CN115850594A - Environment-friendly waterproof polymer fluorescent tattoo material and preparation method and application thereof - Google Patents

Abstract

The invention discloses a preparation method of a green and environment-friendly waterproof polymer fluorescent tattoo material, which comprises the following steps: (1) The lipoic acid monomer reacts to obtain a poly lipoic acid polymer; (2) Poly-lipoic acid polymer and tetraphenylethylene TPE gather and induce luminescent monomer TPEE to react to obtain poly-lipoic acid-poly-TPEE polymer material PLA-TPEE; (3) And (3) adding the polymer material PLA-TPEE obtained in the step (2) into a solvent to obtain the waterproof polymer fluorescent tattoo material. The invention also discloses the green and environment-friendly waterproof polymer fluorescent tattoo material prepared by the preparation method and application thereof in preparing invisible tattoos. The polymer fluorescent tattoo material can be sprayed on the surface of skin to form a polymer tattoo without puncturing the skin, and the polymer fluorescent tattoo is invisible to naked eyes under natural light and is visible only under ultraviolet excitation, thereby having the function of invisibility.

Description

A kind of green and environment-friendly waterproof polymer fluorescent tattoo material and its preparation method and application

technical field

The invention relates to the field of polymer fluorescent materials prepared by chemical synthesis, in particular to a green and environment-friendly waterproof polymer fluorescent tattoo material and its preparation method and application.

Background technique

Tattoo, also known as tattoo, is to use colored needles to penetrate the bottom layer of the skin to create some patterns or words on the skin. That is to say, puncture the skin and apply paint on the wound to make the body have permanent patterns. The practice of creating raised, striated scars on the skin, tattooing is practiced in most parts of the world and is relatively common in China.

However, piercing and tattooing the human body with the tip of a needle is undoubtedly a kind of damage to human skin cells and nerve cells, and is a behavior that is not conducive to health. Secondly, if the needles specially used for tattooing are not sterilized, they can spread various diseases, and may even spread viruses such as hepatitis B and AIDS.

Again, some people with idiosyncratic constitutions often experience skin allergies, morbid reactions or scars after tattooing. Most of the traditional tattoo materials are tattoo pigments containing heavy metals such as lead and chromium and other compounds. These substances may also cause some potential harm to the body. If you tattoo frequently, it is likely that the skin will accumulate more and more toxins, which may also induce skin cancer.

In addition to the above-mentioned risks of infection with bacteria, skin allergies, and skin cancer, traditional tattoos are harmful to individuals because if they are tattooed on more obvious parts, and it is extremely difficult to remove after tattooing, there is no research yet. There is a special drug that can remove it. The only way is to do laser removal or plastic surgery, which will be a painful process for tattooers.

Fluorescent tattoos are often mentioned by tattoo lovers as tattoos that can glow, and some people call them "luminous tattoos". Fluorescent tattoo, as a newly developed tattoo technology, is pursued by people because of its unique advantages such as invisible light. Fluorescent tattoos are extracted from Blacklightreactive, but the specific components of this material are unknown. Generally, the pigments used in fluorescent tattoos contain phosphors. Although it glows at night or when excited by ultraviolet light, phosphors are harmful to the body. It contains many metal substances such as lead and mercury, as well as some radioactive substances that are harmful to the human body. If you tattoo with pigments that contain fluorescent powder, it can cause skin infections and sores, which can be dangerous. At present, the research on fluorescent tattoos in this field is relatively small. For example, the Chinese patent with the publication number CN108250829A discloses a tattoo ink containing quantum dots. In terms of mass percentage, the raw material composition of the tattoo ink is: water 98%-99.95%, Quantum dots 0.05%-2%. The quantum dot tattoo made of the tattoo ink containing quantum dots of the present invention can emit light under the sun and be covered to achieve an invisible effect, and the tattoo only shows different luminescence under the specific environment excited by different wavelengths of light generated by the electromagnetic radiation source pattern.

Therefore, it is a research hotspot in this field to provide a material and method for tattoos that are easy to remove, do not contain heavy metals, and are safe and non-toxic.

Contents of the invention

The purpose of the present invention is to provide a green and environmentally friendly waterproof polymer fluorescent tattoo material and its preparation method and application. The polymer fluorescent tattoo material can be sprayed on the surface of the skin to form a polymer tattoo without piercing the skin. Fluorescent tattoos are invisible to the naked eye under natural light, and can only be seen when excited by ultraviolet rays, thus serving as an invisible function.

The present invention provides following technical scheme:

A preparation method of a green and environment-friendly waterproof polymer fluorescent tattoo material, the preparation method comprising the following steps:

(1) lipoic acid monomer is reacted to obtain polylipoic acid polymer;

(2) Reaction of polylipoic acid polymer and aggregation-induced light-emitting monomer TPEE containing double bonds to obtain PLA-TPEE, a polymer material of polylipoic acid-polyTPEE;

(3) adding the polymer material PLA-TPEE obtained in step (2) into a solvent to obtain a waterproof polymer fluorescent tattoo material.

In the present invention, tetraphenylethylene TPE aggregation-induced luminescent monomer TPEE refers to a series of chemical structures containing double bond monomers with conjugated benzene ring structure, or called tetraphenylene with different numbers of double bonds. Ethylene (TPE) AIE can adopt but not limited to the following structure:

Wherein, R represents a series of functional groups, including but not limited to carbon-carbon, carbon-oxygen, benzene ring and other functional groups and their derivatives.

The preparation method provided by the present invention uses chemical synthesis and polymerization to polymerize the green natural molecule lipoic acid to prepare a polylipoic acid polymer, and then blends and polymerizes it with the aggregation-induced light-emitting monomer TPEE containing a double bond. In this way, an environmentally friendly and waterproof polymer fluorescent tattoo material with strong adhesion, which will not be washed away by water can be obtained.

In step (1), the reaction condition of the lipoic acid monomer is: react at 0-150° C. for 1-12 hours.

In the present invention, the disulfide bonds that play the role of adhesion and water resistance are derived from lipoic acid and its derivatives. Disulfide bonds are easy to polymerize under high temperature conditions, so temperature control during the reaction is very important, and the temperature is selected at 0-150°C.

In the present invention, the structure of TPEE contains a carbon-carbon double bond that can end the ring-opened polylipoic acid, and the carbon-carbon double bond can react with the sulfur bond to form a carbon-sulfur bond. Moreover, the double-bond monomer contains a conjugated benzene ring structure that induces light emission by aggregation. Under natural light irradiation or dark conditions, the material does not show color; under the excitation of ultraviolet light, the material emits obvious blue light, thus playing an invisible function.

In step (1), the change of chemical shift in the polymer during the reaction is determined by comparing the initial raw material lipoic acid and the final product polylipoic acid with hydrogen nuclear magnetic resonance spectrum.

In step (2), the feed ratio of the polylipoic acid polymer and the aggregation-induced light-emitting monomer TPEE containing double bonds is 0.1-10 g: 0.01-5 g. A series of polymer fluorescent materials with different viscosities and fluorescence intensities can be obtained by controlling the polymerization ratio of the two. Wherein, the carbon-carbon double bond in TPEE caps the polylipoic acid to obtain the PLA-TPEE polymer.

In step (2), the reaction condition is to react at 0-150° C. for 1-12 hours.

In step (2), a scanning electron microscope is used to compare the starting material and the final product of the reaction to determine the change in the morphology of the material during the reaction.

In step (3), the solvent is selected from one or more of methanol, ethanol, acetone or water.

The present invention also provides a green and environment-friendly waterproof polymer fluorescent tattoo material obtained according to the above preparation method.

The present invention also provides an application of the above-mentioned green and environment-friendly waterproof polymer fluorescent tattoo material on invisible tattoos.

The application method is as follows: directly spray the waterproof polymer fluorescent tattoo material on the required parts and patterns to obtain invisible tattoo patterns.

The polymer fluorescent tattoo material prepared by the present invention can be sprayed on the surface of the skin without the risk of bacterial infection, skin allergy and skin cancer induction. The polymer tattoo is non-toxic and non-irritating to the skin, and is invisible to the naked eye under natural light. Visible only when excited by ultraviolet light, thus functioning as invisible. And the polymer tattoo material will gradually disappear naturally (about a week) with the metabolism/natural renewal of skin cells, without leaving permanent marks, and can be sprayed again if necessary.

Compared with the prior art, the advantages of the present invention are as follows: the traditional tattoo method generally uses colored needles to pierce the bottom layer of the skin to make some patterns or words on the skin. That means puncturing the skin and applying paint on the wound to make permanent patterns on the body. This method not only has the risk of bacterial infection, skin allergies, and skin cancer, but also the patterns after tattooing are extremely difficult to remove. The polymer fluorescent tattoo material prepared by the present invention can be sprayed on the surface of the skin without puncturing the skin, and there is no risk of bacterial infection, skin allergy, and skin cancer induction. The polymer tattoo is invisible to the naked eye under natural light. Visible when excited by ultraviolet light, thus playing the role of invisibility. And the polymer tattoo material will gradually and naturally disappear with the metabolism/natural renewal of skin cells (about a week), without leaving permanent marks; and it can be sprayed again as needed. Moreover, the preparation method provided by the invention is simple, convenient to use and has no pollution to the environment.

Description of drawings

A more complete understanding of the invention will be obtained from the detailed description of the invention and accompanying figures given herein, which are given by way of illustration only and do not limit the scope of the intended invention.

Fig. 1 is a schematic diagram of the synthetic application of the waterproof sprayable fluorescent polymer tattoo material of the present invention.

Fig. 2 is the comparison chart before and after proton NMR spectra of lipoic acid and polylipoic acid prepared in Example 1.

Figure 3 is a scanning electron microscope analysis diagram of polylipoic acid and PLA-TPEE prepared in Example 1.

Fig. 4 is the infrared analysis figure of polylipoic acid and PLA-TPEE prepared in embodiment 1.

Fig. 5 is the rheological analysis diagram of the precursor prepared in Example 1 and different proportions of PLA-TPEE.

Fig. 6 is the thermogravimetric analysis diagram of the precursor prepared in Example 1 and different proportions of PLA-TPEE.

Fig. 7 is the actual picture of the dissolution of PLA-TPEE prepared in Example 1 in absolute ethanol.

FIG. 8 is a diagram of an invisible tattoo formed by spraying the waterproof polymer fluorescent tattoo material prepared in Example 1 on human skin.

Detailed ways

In order to make the purpose and technical solution of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings. The following examples are only used to illustrate the present invention and should not be considered as limiting the scope of the present invention. If no specific technique or condition is indicated in the examples, it shall be carried out according to the technique or condition described in the literature in this field or according to the product specification.

Example 1

Put the lipoic acid monomer into the reaction container, react at 90° C. for 2 hours, and after the reaction, let it stand still and return to room temperature to obtain polylipoic acid polymer. The chemical structures of lipoic acid and polylipoic acid products were characterized by nuclear magnetic resonance (NMR), and the results are shown in Figure 2.

Polylipoic acid polymer and double bond-containing aggregation-induced luminescence monomer TPEE (tetraphenylethylene TPE is used in this embodiment) according to a suitable feed ratio, the mass of polylipoic acid polymer 1g, double-bond-containing aggregation-induced luminescence monomer The mass of bulk TPEE is 0.2g, reacted at 90°C for 5h, and after the reaction was completed, it was allowed to stand and return to room temperature to obtain a polymer of polylipoic acid-polyTPEE (abbreviated as PLA-TPEE).

The scanning electron microscope was used to compare the reaction starting material and the final product, and the results are shown in Figure 3; the infrared analysis chart of the reaction starting material and the final product is shown in Figure 4; the PLA-TPEE rheological analysis of the reaction starting material and the final product The figure is shown in Fig. 5; the thermogravimetric analysis diagram of the reaction starting material and the final product is shown in Fig. 6.

The PLA-TPEE polymer obtained in the above steps is fully dissolved by adding a non-toxic and harmless ethanol solvent, and then ultrasonicated to prepare a green and environmentally friendly waterproof polymer fluorescent tattoo material. A uniform and transparent sprayable solution was obtained, and the results are shown in Figure 7 for details. Then spray this solution on the surface of human skin to obtain a waterproof polymer fluorescent tattoo material that is invisible under natural light but visible under ultraviolet light. The results are shown in Figure 8.

The foregoing embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still understand the foregoing embodiments. Modifications to the technical solutions recorded, or equivalent replacements for some of the technical features. Within the essential scope of the present invention, the changes, modifications, additions or substitutions made shall all belong to the protection scope of the present invention.

Claims (8)

1. A preparation method of a green and environment-friendly waterproof polymer fluorescent tattoo material is characterized by comprising the following steps:

(1) The lipoic acid monomer reacts to obtain a poly lipoic acid polymer;

(2) Poly-lipoic acid polymer and tetraphenylethylene TPE gather and induce luminescent monomer TPEE to react to obtain poly-lipoic acid-poly-TPEE polymer material PLA-TPEE;

(3) And (3) adding the polymer material PLA-TPEE obtained in the step (2) into a solvent to obtain the waterproof polymer fluorescent tattoo material.

2. The method for preparing a green, environment-friendly, waterproof type polymer fluorescent tattoo material according to claim 1, wherein in the step (1), the lipoic acid monomer is reacted under the following conditions: reacting for 1-12 h at 0-150 ℃.

3. The method for preparing a green and environment-friendly waterproof type polymer fluorescent tattoo material according to claim 1, wherein in the step (2), the feeding ratio of the polythiooctanoic acid polymer to the TPEE is 0.1-10 g:0.01 to 5g.

4. The method for preparing a green and environment-friendly waterproof type polymer fluorescent tattoo material according to claim 1, wherein in the step (2), the reaction condition is a reaction at 0-150 ℃ for 1-12 hours.

5. The method for preparing a fluorescent tattooing material according to claim 1, wherein in step (3), the solvent is selected from one or more of methanol, ethanol, acetone, or water.

6. An environment-friendly waterproof polymer fluorescent tattoo material obtained by the preparation method according to any one of claims 1-5.

7. The use of the green, environmentally friendly, water-resistant, polymeric, fluorescent tattoo material according to claim 6, for the preparation of invisible tattoos.

8. The use of the green and environment-friendly waterproof type polymer fluorescent tattoo material according to claim 7, wherein the method comprises: the waterproof polymer fluorescent tattoo material is directly sprayed on the required position and pattern to obtain the invisible tattoo pattern.

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