Photochromic anti-counterfeiting silicone oil and preparation method thereof

Abstract

The invention discloses photochromic anti-counterfeiting silicone oil and a preparation method thereof. The photochromic anti-counterfeiting silicone oil is prepared from the following raw materials in parts by weight: 100 parts of silicone oil and 0.001 to 0.1 part of a photochromic agent, wherein the photochromic agent is a spiropyrane compound or a thiophene compound. The photochromic anti-counterfeiting silicone oil obtained by the invention can realize color change under irradiation of ultraviolet light with a very small dosage of a photochromic agent and a specific wavelength, and can recover to an initial state under white light, that is, the color change is reversible, and the anti-counterfeiting identification effect is good. Experimental results also show that the photochromic anti-counterfeiting silicone oil can still keep good color changing performance through ultraviolet irradiation after high-temperature treatment or low-temperature freezing, namely, the photochromic stability is good. In addition, the preparation method disclosed by the invention is simple to operate and has relatively high industrial value. Therefore, the method has a wide application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of silicone oil preparation, and particularly relates to a photochromic anti-counterfeiting silicone oil and a preparation method thereof. Background Art

[0002] Silicone oil is an organic silicon compound composed of silicon atoms and carbon atoms. It has unique properties that general organic compounds do not have. Its molecular structure is mainly composed of silicon-oxygen bonds and carbon-oxygen bonds. Silicone-oxygen bonds are much stronger than carbon-oxygen bonds, which makes silicone oil have excellent high-temperature stability. It maintains excellent chemical stability in high-temperature environments and is not easy to react with other substances. It is often used for high-temperature heat conduction. Silicone oil is usually a transparent, colorless, viscous liquid with low surface tension and viscosity. Silicone oil has a wide range of applications and can be used in electronics, chemicals, textiles, and medical fields. There are various types of silicone oils on the market with uneven quality, and counterfeit and shoddy products are emerging in an endless stream. However, there are currently no anti-counterfeiting products for silicone oil on the market, especially for silicone oil with high temperature sensing requirements. If there are quality problems with silicone oil, it will have a great impact on consumers' use. Since the anti-counterfeiting of temperature sensing silicone oil needs to take into account the high and low temperature resistance of the anti-counterfeiting material, it is difficult to select anti-counterfeiting materials, and stable anti-counterfeiting materials with high and low temperature resistance are required.

[0003] As an important anti-counterfeiting technology, photochromism has been widely used in coating and ink anti-counterfeiting. Its principle is that the color of the product can be changed by irradiation with a certain wavelength of ultraviolet light, and it can return to its original colorless state after the ultraviolet light is removed.

[0004] Currently, commonly used photochromic materials are divided into organic photochromic compounds and inorganic photochromic compounds. Inorganic photochromic compounds have poor compatibility with silicone oil. Therefore, organic photochromic compounds are more suitable for photochromic anti-counterfeiting silicone oil. However, not all organic photochromic compounds are suitable for the development of photochromic anti-counterfeiting silicone oil. It is also necessary to consider the high and low temperature resistance of the photochromic compound, as well as the impact of the introduction of the photochromic compound on the stability and appearance of the silicone oil. Therefore, choosing a suitable organic photochromic compound is very important for the development of photochromic anti-counterfeiting silicone oil. Summary of the invention

[0005] In view of the problems existing in the background technology, the purpose of the present invention is to provide a photochromic anti-counterfeiting silicone oil and a preparation method thereof.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions: A first aspect of the present invention provides a photochromic anti-counterfeiting silicone oil, comprising the following raw materials in parts by weight: 100 parts of silicone oil and 0.001-0.1 parts of a photochromic agent; wherein the photochromic agent is a spiropyran compound or a thiophene compound.

[0007] Preferably, the viscosity of the silicone oil at 25° C. is 0.65-350 cps.

[0008] Preferably, the silicone oil is one of dimethyl silicone oil, methyl hydrogen silicone oil, and hydroxy silicone oil, or a combination of two or more thereof.

[0009] Preferably, the viscosity of the dimethyl silicone oil at 25° C. is 1 to 350 cps; its chemical structure is shown in formula (I):

[0010] (I).

[0011] Preferably, the viscosity of the methyl hydrogen silicone oil at 25° C. is 40-300 cps, and its chemical structure is shown in formula (II):

[0012] (II) Among them, n / m=100.

[0013] Preferably, the viscosity of the hydroxy silicone oil at 25° C. is 0.65-70 cps, and its chemical structure is shown in formula (III):

[0014] (III).

[0015] Preferably, the structural formula of the spiropyran compound is as shown in the following formula (IV):

[0016] (IV) Wherein, R1 is selected from methyl or hydroxyethyl; R2 is selected from nitro, halogen, hydrogen, methyl or methoxy; R3 is selected from hydrogen or methoxy.

[0017] Preferably, the chemical structure of the thiophene compound is as shown in formula (V) or (VI):

[0018] (V) (VI) Wherein, R1 is hydrogen or methyl; R2 is phenyl or methyl.

[0019] The second aspect of the present invention provides a method for preparing the above-mentioned photochromic anti-counterfeiting silicone oil, comprising the steps of: mixing silicone oil and a photochromic agent at room temperature, stirring to fully disperse the photochromic agent in the silicone oil, and obtaining the photochromic anti-counterfeiting silicone oil.

[0020] Compared with the prior art, the present invention has the following beneficial effects: (1) In the photochromic anti-counterfeiting silicone oil obtained by the present invention, the selected photochromic agent has good compatibility with the silicone oil, and the photochromic agent will not affect the performance of the silicone oil itself.

[0021] (2) The photochromic anti-counterfeiting silicone oil obtained by the present invention contains a very small amount of photochromic agent, which can change color under the irradiation of ultraviolet light of a specific wavelength and return to the initial state under white light. The color change is reversible and the anti-counterfeiting identification effect is good.

[0022] (3) The photochromic anti-counterfeiting silicone oil obtained in the present invention can still maintain good color-changing performance even after being treated at high temperature or frozen at low temperature and then irradiated with ultraviolet light, that is, the photochromic anti-counterfeiting silicone oil has good stability.

[0023] (4) The preparation method of the present invention is simple to operate and easy to realize industrial promotion, and therefore has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0025] Figure 1 The following are: (a) the color change performance of the photochromic silicone oil prepared in Example 1 is tested by a UV spectrophotometer when it is first cooled to -80°C and then irradiated with specific UV light; (b) the color change performance of the photochromic silicone oil is tested by a UV spectrophotometer when it is first heated to 160°C and then irradiated with specific UV light; (c) a comparison of color changes when irradiated with specific UV light at -40°C and -80°C; Figure 2 The following are: (a) the color change performance of the photochromic silicone oil prepared in Example 2 is tested by a UV spectrophotometer when it is first cooled to -80°C and then irradiated with specific UV light; (b) the color change performance of the photochromic silicone oil is tested by a UV spectrophotometer when it is first heated to 160°C and then irradiated with specific UV light; (c) a comparison of color changes when irradiated with specific UV light at room temperature, -20°C and -40°C; Figure 3 The following are: (a) the color change performance of the photochromic silicone oil prepared in Example 3 is tested by a UV spectrophotometer when it is first cooled to -80°C and then irradiated with specific UV light; (b) the color change performance of the photochromic silicone oil is tested by a UV spectrophotometer when it is first heated to 160°C and then irradiated with specific UV light; (c) a comparison of color changes when irradiated with specific UV light at room temperature, -20°C and -40°C; Figure 4The following are: (a) the color change performance of the photochromic silicone oil prepared in Example 4 was tested by a UV spectrophotometer when it was first cooled to -80°C and then irradiated with specific ultraviolet light; (b) the color change performance of the photochromic silicone oil was tested by a UV spectrophotometer when it was first heated to 160°C and then irradiated with specific ultraviolet light; (c) a comparison of color changes when irradiated with specific ultraviolet light at room temperature, -20°C and -40°C; Figure 5 The following are: (a) the color change performance of the photochromic silicone oil prepared in Example 5 is tested by a UV spectrophotometer when it is first cooled to -80°C and then irradiated with specific ultraviolet light; (b) the color change performance of the photochromic silicone oil is tested by a UV spectrophotometer when it is first heated to 160°C and then irradiated with specific ultraviolet light; (c) a comparison of color changes when irradiated with specific ultraviolet light at room temperature, -20°C and -40°C. DETAILED DESCRIPTION In the following description, for the purpose of illustration rather than limitation, specific details such as specific system structures and technologies are provided to provide a thorough understanding of the embodiments of the present invention. However, it should be clear to those skilled in the art that the present invention may also be implemented in other embodiments without these specific details.

[0026] Example 1 (1) 100 parts of methyl hydrogenated silicone oil (with a viscosity of 202 cps at 25°C) and 0.007 parts of a spiropyran compound having a structural formula as shown in formula (1) (as a photochromic agent) are added into a container and stirred thoroughly at room temperature to make the spiropyran compound fully dispersed in the methyl hydrogenated silicone oil, thereby obtaining a photochromic (anti-counterfeiting) silicone oil. Example 2 100 parts of dimethyl silicone oil (with a viscosity of 100 cps at 25°C) and 0.01 parts of a spiropyran compound having a structural formula as shown in formula (1) (as a photochromic agent) are added into a container and stirred thoroughly at room temperature to make the spiropyran compound fully dispersed in the dimethyl silicone oil, thereby obtaining a photochromic (anti-counterfeiting) silicone oil. Example 3 (2) 100 parts of hydroxy silicone oil (with a viscosity of 70 cps at 25°C) and 0.1 parts of a spiropyran compound having a structural formula as shown in formula (2) (as a photochromic agent) are added into a container and stirred thoroughly at room temperature to allow the spiropyran compound to be fully dispersed in the hydroxy silicone oil, thereby obtaining a photochromic (anti-counterfeiting) silicone oil.

[0029] Example 4 (3) 100 parts of hydroxy silicone oil (with a viscosity of 50 cps at 25°C) and 0.05 parts of a spiropyran compound having a structural formula as shown in formula (3) (as a photochromic agent) are added into a container and stirred thoroughly at room temperature to allow the spiropyran compound to be fully dispersed in the hydroxy silicone oil, thereby obtaining a photochromic (anti-counterfeiting) silicone oil.

[0031] Example 5 100 parts of dimethyl silicone oil (with a viscosity of 100 cps at 25°C) and 0.05 parts of a spiropyran compound having a structural formula as shown in formula (2) (as a photochromic agent) are added into a container and stirred thoroughly at room temperature to allow the spiropyran compound to be fully dispersed in the dimethyl silicone oil, thereby obtaining a photochromic (anti-counterfeiting) silicone oil.

[0032] Example 6 100 parts of methyl hydrogenated silicone oil (with a viscosity of 202 cps at 25°C) and 0.001 parts of a spiropyran compound having a structural formula as shown in formula (1) (as a photochromic agent) are added into a container and stirred thoroughly at room temperature to allow the spiropyran compound to be fully dispersed in the methyl hydrogenated silicone oil, thereby obtaining a photochromic (anti-counterfeiting) silicone oil.

[0033] Example 7 (4) 100 parts of hydroxy silicone oil (with a viscosity of 0.65 cps at 25°C) and 0.015 parts of a thiophene compound having a structural formula as shown in formula (4) (as a photochromic agent) are added into a container and stirred thoroughly at room temperature to make the thiophene compound fully dispersed in the dimethyl silicone oil to obtain a photochromic (anti-counterfeiting) silicone oil.

[0035] Example 8 (5) 100 parts of dimethyl silicone oil (with a viscosity of 350 cps at 25°C) and 0.01 parts of a thiophene compound having a structural formula as shown in formula (5) (as a photochromic agent) are added into a container and stirred thoroughly at room temperature to make the thiophene compound fully dispersed in the dimethyl silicone oil, thereby obtaining a photochromic (anti-counterfeiting) silicone oil.

[0037] Comparative Example 1 The steps are basically the same as those in Example 2, except that no photochromic agent is added.

[0038] Comparative Example 2 100 parts of dimethyl silicone oil (with a viscosity of 100 cps at 25°C) and 0.01 parts of molybdenum trioxide (a commercially available photochromic agent) were added into a container and stirred thoroughly at room temperature to fully disperse the molybdenum trioxide in the dimethyl silicone oil to obtain photochromic silicone oil.

[0039] Comparative Example 3 (6) 100 parts of dimethyl silicone oil (with a viscosity of 100 cps at 25° C.) and 0.01 parts of cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thiophene)ethylene (a commercially available photochromic agent) having a structural formula as shown in formula (6) are added into a container and stirred thoroughly at room temperature to allow the photochromic agent to be fully dispersed in the dimethyl silicone oil, thereby obtaining a photochromic silicone oil.

[0041] Comparative Example 4 100 parts of hydroxy silicone oil (with a viscosity of 500 cps at 25° C.) and 0.05 parts of a spiropyran compound having a structural formula as shown in formula (3) (as a photochromic agent) are added into a container and stirred thoroughly at room temperature to allow the spiropyran compound to be fully dispersed in the hydroxy silicone oil, thereby obtaining a photochromic silicone oil.

[0042] Comparative Example 5 100 parts of dimethyl silicone oil (with a viscosity of 400 cps at 25° C.) and 0.05 parts of a spiropyran compound having a structural formula as shown in formula (2) (as a photochromic agent) are added into a container and stirred thoroughly at room temperature to allow the spiropyran compound to be fully dispersed in the dimethyl silicone oil to obtain a photochromic silicone oil.

[0043] 1. Detect the photochromic performance of photochromic silicone oil after use at different temperatures Specifically, the photochromic (anti-counterfeiting) silicone oils prepared in Examples 1-8 and Comparative Examples 1-5 were heated or cooled to a certain temperature, and then irradiated with ultraviolet light of a specific wavelength, and their color changes were observed and their photochromic properties were tested with an ultraviolet spectrophotometer. The test results are shown in Figure 1-5 and Table 1.

[0044] Table 1

[0045] From Table 1 and Figure 1-5 The results show that when the photochromic anti-counterfeiting silicone oil prepared in Example 1 is heated to 160°C and then irradiated with 254 nm ultraviolet light, it can be seen that the silicone oil changes from colorless to yellow; when the photochromic silicone oil is cooled to -20°C, -40°C, and -80°C, respectively, and then irradiated with 254 nm ultraviolet light, it can be seen that the silicone oil can still change from colorless to yellow.

[0046] When the photochromic silicone oil prepared in Example 2 is heated to 160°C and then irradiated with 254 nm ultraviolet light, it can be seen that the silicone oil changes from colorless to yellow; when the photochromic anti-counterfeiting silicone oil is cooled from room temperature to -20°C, -40°C, and -80°C, respectively, and then irradiated with 254 nm ultraviolet light, it can be seen that the silicone oil can still change from colorless to yellow.

[0047] When the photochromic silicone oil prepared in Example 3 is heated to 160°C and then irradiated with 365 nm ultraviolet light, it can be seen that the silicone oil changes from colorless to purple; when the photochromic anti-counterfeiting silicone oil is cooled to -20°C, -40°C, and -80°C, respectively, and then irradiated with 365 nm ultraviolet light, it can be seen that the silicone oil can still change from colorless to purple. When the photochromic silicone oil prepared in Example 4 is heated to 160°C and then irradiated with 365 nm ultraviolet light, it can be seen that the silicone oil changes from colorless to rose red; when the photochromic silicone oil is cooled to -20°C, -40°C, and -80°C respectively, and then irradiated with 365 nm ultraviolet light, it can be seen that the silicone oil can still change from colorless to rose red.

[0048] When the photochromic silicone oil prepared in Example 5 is heated to 160°C and then irradiated with 365 nm ultraviolet light, it can be seen that the silicone oil changes from colorless to purple; when the photochromic silicone oil is cooled from room temperature to -20°C, -40°C, and -80°C, respectively, and then irradiated with 365 nm ultraviolet light, it can be seen that the silicone oil can still change from colorless to purple. When the photochromic silicone oil prepared in Example 6 is heated to 160°C and then irradiated with 365 nm ultraviolet light, it can be seen that the silicone oil changes from colorless to light yellow; when the photochromic silicone oil is cooled from room temperature to -20°C, -40°C, and -80°C, respectively, and then irradiated with 365 nm ultraviolet light, it can be seen that the silicone oil can still change from colorless to light yellow.

[0049] When the photochromic silicone oil prepared in Example 7 is heated to 160°C and then irradiated with 310 nm ultraviolet light, it can be seen that the silicone oil changes from colorless to pink; when the photochromic silicone oil is cooled from room temperature to -20°C, -40°C, and -80°C, respectively, and then irradiated with 310 nm ultraviolet light, it can be seen that the silicone oil can still change from colorless to pink.

[0050] When the photochromic silicone oil prepared in Example 8 is heated to 160°C and then irradiated with 310 nm ultraviolet light, it can be seen that the silicone oil changes from colorless to purple; when the photochromic silicone oil is cooled from room temperature to -20°C, -40°C, and -80°C, respectively, and then irradiated with 310 nm ultraviolet light, it can be seen that the silicone oil can still change from colorless to purple.

[0051] However, since the silicone oil in Comparative Example 1 does not have a photochromic agent introduced therein, no color change occurs when irradiated with ultraviolet light.

[0052] By comparing the test results of Examples 1 to 8 with Comparative Example 1, it can be seen that the photochromic agent used in the present invention has good compatibility in silicone oil, can be dispersed evenly, has a stable color-changing effect, and the introduction of the photochromic agent has no effect on the high and low temperature thermal conductivity and appearance of the silicone oil itself.

[0053] By comparing the test results of Example 2 with those of Comparative Examples 2-3, it can be seen that the photochromic agent selected in the present invention can significantly improve the color changing effect and has excellent stability.

[0054] By comparing the test results of Examples 4-5 with Comparative Examples 4-5, it can be seen that the viscosity of the silicone oil used in the present invention needs to be controlled within a certain range in order to obtain a photochromic anti-counterfeiting silicone oil with better comprehensive performance.

[0055] In summary, the photochromic anti-counterfeiting silicone oil prepared by the present invention can change color under ultraviolet light of a specific wavelength when the amount of the photochromic agent used is very small, and returns to the initial state under white light, the color change is reversible, and the anti-counterfeiting identification effect is good. At the same time, the photochromic anti-counterfeiting silicone oil prepared by the present invention can still maintain good color change performance even after high-temperature treatment or low-temperature freezing and then irradiated with ultraviolet light, that is, the photochromic anti-counterfeiting silicone oil prepared by the present invention has good stability.

[0056] The present invention is not limited to the above-mentioned specific implementation modes. Various changes made by ordinary technicians in this field based on the above-mentioned concepts without creative work are all within the protection scope of the present invention.

Claims

1. A photochromic anti-counterfeiting silicone oil, characterized in that: The invention comprises the following raw materials in parts by weight: 100 parts of silicone oil and 0.001-0.1 parts of a photochromic agent; wherein the photochromic agent is a spiropyran compound or a thiophene compound.

2. The photochromic anti-counterfeiting silicone oil according to claim 1, characterized in that: The viscosity of the silicone oil at 25° C. is 0.65-350 cps.

3. The photochromic anti-counterfeiting silicone oil according to claim 1, characterized in that: The silicone oil is one of dimethyl silicone oil, methyl hydrogen silicone oil, and hydroxy silicone oil, or a combination of two or more thereof.

4. The photochromic anti-counterfeiting silicone oil according to claim 3, characterized in that: The viscosity of the dimethyl silicone oil at 25° C. is 1 to 350 cps, and the chemical structure is shown in formula (I): （Ⅰ）。 5. The photochromic anti-counterfeiting silicone oil according to claim 3, characterized in that: The viscosity of the methyl hydrogen silicone oil at 25° C. is 40-300 cps, and the chemical structure is shown in formula (II): （Ⅱ） Among them, n / m=100.

6. The photochromic anti-counterfeiting silicone oil according to claim 3, characterized in that: The viscosity of the hydroxy silicone oil at 25° C. is 0.65-70 cps, and the chemical structure is shown in formula (III): （Ⅲ）。 7. The photochromic anti-counterfeiting silicone oil according to claim 1, characterized in that: The structural formula of the spiropyran compound is shown in the following formula (IV): （Ⅳ） Wherein, R1 is selected from methyl or hydroxyethyl; R2 is selected from nitro, halogen, hydrogen, methyl or methoxy; R3 is selected from hydrogen or methoxy.

8. The photochromic anti-counterfeiting silicone oil according to claim 1, characterized in that: The chemical structural formula of the thiophene compound is shown in formula (V) or (VI): （Ⅴ）（Ⅵ） Wherein, R1 is hydrogen or methyl; R2 is phenyl or methyl.

9. A method for preparing the photochromic anti-counterfeiting silicone oil according to any one of claims 1 to 8, characterized in that: The method comprises the steps of mixing silicone oil and a photochromic agent at room temperature, stirring, and fully dispersing the photochromic agent in the silicone oil to obtain the photochromic anti-counterfeiting silicone oil.

Images