CN112552710B - Surface treatment method of titanium dioxide pigment with high hydrophobicity and high dispersibility for cosmetics - Google Patents
Surface treatment method of titanium dioxide pigment with high hydrophobicity and high dispersibility for cosmetics Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3669—Treatment with low-molecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
Abstract
The invention provides a surface treatment method of a titanium dioxide pigment with high hydrophobicity and high dispersibility for cosmetics. The method of the invention comprises the following steps: firstly, grinding and grading a rutile type titanium dioxide pigment raw material under the action of a grinding aid to remove agglomerated particles in the titanium dioxide pigment raw material; then the treated titanium dioxide pigment is prepared into paste and then transferred into a reaction device, stirring is started, the PH value is adjusted to be alkalescent, and then the temperature is increased to 50-100 ℃ for reaction bonding; then heating and drying to obtain titanium dioxide pigment cake material, and finally crushing and removing impurities to obtain the titanium dioxide pigment product with high hydrophobicity and high dispersibility for cosmetics. The preparation process can effectively improve the coating feeling of the titanium dioxide pigment, endow the titanium dioxide pigment with excellent hydrophobicity, and have good compatibility and dispersibility with oil components in a cosmetic formula, thereby meeting the use requirements of cosmetics and ensuring the use effect of the cosmetics.
Description
The technical field is as follows:
the invention relates to a surface treatment method of a titanium dioxide pigment with high hydrophobicity and high dispersibility for cosmetics, belonging to the technical field of cosmetic raw materials.
Background art:
titanium dioxide (TiO)2) Commonly known as titanium dioxide, is the most important white pigment and accounts for 80 percent of the total white pigment. The white pigment has stable physicochemical properties and excellent photoelectric properties, has the highest refractive index among known white pigments, has the best opacity (hiding power), whiteness and brightness, is considered to be the white pigment with the best performance in the world at present, is called as 'king of white pigment', and is widely applied to a plurality of industries such as coating, plastics, papermaking, printing ink, chemical fiber, rubber, cosmetics and the like. Titanium dioxide (TiO) is being used in many developed countries2) The key chemical ranks are listed, and in some countries and regions, the consumption is proportional to the total production value (GDP) of the country, even titanium dioxide (TiO)2) Is used as a measure of the amount of consumption of a countryOne of the important signs of the economic development and the high and low living standard of people.
Titanium dioxide has three crystal forms in nature, Anatase type (Anatase, abbreviated as a type), rutile type (Rutail, abbreviated as R type), and brookite type. The brookite type is rare in nature, belongs to an orthorhombic crystal system, is an unstable crystal form, can be converted into a rutile type at about 650 ℃, and has no industrial value. In practice, only anatase type and rutile type are available. The rutile type is the most stable crystal form of the titanium dioxide, has compact structure, wider application range and better performance compared with other crystal forms.
Titanium dioxide has better ultraviolet absorption capacity, excellent chemical stability, thermal stability, nontoxicity, achromatism, covering power, clear color tone, lower abrasiveness and good easy dispersibility, is more and more favored by cosmetic formulation designers at home and abroad, becomes the most important inorganic pigment additive with the largest dosage in high-grade cosmetics, and particularly takes rutile titanium dioxide as the main component.
By utilizing the whiteness and the opacity of the titanium dioxide, the color range of the cosmetic is wide. Titanium dioxide can be used in pressed powder and foundation cream due to its high covering power, and the skin color can be masked with a relatively small amount of titanium dioxide. And can be used for manufacturing a skin cream so that ultraviolet components in incident light can be shielded (scattered or absorbed) by titanium dioxide due to the high opacity of titanium dioxide, thereby protecting the skin from ultraviolet rays, and lipophilic titanium dioxide can also be used in a lipstick, which is a white pigment most effective in giving a red color to the lipstick formed on the lips and producing a hiding power.
With the increase in the life of people and the increasing demand for cosmetics, more cosmetic grade titanium dioxide is consumed. On the surface of data, the annual usage amount of titanium dioxide in the global cosmetics industry is more than 10 million tons, and in recent years, the titanium dioxide is increased at a speed of more than 10%, and the development momentum and the market potential are better.
However, titanium dioxide has strong optical activity and is a strong polar substance, so that titanium dioxide is not easy to disperse in an organic medium, and becomes a main defect of application of titanium dioxide in cosmetics. Firstly, titanium dioxide pigment without surface modification treatment has dry skin feel and poor smearing performance and pasting performance, directly influences the makeup effect of a finished product of the cosmetic, and limits the use of the cosmetic. Secondly, the titanium dioxide has stronger hydrophilic performance (non-hydrophobic), is easy to appear in a flower shape after meeting water and sweat secreted by skin after being made up, has short make-up holding time, brings bad use experience to consumers, and deviates from the desire of the consumers that the make-up holding time can be prolonged as far as possible. Thirdly, although the titanium dioxide treated by stearic acid, organic silicon and the like in the prior art can overcome the influence of incapability of dewatering, the titanium dioxide has the problems of sour taste of raw materials, poor compatibility and dispersibility with oil ester components in a cosmetic formula, easy bleaching, floating color and the like, and is difficult to be used in products such as foundation liquid BB cream with high titanium dioxide components.
In order to solve the above problems, many countries have studied processes and techniques for surface modification treatment of titanium dioxide pigments for cosmetics, to enhance weather resistance and to improve dispersibility. Due to the large demand and high added value, the surface treatment technology of titanium dioxide pigment for cosmetics becomes a hot spot for competitive development and production of a plurality of titanium dioxide pigment manufacturers in the world.
At present, the surface treatment technology of titanium dioxide pigment for cosmetics generally comprises a dry method and a wet method, but the surface treatment technology also has the problems and defects of environmental protection, cost, smell and the like, and the modification mechanism, the modification method, the modification effect representation and the like of the titanium dioxide pigment for cosmetics are still not perfect. Therefore, there is a need to develop a surface treatment technique for titanium dioxide pigments with high hydrophobicity and high dispersibility to improve and solve the above problems.
Through searching, relevant technical schemes are disclosed in the prior art for how to obtain titanium dioxide with high hydrophobicity.
For example, patent publication nos.: CN101367548B, published: in 2011, 29 months 06 and 29 days, the invention and creation names are: the invention discloses a preparation method of hydrophobic nano titanium dioxide powder, which comprises the steps of firstly carrying out inorganic surface treatment on aluminum phosphate, silicon oxide hydrate and aluminum oxide hydrate on nano titanium dioxide in a liquid phase of a nano titanium dioxide aqueous dispersion, then carrying out organic surface treatment on anionic surfactants such as higher fatty acid, higher fatty acid sodium, alkyl sodium laurate, alkyl sodium sulfonate and alkyl potassium phosphate, finally filtering and washing nano titanium dioxide slurry until the conductivity of filtrate is less than 500 mu S/cm, drying and crushing to obtain the hydrophobic nano titanium dioxide powder. The titanium dioxide raw material is nano-scale water dispersion, the technical route adopts multiple coating and wet process, the process is complex, the equipment requirement is high, the energy consumption is large, and the like, and the titanium dioxide is not suitable for pigment-grade titanium dioxide.
For example, patent application publication No.: CN108117775A, published: in 2018, on the day of 06 and 05, the invention and creation name is as follows: the application discloses a hydrophobic and oleophobic inorganic pigment and a preparation method thereof, wherein the hydrophobic and oleophobic inorganic raw material consists of an inorganic pigment, a fluorine surface treatment agent, a fluorine surfactant, an organic solvent, an organic weak acid and deionized water. The preparation method comprises (1) placing the fluorine surface treating agent in organic solvent, adding deionized water, adjusting pH to 3-5 with organic weak acid, heating to 40-50 deg.C, stirring and hydrolyzing at 100-; (2) placing the inorganic pigment in a high-speed stirrer, spraying the mixed solution A, and then stirring at a high speed for dispersion to obtain a mixed material B; (3) and heating the mixed material B at 90-110 ℃ for 5-7 hours to obtain a finished product. The application adopts a dry high-speed mixing technical route which takes one or two of glacial acetic acid and citric acid as a pH regulator and takes tridecafluorooctyltriethoxysilane as a surface treating agent, and the obtained product has poor compatibility and dispersibility with oil and ester components in a cosmetic formula, and the problems of sourness, bleaching, flooding and the like of the product can not be solved.
In conclusion, how to solve the problems of poor skin feel, insufficient hydrophobic property and dispersibility and the like when the conventional titanium dioxide pigment is used as a cosmetic raw material is a technical problem to be solved urgently in the prior art.
The invention content is as follows:
the invention aims to overcome the defects of poor skin feeling, poor hydrophobicity, and poor compatibility and dispersibility with ester components in a cosmetic formula of the existing titanium dioxide pigment for cosmetics, and provides a surface treatment method of the titanium dioxide pigment with high hydrophobicity and high dispersibility for cosmetics.
The above purpose is realized by the following technical scheme:
a surface treatment method of a titanium dioxide pigment with high hydrophobicity and high dispersibility for cosmetics comprises the following steps:
step one, crushing and depolymerizing: grinding and grading a rutile type titanium dioxide pigment raw material under the action of a grinding aid to remove agglomerated particles in the titanium dioxide pigment raw material;
step two, PH adjustment: preparing the titanium dioxide pigment treated in the step one into paste, transferring the paste into a reaction device, starting stirring, adjusting the pH value to be alkalescent, and then heating to 50-100 ℃;
step three, reaction bonding: the mixed solution of the surface treating agent and the auxiliary agent is sprayed on the surface of the pasty titanium dioxide pigment obtained in the step two after being metered, and the reaction bonding is carried out at the temperature of 50-100 ℃;
step four, heating and drying: heating and drying the pasty titanium dioxide pigment obtained in the step three for 5-24 hours at the temperature of 100-180 ℃ to obtain a titanium dioxide pigment cake material;
step five, crushing and impurity removal: and D, crushing and removing impurities from the titanium dioxide pigment cake material obtained in the step four to obtain the titanium dioxide pigment product with high hydrophobicity and high dispersibility for cosmetics.
According to the surface treatment method of the titanium dioxide pigment with high hydrophobicity and high dispersibility for cosmetics, in the first step, the rutile type titanium dioxide pigment raw material meets the following requirements:
the particle size requirement is as follows: d50 of 0.15-0.30 μm and D90 of 0.4-1.0 μm;
the purity meets the requirements: TiO 22≥99％，Al2O3+SiO2≤2％；
The heavy metal content requirement is as follows: pb is less than or equal to 10mg/kg, As is less than or equal to 2mg/kg, Hg is less than or equal to 1mg/kg, and Cd is less than or equal to 5 mg/kg;
other requirements are as follows: the water content is less than or equal to 1.0 percent, the water soluble substance content is less than or equal to 0.3 percent, the acid soluble substance content is less than or equal to 0.5 percent, the ignition loss at 800 ℃ is less than or equal to 0.5 percent, and the whiteness is more than or equal to 93 percent.
In the method for treating the surface of the titanium dioxide pigment with high hydrophobicity and high dispersibility for the cosmetics, in the first step, the grinding aid is one or more of polyacrylic acid, sodium silicate, sodium hexametaphosphate or sodium pyrophosphate, and the addition proportion is 0.5-4.0 per mill of the weight of the titanium dioxide pigment raw material; the 325-mesh screen residue rate of the titanium dioxide pigment obtained after grinding is less than or equal to 0.02 percent through wet screening, and the 200-mesh screen residue rate of the titanium dioxide pigment is less than or equal to 0.1 percent through dry screening.
The surface treatment method of the titanium dioxide pigment with high hydrophobicity and high dispersibility for cosmetics comprises the following specific steps of: placing the titanium dioxide pigment treated in the step one and deionized water in a mass ratio of 70: 30-30: 70 in equipment with electric heating and stirring, starting stirring and electric heating, heating to 80-90 ℃, and preparing into a pasty material at constant temperature.
In the method for treating the surface of the titanium dioxide pigment with high hydrophobicity and high dispersibility for the cosmetics, the pH value regulator used for regulating the pH value to be alkalescent in the step two is an aluminum hydroxide solution with the mass percentage concentration of 0.5-1.5%, and the pH value is regulated to 7.5-9.0.
The surface treatment agent in the third step is triisostearic acid isopropyl titanate, or a mixture of triisostearic acid isopropyl titanate and one or two of polydimethylsiloxane, polymethylsiloxane and octyl triethoxysilane, and the mass ratio of the mixture is triisostearic acid isopropyl titanate: (polydimethylsiloxane and/or polymethylsiloxane and/or octyltriethoxysilane) ═ 1:1 to 10:1, and the addition ratio of the surface treatment agent is 1 to 10% by mass of the titanium dioxide pigment.
The surface treatment method of the titanium dioxide pigment with high hydrophobicity and high dispersibility for the cosmetics comprises the following steps of: the auxiliary agent is 1: 1-1: 20.
The surface treatment method of the titanium dioxide pigment with high hydrophobicity and high dispersibility for the cosmetics comprises the steps of adopting atomization metering pump as spraying equipment in the third step, and carrying out reaction bonding for 30-200 minutes in the third step.
The method for treating the surface of the titanium dioxide pigment with high hydrophobicity and high dispersibility for the cosmetics comprises the step four, wherein the heating and drying equipment is a table-type drying box with air exhaust equipment, and the moisture content of the titanium dioxide pigment cake is less than or equal to 0.5 percent after the titanium dioxide pigment cake is heated and dried for 5 to 24 hours.
And in the fifth step, the crushing equipment is one of a hammer mill and an airflow mill, and the impurity removing equipment is one or a combination of an airflow classifier and a high-frequency ultrasonic vibration sieve.
Has the advantages that:
1. the main treating agent of the invention is isopropyl titanium triisostearate which is of a monoalkoxy type, one end of a molecule is isopropoxy, Ti-O-is easy to react with hydroxyl on the surface of titanium dioxide, and a monomolecular layer is formed on the surface of the titanium dioxide, so that the isopropyl titanium triisostearate shows excellent activity on titanium dioxide pigment. The other end has a long straight carbon chain, so that stronger hydrophobicity can be generated, and a large amount of fatty acid ester groups are arranged on the surface of the treated powder, so that the titanium dioxide pigment treated by the isopropyl triisostearate titanate is easily wetted and dispersed in an organic medium, and the oil absorption is greatly reduced.
2. The titanium dioxide pigment surface treatment product for cosmetics does not contain agglomerated titanium dioxide particle particles and hard particles after multiple times of crushing, depolymerization, impurity removal and the like. Has excellent application and smearing in cosmetic formulation, and does not have 'bleached' hard particles.
3. The surface-treated titanium dioxide pigment for cosmetics has excellent hydrophobic property, good compatibility and dispersibility with oil ester in a cosmetic formula, and no problem of sour taste and the like.
4. The titanium dioxide pigment surface treatment technology for cosmetics belongs to a semi-dry semi-wet method, can well overcome the defects of the existing dry method and wet method surface treatment technology and products, and has remarkable value. The existing ' dry method ' surface treatment technology has the environmental problems of easy generation of dust and the like in a high-speed mixing link, and the problems of low coating rate, poor hydrophobicity, ' bleaching ' and flooding ' of a surface treatment agent. The existing 'wet method' surface treatment technology has the problems of long production flow, high cost, low utilization rate of a surface treatment agent, environmental pollution, sour taste of a product and the like.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the 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.
A surface treatment method of a titanium dioxide pigment with high hydrophobicity and high dispersibility for cosmetics comprises the following steps:
step one, crushing and depolymerizing: grinding and grading a rutile type titanium dioxide pigment raw material under the action of a grinding aid to remove agglomerated particles in the titanium dioxide pigment raw material;
step two, PH adjustment: preparing the titanium dioxide pigment treated in the step one into paste, transferring the paste into a reaction device, starting stirring, adjusting the pH value to be alkalescent, and then heating to 50-100 ℃;
step three, reaction bonding: the mixed solution of the surface treating agent and the auxiliary agent is sprayed on the surface of the pasty titanium dioxide pigment obtained in the step two after being metered, and the reaction bonding is carried out at the temperature of 50-100 ℃;
step four, heating and drying: heating and drying the pasty titanium dioxide pigment obtained in the step three for 5-24 hours at the temperature of 100-180 ℃ to obtain a titanium dioxide pigment cake material;
step five, crushing and impurity removal: and D, crushing and removing impurities from the titanium dioxide pigment cake material obtained in the step four to obtain the titanium dioxide pigment product with high hydrophobicity and high dispersibility for cosmetics.
According to the surface treatment method of the titanium dioxide pigment with high hydrophobicity and high dispersibility for cosmetics, in the first step, the rutile type titanium dioxide pigment raw material meets the following requirements:
the particle size requirement is as follows: d50 of 0.15-0.30 μm and D90 of 0.4-1.0 μm;
the purity meets the requirements: TiO 22≥99％，Al2O3+SiO2≤2％；
The heavy metal content requirement is as follows: pb is less than or equal to 10mg/kg, As is less than or equal to 2mg/kg, Hg is less than or equal to 1mg/kg, and Cd is less than or equal to 5 mg/kg;
other requirements are as follows: the water content is less than or equal to 1.0 percent, the water soluble substance content is less than or equal to 0.3 percent, the acid soluble substance content is less than or equal to 0.5 percent, the ignition loss at 800 ℃ is less than or equal to 0.5 percent, and the whiteness is more than or equal to 93 percent.
In the method for treating the surface of the titanium dioxide pigment with high hydrophobicity and high dispersibility for the cosmetics, in the first step, the grinding aid is one or more of polyacrylic acid, sodium silicate, sodium hexametaphosphate or sodium pyrophosphate, and the addition proportion is 0.5-4.0 per mill of the weight of the titanium dioxide pigment raw material; the 325-mesh screen residue rate of the titanium dioxide pigment obtained after grinding is less than or equal to 0.02 percent through wet screening, and the 200-mesh screen residue rate of the titanium dioxide pigment is less than or equal to 0.1 percent through dry screening.
The surface treatment method of the titanium dioxide pigment with high hydrophobicity and high dispersibility for cosmetics comprises the following specific steps of: placing the titanium dioxide pigment treated in the step one and deionized water in a mass ratio of 70: 30-30: 70 in equipment with electric heating and stirring, starting stirring and electric heating, heating to 80-90 ℃, and preparing into a pasty material at constant temperature.
In the method for treating the surface of the titanium dioxide pigment with high hydrophobicity and high dispersibility for the cosmetics, the pH value regulator used for regulating the pH value to be alkalescent in the step two is an aluminum hydroxide solution with the mass percentage concentration of 0.5-1.5%, and the pH value is regulated to 7.5-9.0.
The surface treatment agent in the third step is triisostearic acid isopropyl titanate, or a mixture of triisostearic acid isopropyl titanate and one or two of polydimethylsiloxane, polymethylsiloxane and octyl triethoxysilane, and the mass ratio of the mixture is triisostearic acid isopropyl titanate: (polydimethylsiloxane and/or polymethylsiloxane and/or octyltriethoxysilane) ═ 1:1 to 10:1, and the addition ratio of the surface treatment agent is 1 to 10% by mass of the titanium dioxide pigment.
The surface treatment method of the titanium dioxide pigment with high hydrophobicity and high dispersibility for the cosmetics comprises the following steps of: the auxiliary agent is 1: 1-1: 20.
The surface treatment method of the titanium dioxide pigment with high hydrophobicity and high dispersibility for the cosmetics comprises the steps of adopting atomization metering pump as spraying equipment in the third step, and carrying out reaction bonding for 30-200 minutes in the third step.
The method for treating the surface of the titanium dioxide pigment with high hydrophobicity and high dispersibility for the cosmetics comprises the step four, wherein the heating and drying equipment is a table-type drying box with air exhaust equipment, and the moisture content of the titanium dioxide pigment cake is less than or equal to 0.5 percent after the titanium dioxide pigment cake is heated and dried for 5 to 24 hours.
And in the fifth step, the crushing equipment is one of a hammer mill and an airflow mill, and the impurity removing equipment is one or a combination of an airflow classifier and a high-frequency ultrasonic vibration sieve.
Example 1
The rutile type titanium dioxide pigment meeting the technical requirements is taken as a raw material and is conveyed into an airflow crusher provided with an airflow classifier through a metering conveyor belt, and a sodium polyacrylate dispersant solution with the feeding amount of titanium dioxide of 0.5 per mill by mass ratio is dripped at the feed inlet of the airflow crusher through a metering pump. And removing agglomerated particles in the titanium dioxide raw material by adjusting parameters such as the rotating speed, air supplement, rotor clearance and the like of the airflow crusher and the airflow classifier. The obtained titanium dioxide pigment was measured to have a 325-mesh screen residue ratio of 0.004% by wet screening and a 200-mesh screen residue ratio of 0.06% by dry screening. In this example, the mass concentration of the sodium polyacrylate dispersant solution was 45%.
Preparing the titanium dioxide pigment obtained in the step (1) into a paste material with the mass concentration of 40% by using deionized water with the conductivity of less than or equal to 10us/cm, placing the paste material into a ribbon blender or a kneader or an internal mixer or a reaction kettle or a grinder with electric heating, starting stirring and electric heating, setting the stirring speed to be 30 revolutions per minute, heating to the temperature of 85 ℃, and keeping the temperature constant. Then, an aluminum hydroxide solution with a titanium dioxide pigment mass ratio of 0.2 ‰ is added into the ribbon blender, and the pH is adjusted to 8.0. In this example, the mass concentration of the aluminum hydroxide solution was 1.2%.
Triisostearic acid isopropyl titanate according to the mass ratio: absolute ethanol ═ 1:1 preparing a mixed solution of the surface treating agent and the surface treating auxiliary agent, and uniformly mixing. And (3) atomizing and spraying the mixed solution to the titanium dioxide paste material in the step (2) according to 6% of the mass ratio of the titanium dioxide pigment through an atomizing metering pump. Stirred for 80 minutes.
And (4) placing the titanium dioxide paste material obtained in the step (3) into a desk type drying box with an air exhaust device, and drying for 12 hours at 120 ℃. The water content was measured to be 0.15%.
And (5) crushing and screening the titanium dioxide cake material obtained in the step (4) to remove impurities through an airflow crusher and a high-frequency ultrasonic vibration screen (with the screen size of 120 meshes). The obtained titanium dioxide pigment surface treatment product with high hydrophobicity and high dispersibility for cosmetics is obtained.
Example 2
The rutile type titanium dioxide pigment meeting the technical requirements is taken as a raw material and is fed into a hammer mill provided with an air classifier through a metering conveyor belt, and sodium polyacrylate with the mass ratio of 0.5 per mill of the feeding amount of titanium dioxide is dropwise added at the feeding port of the air hammer mill through a metering pump: a composite dispersion of 1:1 sodium hexametaphosphate. And removing agglomerated particles in the titanium dioxide raw material by adjusting parameters such as the rotating speed, air supplement, rotor clearance and the like of the hammer mill and the airflow classifier. The obtained titanium dioxide pigment was measured to have a 325-mesh retention by wet screening of 0.005% and a 200-mesh retention by dry screening of 0.04%. The mass concentration of the composite dispersion in this example was 15%.
Preparing the titanium dioxide pigment obtained in the step (1) into a paste material with the mass concentration of 50% by using deionized water with the conductivity of less than or equal to 10us/cm, placing the paste material into a ribbon blender or a kneader or an internal mixer or a reaction kettle or a grinder with electric heating, starting stirring and electric heating, setting the stirring speed to be 28 revolutions per minute, heating to the temperature of 85 ℃, and keeping the temperature constant. Then, an aluminum hydroxide solution with a titanium dioxide pigment mass ratio of 0.15 ‰ is added into the ribbon blender, and the pH is adjusted to 8.5. In this example, the mass concentration of the aluminum hydroxide solution was 2.5%.
Triisostearic acid isopropyl titanate according to the mass ratio: polydimethylsiloxane: anhydrous ethanol ═ 4: 4: 2 preparing a mixed solution of the surface treating agent and the surface treating auxiliary agent, and uniformly mixing. And (3) atomizing and spraying the mixed solution to the titanium dioxide paste material in the step (2) according to 8% of the mass ratio of the titanium dioxide pigment through an atomizing metering pump. Stirred for 130 minutes.
And (4) placing the titanium dioxide paste material in the step (3) into a desk type drying box with an air exhaust device, and drying for 10 hours at 118 ℃. The moisture content was measured to be 0.17%.
And (5) crushing and screening the titanium dioxide cake material obtained in the step (4) to remove impurities through an airflow crusher and a high-frequency ultrasonic vibration screen (with the screen mesh size of 150 meshes). The obtained titanium dioxide pigment surface treatment product with high hydrophobicity and high dispersibility for cosmetics is obtained.
Example 3
The rutile type titanium dioxide pigment meeting the technical requirements is taken as a raw material, the rutile type titanium dioxide pigment is delivered to a turbine type crusher provided with an airflow classifier through a metering conveyor belt, and sodium polyacrylate with the titanium dioxide feeding amount mass ratio of 2.0 thousandths is dropwise added at a feeding port of the turbine type crusher through a metering pump: 1:1 sodium silicate composite dispersion. And removing agglomerated particles in the titanium dioxide raw material by adjusting parameters such as the rotating speed, air supplement, rotor clearance and the like of the turbine type crusher and the airflow classifier. The obtained titanium dioxide pigment was measured to have a 325-mesh screen residue ratio of 0.006% by wet screening and a 200-mesh screen residue ratio of 0.05% by dry screening. The mass concentration of the composite dispersion in this example was 15%.
Preparing the titanium dioxide pigment obtained in the step (1) into a paste material with the mass concentration of 55% by using deionized water with the conductivity of less than or equal to 10us/cm, placing the paste material into a ribbon blender or a kneader or an internal mixer or a reaction kettle or a grinder with electric heating, starting stirring and electric heating, setting the stirring speed to 35 revolutions per minute, heating to the temperature of 85 ℃, and keeping the temperature constant. Then, an aluminum hydroxide solution with a titanium dioxide pigment mass ratio of 0.8 ‰ is added into the ribbon blender, and the pH is adjusted to 8.8. In this example, the mass concentration of the aluminum hydroxide solution was 2.0%.
Triisostearic acid isopropyl titanate according to the mass ratio: octyl triethoxysilane: anhydrous ethanol ═ 4: 3: 3 preparing a mixed solution of the surface treating agent and the surface treating auxiliary agent, and uniformly mixing. And (3) atomizing and spraying the mixed solution to the titanium dioxide paste material in the step (2) according to the mass ratio of 10% of the titanium dioxide pigment by an atomization metering pump. Stirred for 110 minutes.
And (4) placing the titanium dioxide paste material in the step (3) into a desk type drying box with an air exhaust device, and drying for 15 hours at 130 ℃. The water content was measured to be 0.10%.
And (4) crushing and screening the titanium dioxide cake material obtained in the step (4) to remove impurities through a jet mill and a high-frequency ultrasonic vibration screen. The obtained titanium dioxide pigment surface treatment product with high hydrophobicity and high dispersibility for cosmetics is obtained.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It should be understood by those skilled in the art that the present invention is not limited by the above-described embodiments, which are described in the specification and illustrated only to illustrate the present invention
The principles of the invention may be employed with various modifications and adaptations of the invention without departing from its spirit and scope, and such modifications and adaptations are intended to be within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Examples test methods for the samples obtained:
(1) method for testing surplus rate
According to GB 5211.18-1988 manual operation of water method for measuring pigment screen residue
Sour taste
100g of the sample is placed in an 8# plastic self-sealing bag and is sealed for 10 hours. Within 5 seconds after opening, the odor was evaluated.
Sense of coating
Sensory evaluation was performed.
(4) Hydrophobic index testing method
About 5g of sample was weighed to the nearest 0.01 g. The mixture was placed in a 250mL separatory funnel, 200mL deionized water was added, and the mixture was shaken back and forth at a speed of 120 times/min for 1 min. Is lightly placed on the funnel stand. Standing for 20-30 min, after obvious layering, placing the lower sample in a glass sand crucible with constant weight (accurate to 0.001g) at the temperature of 105 ℃ at one time, performing suction filtration to remove water, placing the lower sample in a constant-temperature drying box, and drying at the temperature of 105 ℃ C to constant weight (accurate to 0.001 g).
Calculation of results
The hydrophobicity index is given as mass crush w, the numbers are given as% and are calculated according to the following formula:
in the formula:
m 2: the mass of the crucible and uncoated coupon after drying is given in grams (g); .
m 1: the mass of the crucible is given in grams (g);
m: the mass of the sample is given in grams (g);
taking the arithmetic mean value of the results of the parallel measurement as the measurement result, and the absolute difference value of the results of the parallel measurement is not more than 2%.
The higher the hydrophobicity index, the better the hydrophobic property.
(5) Dispersibility and compatibility testing method
Respectively mixing the sample and the dispersoid at a high speed according to the ratio of 3:7, uniformly mixing the system by a homogenizer, and testing the viscosity by a stormer viscometer to represent the dispersibility. The lower the viscosity number, the better the dispersibility.
After the test is finished, the solution is transferred to a sample bottle for standing and storage, and whether the solution is layered or not is observed for representing the compatibility of the solution.
The invention was tested with three dispersions of liquid paraffin, cyclopentadimethylsiloxane and octyldodecanol pivalate, which are commonly used in cosmetics.
(6) Bleaching
The sample is prepared into a foundation liquid product according to the formula of the cosmetic foundation liquid in the table 1, and whether the surface of the foundation liquid is bleached or not is observed after high-speed centrifugation.
Table 1 foundation make-up formula table:
table 2 example test data
Note: (1) comparative example 1 is a commercially available titanium dioxide pigment for cosmetics which has not been modified by surface treatment; (2) comparative 2 is a commercially available cosmetic dry surface treatment modified titanium dioxide pigment; (3) comparative 3 is a commercially available cosmetically modified titanium dioxide pigment with a wet surface treatment.
The technical solutions disclosed in the present invention are not limited to the technical means disclosed in the above technical features, but also include technical solutions formed by equivalent substitutions of the above technical features. The present invention is not limited to the details given herein, but is within the ordinary knowledge of those skilled in the art.
Claims (5)
1. A surface treatment method of titanium dioxide pigment with high hydrophobicity and high dispersibility for cosmetics is characterized in that: the method comprises the following steps:
step one, crushing and depolymerizing: grinding and grading a rutile type titanium dioxide pigment raw material under the action of a grinding aid to remove agglomerated particles in the titanium dioxide pigment raw material;
step two, pH adjustment: preparing the titanium dioxide pigment treated in the step one into paste, transferring the paste into a reaction device, starting stirring, adjusting the pH value to be alkalescent, and then heating to 50-100 ℃;
step three, reaction bonding: the mixed solution of the surface treating agent and the auxiliary agent is sprayed on the surface of the pasty titanium dioxide pigment obtained in the step two after being metered, and the reaction bonding is carried out at the temperature of 50-100 ℃;
step four, heating and drying: heating and drying the pasty titanium dioxide pigment obtained in the step three for 5-24 hours at the temperature of 100-180 ℃ to obtain a titanium dioxide pigment cake material;
step five, crushing and impurity removal: crushing and removing impurities from the titanium dioxide pigment cake material obtained in the step four to obtain a high-hydrophobicity and high-dispersity titanium dioxide pigment product for cosmetics;
in the first step, the rutile type titanium dioxide pigment raw material meets the following requirements:
the particle size requirement is as follows: d50 of 0.15-0.30 μm and D90 of 0.4-1.0 μm;
the purity meets the requirements: TiO 22≥99%，Al2O3+SiO2≤2%；
The heavy metal content requirement is as follows: pb is less than or equal to 10mg/kg, As is less than or equal to 2mg/kg, Hg is less than or equal to 1mg/kg, and Cd is less than or equal to 5 mg/kg;
other requirements are as follows: the water content is less than or equal to 1.0 percent, the water soluble substance content is less than or equal to 0.3 percent, the acid soluble substance content is less than or equal to 0.5 percent, the ignition loss at 800 ℃ is less than or equal to 0.5 percent, and the whiteness is more than or equal to 93 percent;
in the first step, the grinding aid is one or more of polyacrylic acid, sodium silicate, sodium hexametaphosphate or sodium pyrophosphate, and the adding proportion is 0.5-4.0 per mill of the weight of the titanium dioxide pigment raw material; the 325-mesh screen residue rate of the titanium dioxide pigment obtained after grinding is less than or equal to 0.02 percent through wet screening, and the 200-mesh screen residue rate of the titanium dioxide pigment is less than or equal to 0.1 percent through dry screening;
the specific method for preparing the titanium dioxide pigment into paste in the step two comprises the following steps: placing the titanium dioxide pigment treated in the step one and deionized water in a mass ratio of 70: 30-30: 70 in equipment with electric heating and stirring, starting stirring and electric heating, heating to 80-90 ℃, and preparing into a pasty material at constant temperature;
in the second step, the pH value regulator used for regulating the pH value to be alkalescent is an aluminum hydroxide solution with the mass percentage concentration of 0.5-1.5%, and the pH value is regulated to 7.5-9.0;
the surface treating agent in the third step is triisostearic acid isopropyl titanate, or a mixture of triisostearic acid isopropyl titanate and one or two of polydimethylsiloxane, polymethylsiloxane and octyl triethoxysilane, and the mass ratio of the mixture is triisostearic acid isopropyl titanate: (polydimethylsiloxane and/or polymethylsiloxane and/or octyltriethoxysilane) = (1:1) - (10:1), and the addition ratio of the surface treatment agent is 1-10% of the mass of the titanium dioxide pigment.
2. The method for surface-treating a highly hydrophobic and highly dispersible titanium dioxide pigment for cosmetics according to claim 1, wherein: in the third step, the auxiliary agent is one or a mixture of two of absolute ethyl alcohol and isopropanol, and the mixing mass ratio of the surface treatment agent to the auxiliary agent is as follows: the auxiliary agent =1: 1-4: 1.
3. The method for surface-treating a highly hydrophobic and highly dispersible titanium dioxide pigment for cosmetics according to claim 1, wherein: and the spraying adopted equipment in the third step is an atomizing metering pump, and the reaction bonding time in the third step is 30-200 minutes.
4. The method for surface treatment of highly hydrophobic and highly dispersible titanium dioxide pigment for cosmetics according to claim 1, wherein the heating and drying device in the fourth step is a desk type drying box with an air exhaust device, and the moisture content of the titanium dioxide pigment cake is less than or equal to 0.5% after heating and drying for 5-24 hours.
5. The method for surface-treating a highly hydrophobic and highly dispersible titanium dioxide pigment for cosmetics according to claim 1, wherein: and in the fifth step, the crushing equipment is one of a hammer crusher and an airflow crusher, and the impurity removing equipment is one or combination of an airflow classifier and a high-frequency ultrasonic vibration sieve.
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| CN114053202B (en) * | 2021-12-30 | 2024-01-26 | 欧诗漫生物股份有限公司 | Sun-screening composition and sun-screening agent |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030091016A (en) * | 2002-05-24 | 2003-12-01 | 한국화학연구원 | An improved method for preparing spherical porous titania particles |
| CN101367548A (en) * | 2008-09-12 | 2009-02-18 | 江苏工业学院 | Method of preparing hydrophobic nano-titanium dioxide powder |
| CN103919693A (en) * | 2014-03-26 | 2014-07-16 | 上海得高实业有限公司 | Water dispersible powder syrup for oleophylic treatment and product applying powder syrup |
| CN107550742A (en) * | 2017-07-27 | 2018-01-09 | 武汉华丽生物股份有限公司 | Microballon used for cosmetic and preparation method |
-
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- 2020-12-17 CN CN202011498754.6A patent/CN112552710B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030091016A (en) * | 2002-05-24 | 2003-12-01 | 한국화학연구원 | An improved method for preparing spherical porous titania particles |
| CN101367548A (en) * | 2008-09-12 | 2009-02-18 | 江苏工业学院 | Method of preparing hydrophobic nano-titanium dioxide powder |
| CN103919693A (en) * | 2014-03-26 | 2014-07-16 | 上海得高实业有限公司 | Water dispersible powder syrup for oleophylic treatment and product applying powder syrup |
| CN107550742A (en) * | 2017-07-27 | 2018-01-09 | 武汉华丽生物股份有限公司 | Microballon used for cosmetic and preparation method |
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