Photochromic ink and preparation method thereof
By using tetraarylethylene compounds and other materials to prepare photochromic inks and adding ascorbic acid to the material, the problem of insufficient light fastness of existing photochromic inks is solved, and higher fatigue resistance and stability are achieved. Reduces production costs and is suitable for large-scale applications.
Patent Information
- Application Number
- CN202411283524.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-13
- Publication Date
- 2024-12-13
AI Technical Summary
The existing photochromic inks have insufficient light fastness and are susceptible to environmental factors, resulting in poor photochemical fatigue, short service life, complex synthesis steps, high cost, and widespread application.
Using tetraaryl ethylene compounds as photochromic materials, combining polyester epoxy acrylate, polyester acrylate, photoinitiator, thickener, defoaming agent and leveling agent, through specific ratios and preparation methods, Fatigue-resistant photochromic inks were prepared and ascorbic acid was added to the material to inhibit oxidative deterioration.
It improves the fatigue resistance and stability of photochromic inks, reduces production costs, is suitable for large-scale production applications, and extends service life.
Smart Images
Figure CN119119804A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of color-changing inks, and in particular to a photochromic ink and a preparation method thereof. Background Art
[0002] Color-changing inks are mainly used in the anti-counterfeiting industry, toy industry, clothing industry, handicraft industry, etc. The photochromic materials used in current color-changing inks are mainly divided into five categories: spiropyrans, fulgides, azobenzenes, diarylethenes and spirooxazines. Spiropyrans and their derivative spirooxazines are the earliest photochromic materials to be commercialized, but many shortcomings are still found in practical applications. The main problem is that the light fastness of this type of substance is insufficient. Photochromic compounds are easily affected by environmental factors such as pH, light and temperature, which leads to poor photochemical fatigue and degradation after repeated irradiation, affecting the service life of the color-changing ink. Another shortcoming is that the photochromic compound has a complex structure and many synthesis steps, resulting in high costs, which affects its wide application. Summary of the invention
[0003] In order to overcome the shortcomings and deficiencies of the prior art, the present invention aims to provide an anti-fatigue photochromic ink and a preparation method thereof, wherein the prepared photochromic ink has excellent anti-fatigue properties.
[0004] The technical solution adopted by the present invention to solve the technical problem is as follows: A photochromic ink comprises, by weight, 5-8 parts of photochromic components, 15-20 parts of polyester epoxy acrylate, 20-40 parts of polyester acrylate, 5-8 parts of photoinitiator, 1-2 parts of thickener, 0.2-0.5 parts of defoamer and 0.5-1 parts of leveling agent.
[0005] Preferably, the photochromic component comprises a raw material composition including: a tetraarylethene compound, a diisocyanate, an oil-free alkyd resin, a wax powder, a fumed silica, a propyltriethoxysilane, ascorbic acid, and an acetone solvent; the weight proportions of the raw materials in the order described are: (10-15): (1-2): (10-20): (5-10): (1-5): (1-2): (1-2): (40-60).
[0006] Preferably, the wax powder is ultrafine modified micronized polyethylene wax; the diisocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
[0007] Preferably, the photoinitiator is one of acylphosphine oxide or alkylphenone photoinitiators; the defoamer is one of polysiloxane or silicone-modified polymer defoamers; and the leveling agent is one of polyether siloxane copolymer or acrylate-modified polydimethylsiloxane.
[0008] The method for preparing the photochromic ink comprises the following steps: The photochromic component, polyester epoxy acrylate, polyester acrylate, photoinitiator, thickener, defoamer and leveling agent are mixed and stirred evenly to obtain the photochromic ink.
[0009] Preferably, the method for preparing the photochromic component comprises the following steps: Dissolve diisocyanate in twice the weight of acetone solvent to form a solution with a diisocyanate content of 50wt%, then add ascorbic acid and stir evenly to obtain component A; dissolve oil-free alkyd resin in the remaining acetone solvent, add tetraarylethene compound, wax powder, fumed silica, and aminopropyltriethoxysilane, stir evenly to obtain component B; mix component A and component B and stir evenly to obtain a photochromic component.
[0010] Preferably, the tetraarylethylene compound is one of cis-1,2-diphenyl-1,2-di(3-thienyl)ethylene, cis-1,2-diphenyl-1,2-di(3-pyrrolyl)ethylene, and cis-1,2-diphenyl-1,2-di(3-furanyl)ethylene, and its preparation method refers to the method disclosed in patent CN107033121A.
[0011] Compared with the prior art, the present invention has the following beneficial effects: The present invention uses tetraarylethenes as photochromic materials. Tetraarylethenes photochromic materials are developed from diarylethenes materials. The former has four aromatic substituents on the double bonds of olefins, which have greater steric hindrance and hindered rotation of the single bonds of the substituents. Therefore, compared with diarylethenes, spiropyrans and azobenzenes, tetraarylethenes have better fatigue resistance and stability. The color change of tetraarylethenes is a reversible reaction. After absorbing light, the ring is closed to generate a ring-closed product, and the color changes. After the light source is removed, the ring is opened to generate the original substance. When the tetraarylethenes are used to prepare the photochromic component, adding a strong reducing agent ascorbic acid therein can effectively inhibit the oxidation and deterioration of the ring-closed product, thereby further improving the fatigue resistance of the material.
[0012] The present invention prepares the tetraarylethene compound in two steps, uses common and cheap catalysts and reagents, has high reaction selectivity, greatly reduces production costs, and is suitable for large-scale production applications. BRIEF DESCRIPTION OF THE DRAWINGS
[0013] Figure 1The present invention is a synthetic route diagram of the tetraarylethene compound.
[0014] Figure 2 This is the discoloration and deterioration mechanism of the tetraarylethene compound of the present invention.
[0015] Figure 3 This is a color change cycle statistical diagram of Example 1 of the present invention.
[0016] Figure 4 This is a color change cycle statistical diagram of Example 2 of the present invention.
[0017] Figure 5 This is a color change cycle statistical diagram of Example 3 of the present invention.
[0018] Figure 6 It is a color change cycle statistical diagram of comparative example 1 of the present invention.
[0019] Figure 7 It is the color change cycle statistical diagram of comparative example 2 of the present invention. DETAILED DESCRIPTION
[0020] The modified epoxy resin conductive adhesive and its preparation method of the present invention are further described below in conjunction with the embodiments. It is to be understood that the specific embodiments described herein are only used to explain the relevant invention, rather than to limit the invention. Embodiment 1:
[0021] A photochromic ink, the raw materials of which are measured by weight, and are composed of: 5 parts of photochromic component, 15 parts of polyester epoxy acrylate, 20 parts of polyester acrylate, 5 parts of acylphosphine oxide, 1 part of thickener, 0.2 parts of polysiloxane defoamer, and 0.5 parts of polyether siloxane copolymer. The raw materials of the photochromic component include: tetraarylethylene compound, dicyclohexylmethane diisocyanate, oil-free alkyd resin, ultrafine modified micronized polyethylene wax, fumed silica, propyltriethoxysilane, ascorbic acid, and acetone solvent; the weight ratio of each raw material in the order described is: 10:1:10:5:1:1:1:40. The tetraarylethylene compound is cis-1,2-diphenyl-1,2-di(3-thienyl)ethylene, and its preparation method refers to the method disclosed in patent CN107033121A.
[0022] The preparation method of the photochromic ink described in this embodiment is: (1) dissolving dicyclohexylmethane diisocyanate in twice the weight of acetone solvent to form a solution with a diisocyanate content of 50 wt%, and then adding ascorbic acid and stirring evenly to obtain component A; dissolving oil-free alkyd resin in the remaining acetone solvent, adding cis-1,2-diphenyl-1,2-di(3-thienyl)ethylene, ultrafine modified micronized polyethylene wax, fumed silica, and aminopropyltriethoxysilane, and stirring evenly to obtain component B; mixing components A and B and stirring evenly to obtain a photochromic component; (2) Mix 5 parts of photochromic component, 15 parts of polyester epoxy acrylate, 20 parts of polyester acrylate, 5 parts of acylphosphine oxide, 1 part of thickener, 0.2 parts of polysiloxane defoamer and 0.5 parts of polyether siloxane copolymer, and stir well to obtain photochromic ink. Embodiment 2:
[0023] A photochromic ink, the raw materials of which are measured by weight, and are composed of: 6 parts of photochromic component, 17 parts of polyester epoxy acrylate, 30 parts of polyester acrylate, 6 parts of alkyl phenone photoinitiator, 1.5 parts of thickener, 0.3 parts of organosilicon modified polymer defoamer, and 0.7 parts of acrylate modified polydimethylsiloxane. The raw materials of the photochromic component include: tetraarylethylene compound, diphenylmethane diisocyanate, oil-free alkyd resin, ultrafine modified micronized polyethylene wax, fumed silica, propyltriethoxysilane, ascorbic acid, and acetone solvent; the weight ratio of each raw material in the order described is: 12:1:10:7:3:1:2:50. The tetraarylethylene compound is cis-1,2-diphenyl-1,2-di(3-pyrrolyl)ethylene, and its preparation method refers to the method disclosed in patent CN107033121A.
[0024] The preparation method of the photochromic ink described in this embodiment is: (1) Dissolving diphenylmethane diisocyanate in twice the weight of acetone solvent to form a solution with a diisocyanate content of 50 wt%, then adding ascorbic acid and stirring evenly to obtain component A; dissolving oil-free alkyd resin in the remaining acetone solvent, adding cis-1,2-diphenyl-1,2-di(3-pyrrolyl)ethylene, ultrafine modified micronized polyethylene wax, fumed silica, and aminopropyltriethoxysilane, and stirring evenly to obtain component B; mixing components A and B and stirring evenly to obtain a photochromic component; (2) Mix 6 parts of photochromic component, 17 parts of polyester epoxy acrylate, 30 parts of polyester acrylate, 6 parts of alkyl phenone photoinitiator, 1.5 parts of thickener, 0.3 parts of silicone modified polymer defoamer, and 0.7 parts of acrylate modified polydimethylsiloxane, and stir evenly to obtain a photochromic ink. Embodiment 3:
[0025] A photochromic ink, the raw materials of which are measured by weight, and are composed of: 8 parts of photochromic component, 20 parts of polyester epoxy acrylate, 40 parts of polyester acrylate, 8 parts of acylphosphine oxide photoinitiator, 2 parts of thickener, 0.5 parts of organosilicon modified polymer defoamer, and 1 part of acrylate modified polydimethylsiloxane. The raw materials of the photochromic component include: tetraarylethylene compound, hexamethylene diisocyanate, oil-free alkyd resin, ultrafine modified micronized polyethylene wax, fumed silica, propyltriethoxysilane, ascorbic acid, and acetone solvent; the weight ratio of each raw material in the order described is: 15:2:20:10:5:2:2:60. The tetraarylethylene compound is cis-1,2-diphenyl-1,2-di(3-furanyl)ethylene, and its preparation method refers to the method disclosed in patent CN107033121A.
[0026] The preparation method of the photochromic ink described in this embodiment is: (1) dissolving hexamethylene diisocyanate in twice the weight of acetone solvent to form a solution with a diisocyanate content of 50 wt%, then adding ascorbic acid and stirring evenly to obtain component A; dissolving oil-free alkyd resin in the remaining acetone solvent, adding cis-1,2-diphenyl-1,2-di(3-furyl)ethylene, ultrafine modified micronized polyethylene wax, fumed silica, and aminopropyl triethoxysilane, and stirring evenly to obtain component B; mixing components A and B and stirring evenly to obtain a photochromic component; (2) Mix 8 parts of photochromic component, 20 parts of polyester epoxy acrylate, 40 parts of polyester acrylate, 8 parts of acylphosphine oxide photoinitiator, 2 parts of thickener, 0.5 parts of silicone modified polymer defoamer, and 1 part of acrylate modified polydimethylsiloxane, and stir evenly to obtain a photochromic ink.
[0027] Comparative Example 1: Compared with Example 1, except for the lack of ascorbic acid, the other raw materials and preparation steps are consistent with Example 1.
[0028] Comparative Example 2: Compared with Example 1, except that cis-1,2-difluoro-1,2-di(3-thienyl)ethylene was used instead of cis-1,2-diphenyl-1,2-di(3-thienyl)ethylene, the other raw materials and preparation steps were the same as those in Example 1.
[0029] Color-changing ink performance test: The photochromic ink obtained in Examples 1-3 and Comparative Examples 1-2 was coated on a transparent glass plate, irradiated with 365nm ultraviolet light for 1h, and left in a dark environment for 12h for a cycle test of anti-fatigue performance. The absorbance was measured using an ultraviolet-visible spectrophotometer for characterization. The absorbance at a wavelength of 547nm was taken and recorded in Table 1, and a cycle statistical diagram was drawn, as shown in Table 1. Figure 3-7 shown.
[0030] Table 1: Absorbance of the photochromic ink in Examples 1-3 and Comparative Examples 1-2 in each cycle
[0031] From Table 1 and Figure 3-7 It can be concluded that the absorbance loss of the color-changing inks of Examples 1-3 and Comparative Examples 1-2 after 20 cycles is 15.19%, 17.50%, 19.38%, 29.30%, and 35.44%, respectively. The absorbance loss of Comparative Example 1 is smaller than that of Comparative Example 2, and the fatigue resistance is better. This is because Comparative Example 2 uses a diarylethylene compound, while Comparative Example 1 uses a tetraarylethylene compound, which has a larger steric hindrance and hinders the single bond rotation of the substituent. Therefore, compared with diarylethylene materials, tetraarylethylene has better fatigue resistance and stability; Example 1 has a smaller absorbance loss than Comparative Example 1, because Comparative Example 1 does not contain ascorbic acid, and the ascorbic acid in Example 1 can effectively inhibit the oxidation and deterioration of the tetraarylethylene compound during the ring-closing color change process, thereby further improving the fatigue resistance.
[0032] The above is a preferred embodiment of the present invention. It should be pointed out that a person skilled in the art can make several improvements and modifications without departing from the principle of the present invention. These improvements and modifications are also considered to be within the scope of protection of the present invention.
Claims
1. A photochromic ink, characterized in that: The raw materials thereof are calculated by weight and comprise: 5-8 parts of photochromic components, 15-20 parts of polyester epoxy acrylate, 20-40 parts of polyester acrylate, 5-8 parts of photoinitiator, 1-2 parts of thickener, 0.2-0.5 parts of defoamer and 0.5-1 parts of leveling agent.
2. A photochromic ink according to claim 1, characterized in that: The photochromic component comprises raw materials including: tetraarylethene compound, diisocyanate, oil-free alkyd resin, wax powder, fumed silica, propyltriethoxysilane, ascorbic acid and acetone solvent; the weight proportions of the raw materials in the order described are: (10-15): (1-2): (10-20): (5-10): (1-5): (1-2): (1-2): (40-60).
3. A photochromic ink according to claim 2, characterized in that: The wax powder is ultrafine modified micronized polyethylene wax; the diisocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
4. The photochromic ink according to claim 1, characterized in that: The photoinitiator is one of acylphosphine oxide or alkylphenone photoinitiators; the defoamer is one of polysiloxane or organosilicon-modified polymer defoamers; and the leveling agent is one of polyether siloxane copolymer or acrylate-modified polydimethylsiloxane.
5. The method for preparing the photochromic ink according to any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: The photochromic component, polyester epoxy acrylate, polyester acrylate, photoinitiator, thickener, defoamer and leveling agent are mixed and stirred evenly to obtain the photochromic ink.
6. The method for preparing the photochromic ink according to claim 5, characterized in that: The preparation method of the photochromic component comprises the following steps: Dissolve diisocyanate in twice the weight of acetone solvent to form a solution with a diisocyanate content of 50wt%, then add ascorbic acid and stir evenly to obtain component A; dissolve oil-free alkyd resin in the remaining acetone solvent, add tetraarylethene compound, wax powder, fumed silica, and aminopropyltriethoxysilane, stir evenly to obtain component B; mix component A and component B and stir evenly to obtain a photochromic component.