Color-changing ink for anti-drilling identification of bottle body of wine bottle as well as preparation method and application of color-changing ink

Abstract

The invention belongs to the technical field of functional materials, and particularly relates to color-changing ink for anti-drilling identification of a wine bottle body as well as a preparation method and application of the color-changing ink. The color-changing ink provided by the invention is prepared by taking a novel terpyridyl diyne compound as a raw material; the terpyridyl diyne compound is formed by connecting diyne compounds with different chain lengths and terpyridyl with different structures through amido bonds, has excellent color change performance, can improve the change temperature, and is good in color change stability; the color-changing performance of the paint is not influenced when the paint is dispersed in various paints; the method has sensitive responsiveness to the temperature and has potential application prospects in the aspects of temperature warning, safety protection and the like. The material is used for preparing the color-changing ink, the bottle body of the wine bottle is coated with the color-changing ink, and anti-drilling identification can be effectively carried out.

Description

Technical Field

[0001] The invention belongs to the technical field of functional materials, and in particular relates to color-changing ink for anti-drilling identification of wine bottle bodies, as well as a preparation method and application thereof. Background Art

[0002] Wine bottle anti-drilling identification technology plays a crucial role in the modern beverage industry, particularly in protecting consumer rights and maintaining brand image. With the rise of counterfeit and substandard products on the market, consumers are increasingly concerned about product safety. As the primary packaging for beverages, the integrity of the wine bottle is directly related to product quality and safety. Illegal drilling of the bottle can not only lead to leakage or contamination of the beverage, but can also cause consumer distrust of the brand. Therefore, implementing effective anti-drilling identification technology can promptly detect and prevent potential tampering, ensuring consumers receive safe and reliable products.

[0003] The application of thermochromic materials in anti-drilling technology for wine bottles stems from the growing demand for product safety and anti-counterfeiting measures, particularly in the high-value consumer goods market. As traditional anti-tampering methods no longer meet market demands, thermochromic materials are gaining popularity due to their sensitivity to temperature fluctuations. These materials undergo a significant color change when the temperature reaches a specific threshold, providing consumers with a visual warning that the bottle may have been subjected to external interference, such as illegal drilling or tampering. This characteristic has made thermochromic materials an increasingly effective anti-counterfeiting measure in the packaging of high-end alcoholic beverages.

[0004] The application of thermochromic materials in wine bottle anti-drilling technology is rapidly developing. Modern thermochromic materials are typically composed of temperature-responsive polymers or phase-change materials, which rapidly change their optical properties in response to temperature fluctuations. Among these, polydiyne materials have attracted considerable attention, primarily due to their excellent moldability in self-assembly systems. These materials achieve effective signal transmission through a color change effect triggered by chain segment motion.

[0005] Air spraying is an efficient and economical surface treatment method for wine bottles. Air spray uses compressed air to atomize the paint, achieving uniform and detailed coating coverage. This uniformity not only improves the coating's appearance but also effectively reduces paint waste and lowers production costs. Air spraying is simple to operate and easy to control. During the spraying process, the operator can precisely control the coating thickness and drying time by adjusting the air pressure and spray speed. This flexibility provides greater control over the production process and reduces rework and waste caused by uneven coating or inappropriate thickness.

[0006] Air spray also offers excellent environmental performance. The atomization of the paint during the spraying process effectively reduces solvent volatilization, minimizing environmental pollution and operator health impacts. Combined with low-VOC waterborne paints, air spray technology can further enhance its environmental performance, meeting the requirements of modern industry for sustainable development.

[0007] This invention uses a terpyridinediyne compound, produced by introducing a sterically hindered terpyridine group into a diyne carboxylic acid via an ester bond. After compounding with an acrylic resin, a suitable white ink is selected as the outer coating to mask the blue color of the material. This achieves a distinct and irreversible transition from white to red under perforation stimulation. This invention has potential applications in temperature warnings and safety protection for wine bottles, providing more possibilities and options for anti-counterfeiting technology. Summary of the Invention

[0008] The purpose of the present invention is to provide a color-changing ink for anti-drilling identification of wine bottle bodies, which has good color-changing effect, high sensitivity, small ink color difference, uniform spraying and is environmentally friendly, as well as a preparation method and application thereof.

[0009] The present invention first provides a novel terpyridinediyne compound, which is obtained by connecting diyne compounds of different chain lengths and terpyridines of different structures via an amide bond, and has the structural formula shown below (I):

[0010]

[0011] Wherein, n and m are the number of carbon atoms in the alkyl group, n is 0-20, preferably n is 1-20, and more preferably n is 10-15; m is 0-14, preferably m is 1-14, and more preferably m is 5-10; q is the number of benzene rings, q is 0-3, and preferably q is 1-3.

[0012] The terpyridinediyne compound exhibits excellent color-changing properties, can increase the color-changing temperature, and exhibits excellent color-changing stability. It can be dispersed in a variety of coatings without affecting its color-changing properties. Its sensitive response to temperature also suggests potential applications in temperature warning and safety protection.

[0013] The color-changing ink for anti-drilling identification of wine bottle bodies provided by the present invention is prepared using the above-mentioned terpyridinediyne compound as a basic material.

[0014] The method for preparing the color-changing ink for anti-drilling identification of wine bottle bodies provided by the present invention comprises the following specific steps:

[0015] (1) preparing an acrylic resin composite emulsion, specifically comprising: mixing an acrylic resin (1-50 g) with water, stirring at 20-100 degrees Celsius for 1-30 minutes to completely dissolve the acrylic resin, thereby obtaining a clear and transparent acrylic resin aqueous solution having an acrylic resin mass concentration of 5-50%; simultaneously weighing 1-20 mg of a terpyridinediyne compound and dissolving it in 1-20 mL of N,N-dimethylformamide, and slowly dripping the solution into the acrylic resin solution using a dropper; and stirring the mixture at 20-100 degrees Celsius for 1-30 minutes to prepare an acrylic resin composite emulsion;

[0016] (2) Preparation of white ink: The specific process is as follows: 50 g of HG-54C water-based acrylic emulsion (commercially available, for example, from Rohm and Haas) is placed in a beaker, 1 to 100 g of acrylic resin composite solution is slowly added to the beaker using a dropper, and stirred evenly to obtain a composite white ink.

[0017] The present invention also provides the use of the white ink in anti-drilling identification of wine bottle bodies. Specifically, the white ink is applied to the wine bottle body, and the specific steps are as follows:

[0018] (1) Add AD01 wetting agent (5-20‰) to the white ink, stir evenly, and then add SN-9709 thickener (5-20‰). Use a 1.0-10.0mm diameter nozzle to move the spray gun at a uniform speed to spray a circle on the bottle body, then dry it in an oven, and repeat the spraying and drying 2-5 times to ensure that the white ink is evenly sprayed on the bottle body;

[0019] (2) Place the dried wine bottle under a 254nm ultraviolet lamp for 1 to 10 minutes until the entire bottle turns blue;

[0020] (3) Spraying varnish: the specific process is as follows: weigh 50g of HG-54C emulsion, add AD01 wetting agent (5-10‰), SN-9709 thickener (5-10‰) and SN-4333 silicone leveling agent (5-10‰) respectively, mix and stir evenly, use a 1.0-10.0mm diameter nozzle to move the spray gun at a uniform speed, spray one circle and dry in an oven, then repeat the spraying and drying 2-5 times to ensure that the varnish is evenly sprayed on the bottle.

[0021] The percentages of the above-mentioned added materials are all based on the mass of the white ink.

[0022] The present invention also provides a method for preparing the above-mentioned terpyridinediyne compound, which comprises the following specific steps:

[0023] (1) Add p-nitrobenzaldehyde (1-20.0 mmol), ethanol (1-10 mL) and deionized water (1-10 mL) to a round-bottom flask. Subsequently, add 2-acetylpyridine (1-30.0 mmol) and stir at room temperature. Add sodium hydroxide (1-30.0 mmol) and ammonia water (1-40 mL) to the above mixed solution and continue stirring at room temperature for 1-10 hours. Filter and wash with deionized water and ethanol to obtain a solid. Dissolve the solid in concentrated hydrochloric acid, add excess stannous chloride, and react at 50-100 degrees Celsius overnight. Filter and adjust the pH to 7-14 to obtain the ligand 4'-(4-aminophenyl)-2,2':6',2-terpyridine for the next reaction.

[0024] (2) Add 10,12-pentacosadiyne carboxylic acid (0.5-2.0 mmol) and dichloromethane (1-30 mL) to a round-bottom flask. Subsequently, add oxalyl chloride (0.1-1 mL) dropwise and stir at room temperature for 1-2 hours. Add 1-10 drops of DMF to the above mixed solution and continue stirring at room temperature for 1-10 hours. After removing the solvent by rotary evaporation, add 4'-(4-aminophenyl)-2,2':6',2-terpyridine (0.5-5.0 mmol), tetrahydrofuran (1-20 mL) and triethylamine (1-2 mL) in sequence and stir at room temperature for 5-48 hours. Finally, separate the terpyridinediyne compound by column chromatography.

[0025] Compared with the prior art, the characteristics and advantages of the present invention are mainly as follows:

[0026] (1) Compared with the traditional color-changing material diyne carboxylic acid compound, the terpyridine diyne compound selected in the present invention has a higher color-changing temperature (reaching 120 degrees) and is more stable.

[0027] (2) The selected terpyridinediyne compounds have excellent dispersibility and can be easily dispersed in various types of coatings without causing any adverse effects on their color-changing properties.

[0028] (3) By using HG-54C emulsion coating as the outer coating, the problem that the diyne molecules cannot maintain the same appearance as the existing wine bottles when directly coated on the bottle surface can be solved, and the color change can be more intuitively shown after heating.

[0029] (4) The air spraying method adopted is uniform, efficient and economical, and the operation is flexible and controllable, which is suitable for large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is the effect of the wine bottle body being polymerized under 254nm ultraviolet light.

[0031] Figure 2 The effect after spraying the wine bottle with varnish.

[0032] Figure 3 The effect of different temperatures on diyne compounds.

[0033] Figure 4 It is the color change effect under the stimulation of punching. DETAILED DESCRIPTION

[0034] The present invention is further described below through embodiments in conjunction with the accompanying drawings.

[0035] Example 1, preparation of terpyridine compound 1, the specific steps are:

[0036] (1) Preparation of ligand 4'-(4-aminophenyl)-2,2':6',2-terpyridine. The specific steps are as follows: Preparation: Add p-nitrobenzaldehyde (10.0 mmol), ethanol (10 mL) and deionized water (5 mL) to a 100 mL round-bottom flask. Subsequently, add 2-acetylpyridine (20.0 mmol) and stir at room temperature. Add sodium hydroxide (26.0 mmol) and ammonia water (30 mL) to the above mixed solution and continue stirring at room temperature for 8 hours. Filter and wash with deionized water and ethanol to obtain a solid. Dissolve the solid in concentrated hydrochloric acid, add excess stannous chloride, and react at 80 degrees Celsius overnight. Filter and adjust the pH to 12 to obtain the ligand 4'-(4-aminophenyl)-2,2':6',2-terpyridine for the next reaction.

[0037] (2) Preparation of terpyridine compound 1, specifically the following steps: 10,12-pentacosadiyne carboxylic acid (1.0 mmol) and dichloromethane (20 mL) were added to a 50 mL round-bottom flask. Subsequently, oxalyl chloride (0.2 mL) was added dropwise and stirred at room temperature for 1 hour. Two drops of DMF were added to the above mixed solution and the mixture was stirred at room temperature for 6 hours. After the solvent was removed by rotary evaporation, 4'-(4-aminophenyl)-2,2':6',2-terpyridine (1.0 mmol), tetrahydrofuran (10 mL) and triethylamine (0.5 mL) were added in sequence and the mixture was stirred at room temperature for 24 hours. Finally, compound 1 was obtained by column chromatography. Its structural formula is:

[0038]

[0039] Example 2, preparation of terpyridine compound 2, the specific steps are:

[0040] (1) Preparation of ligand 4'-(4-aminophenyl)-2,2':6',2-terpyridine: The specific steps are as follows: p-hydroxybenzaldehyde (10.0 mmol), ethanol (10 mL) and deionized water (5 mL) were added to a 100 mL round-bottom flask. Subsequently, 2-acetylpyridine (20.0 mmol) was added and stirred at room temperature. Sodium hydroxide (26.0 mmol) and ammonia water (30 mL) were added to the above mixed solution and stirred at room temperature for 8 hours. Filtered, washed with deionized water and ethanol to obtain the ligand 4'-(4-hydroxyphenyl)-2,2':6',2-terpyridine.

[0041] (2) Preparation of terpyridine compound 2, specifically the following steps: 10,12-pentacosadiyne carboxylic acid (1.0 mmol) and dichloromethane (20 mL) were added to a 50 mL round-bottom flask. Subsequently, oxalyl chloride (0.2 mL) was added dropwise and stirred at room temperature for 1 hour. Two drops of DMF were added to the above mixed solution and the mixture was stirred at room temperature for 6 hours. After the solvent was removed by rotary evaporation, 4'-(4-hydroxyphenyl)-2,2':6',2-terpyridine (1.0 mmol), tetrahydrofuran (10 mL) and triethylamine (0.5 mL) were added in sequence and the mixture was stirred at room temperature for 24 hours. Finally, compound 2 was obtained by column chromatography. Its structural formula is:

[0042]

[0043] Example 3, preparation of naphthyldiyne compound 3, the specific steps are:

[0044] (1) Preparation of naphthyldiyne compound 3, specifically the following steps: 10,12-pentacosadiyne carboxylic acid (1.0 mmol) and dichloromethane (20 mL) were added to a 50 mL round-bottom flask. Subsequently, oxalyl chloride (0.2 mL) was added dropwise and stirred at room temperature for 1 hour. Two drops of DMF were added to the above mixed solution and the mixture was stirred at room temperature for 6 hours. After the solvent was removed by rotary evaporation, 1-naphthylamine (1.0 mmol), tetrahydrofuran (10 mL) and triethylamine (0.5 mL) were added in sequence and the mixture was stirred at room temperature for 24 hours. Finally, compound 3 was obtained by column chromatography. Its structural formula is:

[0045]

[0046] Example 4, preparation and coating of white ink composite emulsion, the specific steps are as follows:

[0047] (1) Preparing an acrylic resin composite emulsion, specifically comprising the following steps: mixing 25 g of acrylic resin with 30 g of water, and stirring at 50°C for 30 minutes to completely dissolve the acrylic resin and render it clear and transparent. Simultaneously, weighing 500 mg of a terpyridinediyne compound, dissolving it in 50 mL of N,N-dimethylformamide, and slowly dripping the solution into the acrylic resin solution using a dropper. The mixture was stirred at 50°C for 20 minutes to prepare a composite emulsion.

[0048] (2) Prepare white ink. The specific steps are as follows: take 50g of HG-54C water-based acrylic emulsion in a beaker, slowly add 50g of acrylic resin composite solution to the beaker with a dropper, and stir evenly.

[0049] (3) Spraying ink: The specific steps are as follows: add 2.5g (8‰) of AD01 wetting agent to the white ink, stir evenly, and then add 1.5g (5‰) of SN-9709 thickener. Use a 1.0mm diameter nozzle to move the spray gun at a uniform speed, spray once, and then dry in an oven. Repeat the spraying and drying twice to ensure that the white ink is evenly sprayed on the bottle.

[0050] (4) Polymerizing the ink on the bottle body of the wine bottle. The specific steps are as follows: Place the dried wine bottle under a 254nm ultraviolet lamp for 5 minutes until the bottle body turns blue.

[0051] (5) Spraying varnish, the specific steps are as follows: weigh 50g HG-54C emulsion, add 2.5g (8‰) of AD01 wetting agent, 1.5g (5‰) of SN-9709 thickener and 1.5g (5‰) of SN-4333 silicone leveling agent respectively, mix and stir evenly, use a 1.0mm diameter nozzle to move the spray gun at a uniform speed, spray one circle and dry in an oven, repeat the spraying and drying twice to ensure that the varnish is evenly sprayed on the bottle.

[0052] Example 5, preparation of composite film, the specific steps are:

[0053] Weigh 10 mg of a terpyridine diyne compound and dissolve it in 1 mL of N,N-dimethylformamide. Use a dropper to slowly drip the solution into 1.0 g of an acrylate resin. Stir the mixture at 80 degrees Celsius for 10 minutes. After cooling, apply it on a dry glass slide and dry it in an oven at 60 degrees Celsius. When irradiated under a 254 nm ultraviolet lamp, it can be observed that the acrylate resin film turns blue. The color-changing properties of the composite film material prepared by the above method were studied, and the obtained diyne compound film was placed in an oven at different temperatures for 10 minutes. The film was taken out and cooled to room temperature under natural conditions. The terpyridine diyne compounds are terpyridine diyne compounds 1 and 2 and naphthyl diyne compound 3. The effects of different temperatures on the diyne compounds are as follows. Figure 3 As shown:

[0054] For terpyridinediyne compound 1, the effect of different temperatures is Figure 3 (a);

[0055] For terpyridinediyne compound 2, the effect of different temperatures is Figure 3 (b);

[0056] For naphthyldiyne compound 3, the effect of different temperatures is Figure 3 (c).

[0057] In Example 6, a film material of terpyridine compound 1 was used, and a layer of white ink was covered on its outer layer. The color change performance was tested, and it was shown that after punching, the coating color changed significantly and irreversibly, and obvious red holes appeared on the surface of the bottle, which is helpful for preventing punched wine. Figure 4 .

Claims

1. A terpyridinediyne compound, characterized in that It is obtained by connecting diyne compounds of different chain lengths and terpyridines of different structures through amide bonds. Its structural formula is shown below (I): Wherein, n and m are the number of carbon atoms in the alkyl group, n is 0-20, m is 0-14, and q is the number of benzene rings, q is 0-3.

2. A color-changing ink for anti-drilling identification of wine bottles, characterized in that: The terpyridinediyne compound as claimed in claim 1 is used as a raw material for preparation.

3. A method for preparing the color-changing ink according to claim 2, characterized in that: The specific steps are: (1) preparing an acrylic resin composite emulsion, specifically comprising: mixing an acrylic resin (1-50 g) with water, stirring at 20-100 degrees Celsius for 1-30 minutes to completely dissolve the acrylic resin, thereby obtaining a clear and transparent acrylic resin aqueous solution having an acrylic resin mass concentration of 5-50%; simultaneously weighing 1-20 mg of a terpyridinediyne compound and dissolving it in 1-20 mL of N,N-dimethylformamide, and slowly dripping the solution into the acrylic resin solution using a dropper; and stirring the mixture at 20-100 degrees Celsius for 1-30 minutes to prepare an acrylic resin composite emulsion; (2) Preparation of white ink: The specific process is as follows: take 50g of HG-54C water-based acrylic emulsion in a beaker, slowly add 10-100g of acrylic resin composite solution to the beaker with a dropper, and stir evenly to obtain composite white ink.

4. The method for preparing the color-changing ink according to claim 3, wherein: The specific steps for preparing the terpyridinediyne compound are: (1) Add 1-20.0 mmol of p-nitrobenzaldehyde, 1-10 mL of ethanol, and 1-10 mL of deionized water to a round-bottom flask; then add 1-30.0 mmol of 2-acetylpyridine and stir evenly at room temperature; then add 1-30.0 mmol of sodium hydroxide and 1-40 mL of ammonia water and continue stirring at room temperature for 1-10 hours; filter and wash with deionized water and ethanol to obtain a solid; dissolve the solid in concentrated hydrochloric acid, add excess stannous chloride, and react at 50-100 degrees Celsius overnight; filter and adjust the pH to 7-14 to obtain the ligand 4'-(4-aminophenyl)-2,2':6',2-terpyridine; (2) Add 0.5-2.0 mmol of 10,12-pentacosadiyne carboxylic acid and 1-30 mL of dichloromethane to a round-bottom flask; then, add 0.1-1 mL of oxalyl chloride dropwise, and stir at room temperature for 1-2 hours; then add 1-10 drops of DMF, and continue stirring at room temperature for 1-10 hours; after removing the solvent by rotary evaporation, add 0.5-5.0 mmol of 4'-(4-aminophenyl)-2,2':6',2-terpyridine, 1-20 mL of tetrahydrofuran and 1-2 mL of triethylamine in sequence, and stir at room temperature for 5-48 hours; finally, separate by column chromatography to obtain the terpyridinediyne compound.

5. Use of the color-changing ink according to claim 2 in anti-drilling identification of wine bottles.

6. The use according to claim 5, characterized in that Apply white ink on the wine bottle. The specific steps are as follows: (1) Add AD01 wetting agent to the white ink, stir evenly, and then add SN-9709 thickener; use a 1.0-10.0 mm diameter nozzle to move the spray gun at a uniform speed to spray a circle on the bottle body, then dry it in an oven, and repeat the spraying and drying 2-5 times to ensure that the white ink is evenly sprayed on the bottle body; the amount of wetting agent and thickener added is 5-20‰ of the mass of the white ink; (2) Place the dried wine bottle under a 254nm ultraviolet lamp for 1 to 10 minutes until the entire bottle turns blue; (3) Spraying varnish: The specific process is as follows: weigh 50g of HG-54C emulsion, add AD01 wetting agent, SN-9709 thickener and SN-4333 silicone leveling agent respectively, mix and stir evenly, use a 1.0-10.0mm diameter nozzle to move the spray gun at a uniform speed, spray one circle and dry in an oven, repeat the spraying and drying 2-5 times to ensure that the varnish is evenly sprayed on the bottle; the amount of consumables, thickeners and silicone leveling agents added is 5-10‰ of the mass of white ink.

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