Nano titanium dioxide for improving blue light and preparation method thereof

Abstract

The invention discloses nano titanium dioxide for improving blue light. The nano titanium dioxide is prepared from the following raw material components in parts by weight: 20-50 parts of nano titanium dioxide; 0.00001 to 0.1 part of a water soluble pigment; 0.5 to 5 parts of a polymer rich in amino groups; 40 to 80 parts of water; the surface of the nano titanium dioxide is coated with the water-soluble pigment and the polymer rich in amino, and then the surface of the nano titanium dioxide is subjected to hydrophobic treatment. According to a color complementing principle, the nano titanium dioxide is firstly subjected to coloring treatment, then the surface of the nano titanium dioxide is subjected to coating treatment for color fixation, and then the surface of the nano titanium dioxide is subjected to hydrophobic treatment for further color fixation, so that the problem of blue light of the nano titanium dioxide is effectively improved. In addition, the invention also provides a preparation method of the nano titanium dioxide for improving blue light.

Description

Technical Field

[0001] The invention relates to the technical field of cosmetic materials, and in particular to a nano titanium dioxide powder capable of improving blue light emission and a preparation method thereof. Background Art

[0002] Titanium dioxide, scientifically known as titanium dioxide, is an important inorganic chemical product that is used in coatings, inks, papermaking, plastics and rubber, chemical fibers, ceramics, cosmetics and other industries. Among commonly used white pigments, titanium dioxide has the smallest relative density. Among white pigments of the same mass, titanium dioxide has the largest surface area and the highest pigment volume.

[0003] Titanium dioxide is increasingly used in the cosmetics industry. It has become the most important and largest inorganic additive in cosmetics due to its safety, non-toxicity, ability to shield ultraviolet rays, high color-reducing power (or tinting power), strong hiding power, good hue, and wide color spectrum. Titanium dioxide is used as a white pigment and filler in cosmetics such as foundation and eye shadow. It can increase the whiteness and hiding power of the product, making the skin look more delicate and smooth. At the same time, titanium dioxide also has good chemical stability and safety, and will not cause irritation or allergies to the skin.

[0004] Titanium dioxide is divided into nano-level and non-nano-level. The particle size of nano-level titanium dioxide has a significant effect on its ability to scatter light. When the average particle size of titanium dioxide is less than 200nm, it has a strong scattering power for short-wave blue light (400nm) in visible light, and nano titanium dioxide will show a blue luster. This is because the human eye is more sensitive to blue light, and the smaller titanium dioxide particle size enhances the scattering of short-wavelength light (blue-green light), while the scattering of long-wavelength light (red and yellow light) is relatively weak, resulting in a blue luster of titanium dioxide. Directly adding nano titanium dioxide to sunscreen, foundation and other cosmetics will also present a blue luster. This blue luster will make the facial makeup look unnatural and affect the use effect of the cosmetics. However, there is no relevant research on the problem of blue light in nano titanium dioxide in the prior art. Summary of the invention

[0005] In order to solve the problem of blue light emission from nano titanium dioxide in the prior art, which is directly added to cosmetics to affect the facial makeup effect, the present invention provides a nano titanium dioxide with improved blue light emission, which uses the principle of complementary colors to first color the nano titanium dioxide, and then coats its surface for color fixation, thereby effectively improving the problem of blue light emission from the nano titanium dioxide. In addition, the present invention also provides a method for preparing the nano titanium dioxide with improved blue light emission.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] In a first aspect of the present invention, there is provided a nano titanium dioxide for improving blue light emission, wherein the nano titanium dioxide comprises the following raw material components in parts by weight:

[0008] 20-50 parts of nano titanium dioxide;

[0009] Water-soluble pigment 0.00001~0.1 part;

[0010] 0.5 to 5 parts of an amine-rich polymer;

[0011] 40-80 parts of water.

[0012] Furthermore, there are hydroxyl groups on the surface of untreated titanium dioxide, which is hydrophilic. The present invention uses water-soluble pigments to treat the surface of titanium dioxide, wraps the water-soluble pigments on the surface of titanium dioxide, and harmonizes the color presented by the water-soluble pigments with the color presented by titanium dioxide itself, thereby improving the blue light problem of nano titanium dioxide.

[0013] Pigment is a chemical substance that can give color to a substance, and can be divided into natural pigment and synthetic pigment. Natural pigment is usually extracted from plants, animals or minerals, such as cochineal, chlorophyll, etc., while synthetic pigment is obtained by chemical reaction, such as azo, anthraquinone, etc. The water-soluble pigment selected by the present invention includes a mixture of one or more of amaranth, cochineal, yellow 5, red 4, red 28, red 33 and red 22.

[0014] Furthermore, the amine-rich polymer is polyethyleneimine, polyacrylamine or polylysine.

[0015] The present invention selects the polymer rich in amido such as polyethyleneimine, polyacrylamine, polylysine to carry out surface modification to titanium dioxide particles, these amido-rich polymers have high-density amino groups, inorganic nano materials have good affinity, can be efficiently wrapped in the surface of nano titanium dioxide, in addition, water-soluble pigments overwhelmingly have groups such as carboxyl, aldehyde group, ketone, can be combined with the amido-rich polymer by physical / chemical effects such as positive and negative charge, amino-aldehyde / ketone covalent bonds. This step can efficiently adsorb water-soluble pigment on titanium dioxide surface. In addition, the amido on these polymers has good catalytic activity to the hydrolysis-condensation reaction of silane treatment agents such as triethoxyoctylsilane, can promote the subsequent hydrophobic treatment of powder surface, silane treatment agent efficiently generates silicon dioxide layer at the surface selectivity of nano material, can further limit the dissolution of water-soluble pigment.

[0016] Furthermore, the surface of the nano titanium dioxide is subjected to hydrophobic treatment.

[0017] Nano titanium dioxide with hydrophobic surface treatment has hydrophobic substances wrapped on its surface, which makes water-soluble pigments unable to dissolve in water, thus achieving the effect of color fixation.

[0018] The methods of hydrophobic treatment of the surface of nano titanium dioxide include but are not limited to: fluorine compound treatment (perfluoroalkyl ester treatment, perfluoroalkyl silane treatment, perfluoropolyether treatment, fluorosilane treatment, fluorinated silane resin treatment, etc.), silane treatment (triethoxyoctylsilane treatment, dimethylpolysiloxane treatment, etc.), silane resin treatment (trimethylsiloxysilicate treatment, etc.), oil treatment, N-acylated lysine treatment, metal soap treatment (stearate treatment, etc.), etc. In addition, these treatment methods can also be used in combination.

[0019] The second aspect of the present invention provides a method for preparing the above-mentioned nano titanium dioxide with improved blue light emission, comprising the following steps:

[0020] S1, mixing a water-soluble pigment and an amine-rich polymer with water respectively to obtain an aqueous solution of a water-soluble pigment and an aqueous solution of an amine-rich polymer;

[0021] S2, stirring and dispersing the aqueous solution of water-soluble pigment, the aqueous solution of amine-rich polymer and nano titanium dioxide to form a slurry;

[0022] S3, drying the slurry to obtain powder.

[0023] Furthermore, the powder obtained after the drying treatment is subjected to a hydrophobic surface treatment.

[0024] Furthermore, in step S3, the drying method includes spray drying, vacuum drying, freeze drying or other methods that can perform dehydration and drying.

[0025] The nano titanium dioxide for improving blue light emission prepared in the present invention can be added to commonly used cosmetics such as foundation, eye shadow, sunscreen, etc.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] (1) There are hydroxyl groups on the surface of untreated titanium dioxide, which is hydrophilic. The present invention uses water-soluble pigments to treat the surface of titanium dioxide, wrapping the water-soluble pigments on the surface of titanium dioxide. The color presented by the water-soluble pigments is harmonized with the color presented by titanium dioxide itself, thereby improving the blue light problem of nano titanium dioxide.

[0028] (2) Then, an amine-rich polymer is selected to modify the surface of the titanium dioxide particles. These amine-rich polymers have a high density of amino groups and have a good affinity for inorganic nanomaterials, and can be efficiently wrapped on the surface of nano titanium dioxide. In addition, most water-soluble pigments have groups such as carboxyl, aldehyde, and ketone, which can be combined with the amine-rich polymers through physical / chemical effects such as positive and negative charges and amino-aldehyde / ketone covalent bonds, so that the water-soluble pigments can be efficiently adsorbed on the surface of titanium dioxide. In addition, the amine groups on these polymers have good catalytic activity for the hydrolysis and condensation reaction of silane treatment agents such as triethoxyoctylsilane, which can promote the subsequent hydrophobic treatment of the powder surface. The silane treatment agent selectively and efficiently generates a silicon dioxide layer on the surface of the nanomaterial, which can further limit the dissolution of the water-soluble pigment;

[0029] (3) The surface of the nano titanium dioxide is treated with hydrophobicity. The surface of the nano titanium dioxide treated with hydrophobicity is coated with hydrophobic substances, so that the water-soluble pigment cannot be dissolved in water, thereby achieving a further color fixation effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.

[0031] Figure 1 The actual effect pictures of the treated nano titanium dioxide and the untreated nano titanium dioxide prepared in Example 1 being applied to the arm respectively;

[0032] Figure 2 This is a physical picture of a 0.01wt% aqueous solution of nano titanium dioxide and a 0.01wt% aqueous solution of non-nano titanium dioxide in Comparative Example 1;

[0033] Figure 3 The figures are actual test pictures of the powders prepared in Comparative Example 2 and Example 1 added into water respectively;

[0034] Figure 4 The following are the actual effect pictures of the treated nano titanium dioxide powder and the untreated nano titanium dioxide powder prepared in Comparative Example 4 being applied to the arm respectively. DETAILED DESCRIPTION

[0035] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0036] Example 1

[0037] A nano titanium dioxide for improving blue light emission comprises the following raw material components in parts by weight:

[0038] 35 parts of nano titanium dioxide;

[0039] 0.000015 parts of water-soluble pigment;

[0040] 1 part of an amine-rich polymer;

[0041] 64 parts of water.

[0042] The average particle size of the nano titanium dioxide is 30 nm; the water-soluble pigment is red 28, and the amine-rich polymer is polyethyleneimine.

[0043] The method for preparing the nano titanium dioxide with improved blue light emission comprises the following steps:

[0044] S1, mixing a water-soluble pigment and an amine-rich polymer with water respectively to obtain an aqueous solution of a water-soluble pigment and an aqueous solution of an amine-rich polymer;

[0045] S2, stirring and dispersing the aqueous solution of water-soluble pigment, the aqueous solution of amine-rich polymer and nano titanium dioxide to form a slurry;

[0046] S3, drying the slurry to obtain a powder;

[0047] S4, the powder obtained after drying is treated with triethoxyoctylsilane in a mass ratio of 98:2 for hydrophobic surface treatment. The specific steps are as follows: the nano titanium dioxide powder obtained after drying is mixed with triethoxyoctylsilane evenly, and then crushed by a crusher for 3 times until uniform, and the evenly crushed powder is placed in an oven at 120°C for 2 hours.

[0048] Example 2

[0049] A nano titanium dioxide for improving blue light emission comprises the following raw material components in parts by weight:

[0050] 30 parts of nano titanium dioxide;

[0051] 0.00001 parts of water-soluble pigment;

[0052] 0.5 part of an amine-rich polymer;

[0053] 69.5 parts of water.

[0054] The average particle size of the nano titanium dioxide is 30 nm; the water-soluble pigment is red 28, and the amine-rich polymer is polyethyleneimine.

[0055] The preparation method of the nano titanium dioxide for improving blue light emission is the same as that in Example 1.

[0056] Example 3

[0057] A nano titanium dioxide for improving blue light emission comprises the following raw material components in parts by weight:

[0058] 20 parts of nano titanium dioxide;

[0059] 0.00001 parts of water-soluble pigment;

[0060] 1 part of an amine-rich polymer;

[0061] 79 parts of water.

[0062] The average particle size of the nano titanium dioxide is 30 nm; the water-soluble pigment is red 28, and the amine-rich polymer is polyethyleneimine.

[0063] The preparation method of the nano titanium dioxide for improving blue light emission is the same as that in Example 1.

[0064] Example 4

[0065] A nano titanium dioxide for improving blue light emission comprises the following raw material components in parts by weight:

[0066] 40 parts of nano titanium dioxide;

[0067] 0.0005 parts of water-soluble pigment;

[0068] 2 parts of an amine-rich polymer;

[0069] 58 parts of water.

[0070] Among them, the average particle size of nano titanium dioxide is 30nm; the water-soluble pigment is cochineal red, and the amine-rich polymer is polyacrylamine.

[0071] The preparation method of the nano titanium dioxide for improving blue light emission is the same as that in Example 1.

[0072] Example 5

[0073] A nano titanium dioxide for improving blue light emission comprises the following raw material components in parts by weight:

[0074] 46 parts of nano titanium dioxide;

[0075] 0.05 parts of water-soluble pigment;

[0076] 3 parts of an amine-rich polymer;

[0077] 51 parts of water.

[0078] Among them, the average particle size of nano titanium dioxide is 30nm; the water-soluble pigment is yellow 5, and the amino-rich polymer is polylysine.

[0079] The preparation method of the nano titanium dioxide for improving blue light emission is the same as that in Example 1.

[0080] Example 6

[0081] A nano titanium dioxide for improving blue light emission comprises the following raw material components in parts by weight:

[0082] 50 parts of nano titanium dioxide;

[0083] 0.1 part of water-soluble pigment;

[0084] 5 parts of an amine-rich polymer;

[0085] 45 parts of water.

[0086] Among them, the average particle size of nano titanium dioxide is 30nm; the water-soluble pigment is yellow 5, and the amino-rich polymer is polylysine.

[0087] The preparation method of the nano titanium dioxide for improving blue light emission is the same as that in Example 1.

[0088] The blue light phenomenon of the treated nano titanium dioxide prepared in Examples 1-6 was improved, among which the improvement effect of the blue light phenomenon of the treated nano titanium dioxide prepared in Example 1 was the most obvious.

[0089] The treated nano titanium dioxide powder and the untreated nano titanium dioxide powder prepared in Example 1 were applied to the arms respectively. Figure 1 , Figure 1 The left side shows the actual coating effect of untreated nano titanium dioxide. Figure 1 The right side shows the actual coating effect of the treated nano titanium dioxide prepared in Example 1. It can be seen that the blue light phenomenon of the treated nano titanium dioxide in Example 1 is significantly improved.

[0090] Comparative Example 1

[0091] Comparative Example 1 is the untreated nano titanium dioxide raw material with an average particle size of 30 nm in Example 1, which is prepared into a 0.01wt% nano titanium dioxide aqueous solution. Figure 2 On the left, the solution exhibits a blue sheen. Figure 2 The right side is a 0.01wt% aqueous solution of non-nano titanium dioxide with an average particle size of more than 200nm. It can be seen that the solution is milky white and does not have a blue luster.

[0092] Comparative Example 2

[0093] Comparative Example 2 is a comparative test example of Example 1, and the difference between the two is that:

[0094] In Comparative Example 2, the powder obtained after the drying treatment was not subjected to surface hydrophobic treatment.

[0095] The powders prepared in Comparative Example 2 and Example 1 were added to water respectively. Figure 3 The left side is the powder obtained in Comparative Example 2 without surface hydrophobic treatment, and the pigment attached to the surface of the nano titanium dioxide is almost completely dissolved in water, while the right side is the powder after the surface hydrophobic treatment in Example 1, and the pigment attached to the surface of the nano titanium dioxide is isolated by the hydrophobic layer and does not dissolve in water.

[0096] Comparative Example 3

[0097] Comparative Example 3 is a comparative test example of Example 1, and the difference between the two is that:

[0098] In Comparative Example 3, the product formula does not contain the amine-rich polymer-polyethyleneimine, and polyethyleneimine is not used to modify the surface of the nano titanium dioxide particles.

[0099] Theoretically, the adhesion strength of the pigment attached to the surface of the nano titanium dioxide prepared in Comparative Example 3 is lower than that in Example 1, but this cannot be seen visually.

[0100] Comparative Example 4

[0101] Comparative Example 4 is a comparative test example of Example 1, and the difference between the two is that:

[0102] In Comparative Example 4, the product formula does not contain the water-soluble pigment-Red 28, and the nano titanium dioxide particles are not treated with the water-soluble pigment.

[0103] The treated nano titanium dioxide powder and the untreated nano titanium dioxide powder prepared in Comparative Example 4 were applied to the arms respectively. Figure 4 , it can be seen that the powder in Comparative Example 4 still exhibits a blue light effect.

[0104] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A nano titanium dioxide for improving blue light emission, characterized in that: The nano titanium dioxide is prepared from the following raw material components in parts by weight: 20-50 parts of nano titanium dioxide; Water-soluble pigment 0.00001~0.1 part; 0.5 to 5 parts of an amine-rich polymer; 40-80 parts of water; Water-soluble pigments and amine-rich polymers are coated on the surface of nano-titanium dioxide.

2. The nano titanium dioxide for improving blue light according to claim 1, characterized in that: The water-soluble pigment is a natural pigment or a synthetic pigment, and includes one or a mixture of amaranth, cochineal, yellow 5, red 4, red 28, red 33, and red 22.

3. The nano titanium dioxide for improving blue light according to claim 1, characterized in that: The amine-rich polymer includes polyethyleneimine, polyacrylamine or polylysine.

4. The nano titanium dioxide for improving blue light according to claim 1, characterized in that: The surface of the nano titanium dioxide is hydrophobicized.

5. A method for preparing nano titanium dioxide with improved blue light according to any one of claims 1 to 4, characterized in that: The steps include: S1, mixing a water-soluble pigment and an amine-rich polymer with water respectively to obtain an aqueous solution of a water-soluble pigment and an aqueous solution of an amine-rich polymer; S2, stirring and dispersing the aqueous solution of water-soluble pigment, the aqueous solution of amine-rich polymer and nano titanium dioxide to form a slurry; S3, drying the slurry to obtain powder.

6. The method for preparing nano titanium dioxide with improved blue light according to claim 5, characterized in that: The powder obtained after drying is subjected to hydrophobic surface treatment.

7. The method for preparing nano titanium dioxide with improved blue light according to claim 6, characterized in that: The hydrophobic surface treatment methods for the powder include one or more of fluorine compound treatment, silane treatment, silane resin treatment, oil treatment, N-acylated lysine treatment, and metal soap treatment.

8. The method for preparing nano titanium dioxide with improved blue light according to claim 5, characterized in that: In step S3, the drying method includes spray drying, vacuum drying, freeze drying or hot air drying.

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