resistance, friction resistance, liquid smoothness and makeup holding effect of the finally obtained liquid eyeliner.

The color rendering degree includes various dimensions such as tinting strength (color development) and hiding power. In the cosmetic industry, pigments have small particle size, large specific surface area, and high tinting strength (vivid and bright). However, since the pigment particle diameter is small, the light transmittance increases, resulting in deterioration of hiding power. Therefore, the particle size generally decreases, and the color rendering degree decreases. However, as is clear from the above table, the liquid eyeliners of the present application using the nano-iron oxide yellow obtained in examples 1 to 7 were not affected in the color development degree as compared with the liquid eyeliner of the present application using the nano-iron oxide yellow obtained in comparative example 1 in application example 8, and it is possible to analyze the reason that the particle size of the nano-iron oxide yellow obtained in examples 1 to 7 of the present application is 1/2 of the optical band thereof, so that the color development degree is optimal.

As is clear from comparison of application examples 1 to 7 with application examples 9 to 11, application examples 1 to 7 have higher water repellency, oil resistance, abrasion resistance, liquid discharge smoothness and color rendering index than application examples 9 to 11. Therefore, the nano iron oxide yellow prepared by the method for regulating and controlling the size of the iron oxide yellow pigment can improve the water resistance, oil resistance, friction resistance, liquid smoothness and make-up holding effect of the finally obtained liquid eyeliner.

The liquid eyeliners obtained in application examples 1 to 11 were put into a 60 ℃ oven for stability detection, and the trend of the particle size over time was observed. The specific test results are shown in the following table.

As can be seen from the analysis of the performance data of the above tables, the liquid eyeliner obtained in application examples 1 to 7 of the present application is placed at a high temperature of 60 ℃ for 7 days, the particle size change rate is as low as 0.32 to 10.45%, and the liquid eyeliner has great advantages compared with the particle size change rate of application examples 8 to 11, which is up to 17.15 to 24.18%, and shows that the high temperature change of the particle size of application examples 1 to 7 is not easy to coarsen on the basis of small particle size of the ferric oxide pigment compared with application examples 8 to 11. The reason for this analysis is probably that the finer the particle diameter is, the higher the affinity of the dispersing aid to the pigment surface is, and at the same time, the more stable after dispersion is because the particle specific gravity is reduced.

As is clear from comparison of application examples 1 to 2, application examples 3 to 4, and application examples 6 to 7, the particle diameter change rate is from small to large, and is application examples 1 to 2, application examples 3 to 4, and application examples 6 to 7 in this order. Therefore, in the method for regulating the size of the nano iron oxide yellow, the stability of the liquid eyeliner can be improved after the nano iron oxide yellow is used in the liquid eyeliner by controlling the molar ratio of the iron oxide yellow, the nitrogen positive ion protective agent and the acid to be 1 (0.114-0.771) (3.554-35.542), specifically 1 (0.114-0.771) (7.108-28.434) and stirring and mixing the mixed solution for 2-4 hours under the condition of 80-150 ℃.

In the application, the liquid eyeliner consists of 8-10% of humectant, 0.7-0.9% of bactericide, 9.5-10.5% of iron oxide yellow pigment, 21-25% of film forming agent, 0.5-1.0% of suspending agent and 55.45-57.45% of water, wherein the humectant, the bactericide, the film forming agent, the suspending agent and the water are all conventional raw materials sold in the market. The liquid eyeliner pen finally obtained has water resistance, oil resistance, friction resistance, liquid smoothness, makeup holding effect, color rendering degree, makeup removing effect and stability similar to those of application example 1. Therefore, the present application will be briefly described by taking the weight of the components in the liquid eyeliner of application example 1 as an example, but the weight of the other components is not affected in the application of the present application.

The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.

Claims (6)

1. The preparation method for regulating and controlling the size of the nano iron oxide yellow is characterized in that the surface of the iron oxide yellow is coated with a nitrogen positive ion type protective agent layer;

The nano iron oxide yellow is also subjected to chemical acid etching treatment;

The grain diameter of the nano iron oxide yellow after chemical acid etching treatment is 200-600 nm;

The preparation method for regulating the size of the nano iron oxide yellow comprises the following steps:

s1: mixing iron oxide yellow, a nitrogen positive ion type protective agent and acid to obtain a mixed solution;

s2: stirring and mixing the mixed solution for 1-10 hours at the temperature of 40-80 kHz and the temperature of 50-150 ℃ to obtain a reaction solution;

s3: cooling the reaction liquid to 20-25 ℃, filtering, collecting solids, washing and drying the solids to obtain nano iron oxide yellow;

The nitrogen positive ion type protective agent is one or more of hexadecyl trimethyl ammonium bromide, 1-ethyl-3-methylimidazole tetrafluoroborate, tetrabutylammonium bromide, phenyl tripropyl ammonium bromide, tetraoctyl tetrafluoroborate, tetra (4-chlorophenyl) ammonium borate and diethyl ethanol ammonium chloride;

The molar ratio of the iron oxide yellow, the nitrogen positive ion type protective agent and the acid is 1 (0.114-0.771) (3.554-35.542).

2. The method for preparing nano-iron oxide yellow according to claim 1, wherein the molar ratio of the iron oxide yellow to the azotometer to the acid is 1 (0.114-0.771) (7.108-28.434).

3. The method for preparing nano-iron oxide yellow according to claim 1, wherein the mixed solution is stirred and mixed for 2-4 hours at 80-150 ℃ to obtain the reaction solution.

4. The method for preparing nano-iron oxide yellow according to claim 1, comprising the steps of:

s1: mixing iron oxide yellow, a nitrogen positive ion type protective agent and acid to obtain a mixed solution;

s2: stirring and mixing the mixed solution for 2-4 hours at the temperature of 40-60 kHz and the temperature of 80-150 ℃ to obtain a reaction solution;

s3: cooling the reaction liquid to 20-25 ℃, filtering, collecting solids, washing and drying the solids to obtain nano iron oxide yellow;

the molar ratio of the iron oxide yellow, the nitrogen positive ion type protective agent and the acid is 1 (0.321-0.771) (21.325-28.434).

5. The method for preparing nano-iron oxide yellow according to claim 1, wherein the concentration of the acid is 1-5 mol/L.

6. The method for preparing nano-iron oxide yellow according to claim 1, wherein the acid is sulfuric acid or hydrochloric acid.