Waterproof wear-resistant high-fidelity label anti-forgery ink and preparation method thereof

Abstract

The invention provides waterproof, wear-resistant and high-fidelity label anti-forgery ink and a preparation method thereof, relates to the technical field of anti-forgery ink, and aims to provide ink with excellent anti-forgery performance, water resistance and wear resistance. The ink is prepared by a special preparation process which comprises the following steps: mixing, heating and dissolving an organic ultraviolet fluorescent pigment, a cosolvent, an oil-phase solvent and an oil-phase cross-linking agent to form an oil-phase solution, mixing the oil-phase solution with a water-phase solution formed by an emulsifier and deionized water, stirring at a high speed to form an emulsion, and forming a microcapsule shell layer on the surface of an oil drop through an interfacial polymerization reaction to obtain the ink. The fluorescent pigment microcapsule is obtained. In addition, after being modified, the nanoscale silicon dioxide particles are added into the waterborne polyurethane resin and mixed with the fluorescent pigment microcapsules, the metal oxide pigment, the cross-linking agent and the deionized water b, defoaming is conducted after stirring, and the final product is obtained. The printing ink remarkably improves the anti-counterfeiting performance of a label, and has good mechanical strength, thermal stability and waterproof and wear-resistant characteristics.

Description

Technical Field

[0001] The invention relates to the technical field of anti-counterfeiting inks, in particular to a waterproof, wear-resistant and high-fidelity anti-counterfeiting ink for labels and a preparation method thereof. Background Art

[0002] In the field of anti-counterfeiting technology, especially label anti-counterfeiting ink technology, with the development of commodity economy and the increase of counterfeit and inferior products, the demand for technology that can effectively prevent counterfeiting and copying is growing. As an important anti-counterfeiting technology, anti-counterfeiting ink is widely used in various commodity labels and certificates. Its main function is to identify the authenticity of commodities through special printing effects and protect the interests of brands and consumers.

[0003] Traditional anti-counterfeiting inks have significant deficiencies in practical applications. These deficiencies are mainly reflected in the following aspects: poor waterproof performance. Many traditional anti-counterfeiting inks are easy to dissolve or fall off when encountering water or humid environments, which greatly reduces their anti-counterfeiting effect; poor water resistance and abrasion resistance. In environments with high humidity or frequent friction, traditional inks are easy to fade or fall off, affecting the durability and reliability of anti-counterfeiting labels and reducing the fidelity of anti-counterfeiting inks. Summary of the invention

[0004] In view of the above problems, the present invention provides a waterproof, wear-resistant and high-fidelity label anti-counterfeiting ink and a preparation method thereof.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solutions: A method for preparing a waterproof, wear-resistant and high-fidelity label anti-counterfeiting ink, comprising the following steps:

[0006] S1: Mixing an organic ultraviolet fluorescent pigment, a cosolvent, an oil phase solvent, and an oil phase crosslinking agent according to a proportion, heating and dissolving the mixture to obtain an oil phase solution; adding an emulsifier to deionized water a to form an aqueous phase solution, slowly dropping the oil phase solution into the aqueous phase solution, and stirring at a high speed of 1200 to 1500 rpm for 30 to 60 minutes to form a stable emulsion, adding wall material monomers ethylenediamine and hexamethylenediamine, initiator ammonium persulfate, and catalyst tetramethylethylenediamine to the emulsion, and continuing to stir at 500 to 800 rpm, controlling the temperature at 60°C to 80°C and the pH value at 8 to 9, and performing an interfacial polymerization reaction for 40 to 60 minutes to form a microcapsule shell layer on the surface of the oil droplets to obtain fluorescent pigment microcapsules;

[0007] S2: Ultrasonic dispersion of nano-scale silica particles in a mixed solution of ethanol and isopropanol for 30 to 45 minutes to form a uniform nano-scale silica particle suspension, adding γ-glycidyl ether propyl trimethoxysilane to the uniform nano-scale silica particle suspension, controlling the temperature at 55° C. to 65° C. and the pH value at 8 to 9, reacting for 2 to 3 hours, cooling, centrifuging and washing to obtain modified nano-scale silica particles;

[0008] S3: Add modified nano-scale silica particles to water-based polyurethane resin, stir evenly, add fluorescent pigment microcapsules, metal oxide pigments, crosslinking agent and deionized water b in sequence, stir for 20min to 30min, stirring at a speed of 1600 to 2000rpm, add defoaming agent and continue stirring for 5min to 10min, stirring at 800 to 1200rpm. After defoaming, let the mixture stand until the bubbles disappear completely to obtain a waterproof, wear-resistant and high-fidelity label anti-counterfeiting ink.

[0009] Preferably, the organic ultraviolet fluorescent pigment is a coumarin dye.

[0010] Preferably, the co-solvent is 1-hexadecanol.

[0011] Preferably, the oil phase solvent is any one of phenyl benzoate, benzophenone and benzyl phenyl ether.

[0012] Preferably, the oil phase crosslinking agent is toluene diisocyanate.

[0013] Preferably, the emulsifier is composed of gum arabic and sodium lauryl sulfate in a mass ratio of 1:3.

[0014] Preferably, the wall material monomers are composed of ethylenediamine and hexamethylenediamine, and the mass ratio of ethylenediamine to hexamethylenediamine is 1:1.

[0015] Preferably, the initiator is ammonium persulfate.

[0016] Preferably, the catalyst is tetramethylethylenediamine.

[0017] Preferably, the weight proportions of the organic ultraviolet fluorescent pigment, cosolvent, oil phase solvent, oil phase crosslinking agent, deionized water, emulsifier, wall material monomer, initiator and catalyst are 12 to 16 parts of organic ultraviolet fluorescent pigment, 5 to 7 parts of cosolvent, 20 to 30 parts of oil phase solvent, 16 to 28 parts of oil phase crosslinking agent, 40 to 50 parts of deionized water, 7 to 10 parts of emulsifier, 20 to 36 parts of wall material monomer, 2 to 3 parts of initiator and 0.2 to 0.8 parts of catalyst.

[0018] Preferably, the mass ratio of ethanol to isopropanol in the mixed solution of ethanol and isopropanol is 3:1.

[0019] Preferably, the mass ratio of the nano-scale silica particles, γ-glycidyl ether propyl trimethoxy silane and the mixed solution of ethanol and isopropanol is 1:1:5.

[0020] Preferably, the metal oxide pigment is a mixture of yellow iron oxide, red iron oxide and titanium dioxide, and the mass ratio of the yellow iron oxide, red iron oxide and titanium dioxide is 2:2:1.

[0021] Preferably, the cross-linking agent is any one of hexamethylene diisocyanate or toluene diisocyanate.

[0022] Preferably, the waterproof, wear-resistant and high-fidelity label anti-counterfeiting ink is composed by weight of 18 to 25 parts of fluorescent pigment microcapsules, 7 to 10 parts of modified nano-scale silica particles, 30 to 40 parts of water-based polyurethane resin, 5 to 7 parts of metal oxide pigments, 2 to 5 parts of cross-linking agent and 13 to 38 parts of deionized water.

[0023] The various components in the waterproof, wear-resistant and high-fidelity label anti-counterfeiting ink are cross-linked with each other through chemical reactions and physical effects, thereby jointly improving the overall performance of the ink.

[0024] The wall material monomers ethylenediamine and hexamethylenediamine and the oil phase crosslinking agent toluene diisocyanate in the fluorescent pigment microcapsules are crosslinked in an interfacial polymerization reaction to form a stable shell layer surrounding the oil phase solution. This shell layer not only protects the internal thermochromic material, but also gives the microcapsules good mechanical strength and thermal stability.

[0025] After being modified with γ-glycidyl ether propyl trimethoxysilane, the surface activity of the nano-scale silicon dioxide particles is enhanced, which is conducive to combining with the water-based polyurethane resin, thereby improving the wear resistance and waterproof performance of the ink and increasing the durability of the anti-counterfeiting label.

[0026] The cross-linking agent hexamethylene diisocyanate or toluene diisocyanate plays a curing role in the ink, and forms a three-dimensional network structure by reacting with active hydrogen in the resin, thereby significantly improving the mechanical strength and chemical stability of the ink.

[0027] The present invention provides a waterproof, wear-resistant, high-fidelity anti-counterfeiting label ink and a preparation method thereof. It has the following beneficial effects:

[0028] 1. The waterproof, wear-resistant, high-fidelity anti-counterfeiting ink for labels prepared by the present invention significantly improves the anti-counterfeiting performance of the labels by using organic ultraviolet fluorescent pigments and a special preparation method. During the preparation of fluorescent pigment microcapsules, a microcapsule shell is formed on the surface of the oil droplet through an interfacial polymerization reaction. This shell not only protects the fluorescent pigment inside, but also gives the microcapsules good mechanical strength and thermal stability. This structure makes the ink difficult to be copied or imitated, thereby enhancing the safety and anti-counterfeiting ability of the label.

[0029] 2. In the preparation method of waterproof, wear-resistant and high-fidelity anti-counterfeiting label ink, the various components are cross-linked through chemical reactions and physical effects to jointly improve the overall performance of the ink. In particular, the cross-linking agent hexamethylene diisocyanate or toluene diisocyanate plays a curing role in the ink, and reacts with the active hydrogen in the resin to form a three-dimensional network structure, which significantly improves the mechanical strength and chemical stability of the ink. This structure allows the ink to show better fluidity and uniformity during the printing process, while also ensuring the durability and stability of the printed product.

[0030] 3. After the nano-scale silicon dioxide particles used in the present invention are modified with γ-glycidyl ether propyl trimethoxysilane, their surface activity is enhanced, which is conducive to combining with the water-based polyurethane resin, thereby improving the wear resistance and waterproof performance of the ink. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. 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.

[0032] Embodiment 1:

[0033] A waterproof, wear-resistant, high-fidelity label anti-counterfeiting ink and a preparation method thereof, comprising the following contents:

[0034] Material ratio: 12 parts of organic ultraviolet fluorescent pigment, 5 parts of cosolvent, 20 parts of oil phase solvent, 40 parts of deionized water a, 16 parts of oil phase crosslinking agent, 7 parts of emulsifier, 20 parts of wall material monomer, 2 parts of initiator, 0.2 parts of catalyst; 18 parts of fluorescent pigment microcapsules, 7 parts of modified nano-scale silica particles, 30 parts of water-based polyurethane resin, 5 parts of metal oxide pigment, 2 parts of crosslinking agent, 18 parts of deionized water b.

[0035] Preparation steps:

[0036] S1: Mixing an organic ultraviolet fluorescent pigment, a cosolvent, an oil phase solvent, and an oil phase crosslinking agent according to a proportion, heating and dissolving the mixture to obtain an oil phase solution; adding an emulsifier to deionized water a to form an aqueous phase solution, slowly dropping the oil phase solution into the aqueous phase solution, and stirring at a high speed of 1200 to 1500 rpm for 30 to 60 minutes to form a stable emulsion, adding wall material monomers ethylenediamine and hexamethylenediamine, initiator ammonium persulfate, and catalyst tetramethylethylenediamine to the emulsion, continuing to stir at 500 to 800 rpm, controlling the temperature at 60° C. to 80° C. and the pH value at 8 to 9, performing an interfacial polymerization reaction, and reacting for 40 to 60 minutes to form a microcapsule shell layer on the surface of the oil droplets to obtain fluorescent pigment microcapsules;

[0037] S2: Ultrasonic dispersion of nano-scale silica particles in a mixed solution of ethanol and isopropanol for 30 to 45 minutes to form a uniform nano-scale silica particle suspension, adding γ-glycidyl ether propyl trimethoxysilane to the uniform nano-scale silica particle suspension, controlling the temperature at 55° C. to 65° C. and the pH value at 8 to 9, reacting for 2 to 3 hours, cooling, centrifuging and washing to obtain modified nano-scale silica particles;

[0038] S3: Add modified nano-scale silica particles to water-based polyurethane resin, stir evenly, add fluorescent pigment microcapsules, metal oxide pigments, crosslinking agent and deionized water b in sequence, stir for 20min to 30min, stirring at a speed of 1600 to 2000rpm, add defoaming agent and continue stirring for 5min to 10min, stirring at 800 to 1200rpm. After defoaming, let the mixture stand until the bubbles disappear completely to obtain a waterproof, wear-resistant and high-fidelity label anti-counterfeiting ink.

[0039] Embodiment 2:

[0040] A waterproof, wear-resistant, high-fidelity label anti-counterfeiting ink and a preparation method thereof, comprising the following contents:

[0041] Material ratio: 14 parts of organic ultraviolet fluorescent pigment, 6 parts of cosolvent, 25 parts of oil phase solvent, 50 parts of deionized water a, 20 parts of oil phase crosslinking agent, 8 parts of emulsifier, 28 parts of wall material monomer, 2.5 parts of initiator, 0.5 parts of catalyst; 22 parts of fluorescent pigment microcapsules, 8 parts of modified nano-scale silica particles, 35 parts of water-based polyurethane resin, 6 parts of metal oxide pigment, 3 parts of crosslinking agent, and 20 parts of deionized water b.

[0042] Preparation steps:

[0043] The steps in Example 1 were repeated, and the material ratio was adjusted. The rest of the preparation method and operating conditions were the same as those in Example 1.

[0044] Embodiment 3:

[0045] A waterproof, wear-resistant, high-fidelity label anti-counterfeiting ink and a preparation method thereof, comprising the following contents:

[0046] Material ratio: 16 parts of organic ultraviolet fluorescent pigment, 7 parts of cosolvent, 20 parts of oil phase solvent, 40 parts of deionized water a, 28 parts of oil phase crosslinking agent, 10 parts of emulsifier, 36 parts of wall material monomer, 3 parts of initiator, 0.8 parts of catalyst; 10 parts of modified nano-scale silica particles, 25 parts of fluorescent pigment microcapsules, 40 parts of water-based polyurethane resin, 7 parts of metal oxide pigment, 4 parts of crosslinking agent, and 30 parts of solvent.

[0047] Preparation steps:

[0048] The steps in Example 1 were repeated, and the material ratio was adjusted. The rest of the preparation method and operating conditions were the same as those in Example 1.

[0049] Embodiment 4:

[0050] A waterproof, wear-resistant, high-fidelity label anti-counterfeiting ink and a preparation method thereof, comprising the following contents:

[0051] Material ratio: 13 parts of organic ultraviolet fluorescent pigment, 5.5 parts of cosolvent, 22 parts of oil phase solvent, 44 parts of deionized water a, 18 parts of oil phase crosslinking agent, 7.5 parts of emulsifier, 24 parts of wall material monomer, 2.2 parts of initiator, 0.4 parts of catalyst; 25 parts of fluorescent pigment microcapsules, 10 parts of modified nano-scale silica particles, 38 parts of waterborne polyurethane resin, 6 parts of metal oxide pigment, 5 parts of crosslinking agent, 22 parts of deionized water b.

[0052] Preparation steps:

[0053] The steps in Example 1 were repeated, and the material ratio was adjusted. The rest of the preparation method and operating conditions were the same as those in Example 1.

[0054] Embodiment 5:

[0055] A waterproof, wear-resistant, high-fidelity label anti-counterfeiting ink and a preparation method thereof, comprising the following contents:

[0056] Material ratio: 15 parts of organic ultraviolet fluorescent pigment, 6.5 parts of cosolvent, 30 parts of oil phase solvent, 60 parts of deionized water a, 22 parts of oil phase crosslinking agent, 9 parts of emulsifier, 30 parts of wall material monomer, 2.8 parts of initiator, 0.6 parts of catalyst; 23 parts of fluorescent pigment microcapsules, 8 parts of modified nano-scale silica particles, 33 parts of water-based polyurethane resin, 5 parts of metal oxide pigment, 3 parts of crosslinking agent, and 15 parts of deionized water b.

[0057] Preparation steps:

[0058] The steps in Example 1 were repeated, and the material ratio was adjusted. The rest of the preparation method and operating conditions were the same as those in Example 1.

[0059] Comparative Example 1:

[0060] A waterproof, wear-resistant, high-fidelity label anti-counterfeiting ink and a preparation method thereof, comprising the following contents:

[0061] Material ratio: 18 parts of organic ultraviolet fluorescent pigment, 7 parts of modified nano-scale silica particles, 30 parts of waterborne polyurethane resin, 5 parts of metal oxide pigment, 2 parts of cross-linking agent, and 18 parts of deionized water b.

[0062] Preparation steps:

[0063] S1: Ultrasonic dispersion of nano-scale silica particles in a mixed solution of ethanol and isopropanol for 30 to 45 minutes to form a uniform nano-scale silica particle suspension, adding γ-glycidyl ether propyl trimethoxysilane to the uniform nano-scale silica particle suspension, controlling the temperature at 55°C to 65°C and the pH value at 8 to 9, reacting for 2 to 3 hours, cooling and centrifuging to obtain modified nano-scale silica particles;

[0064] S2: Add modified nano-scale silica particles to water-based polyurethane resin, stir evenly, add organic ultraviolet fluorescent pigment, metal oxide pigment, crosslinking agent and deionized water b in sequence, stir for 20min to 30min, stirring speed is 1600 to 2000rpm, add defoaming agent and continue stirring for 5min to 10min, stirring at 800 to 1200rpm. After defoaming, let the mixture stand until the bubbles disappear completely to obtain waterproof, wear-resistant and high-fidelity label anti-counterfeiting ink.

[0065] Comparative Example 2:

[0066] In Comparative Example 2, the nano-sized silica particles were not modified, and nano-sized silica particles were used instead of the modified nano-sized silica particles. The rest of the raw material ratios, preparation methods, and operating conditions were the same as those in Example 1.

[0067] The "ab" after the above material names is only used for marking, and the materials are essentially the same.

[0068] The waterproof, wear-resistant, high-fidelity label anti-counterfeiting inks prepared in Examples 1-5 and Comparative Examples 1-2 were tested according to the testing standard B / T2024-94B / T2024-94. The detailed results are shown in Table 1:

[0069] Table 1

[0070]

[0071] 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 method for preparing a waterproof, wear-resistant and high-fidelity anti-counterfeiting ink for labels, characterized in that: The steps include: S1: Mixing an organic ultraviolet fluorescent pigment, a cosolvent, an oil phase solvent, and an oil phase crosslinking agent according to a ratio, heating and dissolving the mixture to obtain an oil phase solution; adding an emulsifier to deionized water a to form an aqueous phase solution, slowly dropping the oil phase solution into the aqueous phase solution, and stirring at a high speed of 1200 to 1500 rpm for 30 to 60 minutes to form a stable emulsion, adding a wall material monomer, an initiator, and a catalyst to the emulsion, and continuing to stir at 500 to 800 rpm, controlling the temperature at 60° C. to 80° C. and the pH value at 8 to 9, and performing an interfacial polymerization reaction for 40 to 60 minutes to form a microcapsule shell layer on the surface of the oil droplets to obtain fluorescent pigment microcapsules; S2: Ultrasonic dispersion of nano-scale silica particles in a mixed solution of ethanol and isopropanol for 30 to 45 minutes to form a uniform nano-scale silica particle suspension, adding γ-glycidyl ether propyl trimethoxysilane to the uniform nano-scale silica particle suspension, controlling the temperature at 55° C. to 65° C. and the pH value at 8 to 9, reacting for 2 to 3 hours, cooling, centrifuging and washing to obtain modified nano-scale silica particles; S3: Add modified nano-scale silica particles to waterborne polyurethane resin, stir evenly, add fluorescent pigment microcapsules, metal oxide pigments, crosslinking agent and deionized water b in sequence, stir for 20min to 30min, stirring at a speed of 1600 to 2000rpm, add defoaming agent and continue stirring for 5min to 10min, stirring at 800 to 1200rpm. After defoaming is completed, let the mixture stand until the bubbles disappear completely.

2. The method for preparing a waterproof, wear-resistant and high-fidelity anti-counterfeiting ink for labels according to claim 1, characterized in that: The organic ultraviolet fluorescent pigment is coumarin dye; the cosolvent is 1-hexadecanol; the oil phase solvent is any one of phenyl benzoate, benzophenone and benzyl phenyl ether; the oil phase crosslinker is toluene diisocyanate; and the emulsifier is composed of gum arabic and sodium dodecyl sulfate in a mass ratio of 1:

3.

3. The method for preparing a waterproof, wear-resistant and high-fidelity anti-counterfeiting ink for labels according to claim 1, characterized in that: The wall material monomer is composed of ethylenediamine and hexamethylenediamine, and the mass ratio of ethylenediamine to hexamethylenediamine is 1:1; the initiator is ammonium persulfate; and the catalyst is tetramethylethylenediamine.

4. The method for preparing a waterproof, wear-resistant and high-fidelity anti-counterfeiting ink for labels according to claim 1, characterized in that: The weight proportions of the organic ultraviolet fluorescent pigment, cosolvent, oil phase solvent, oil phase crosslinking agent, deionized water, emulsifier, wall material monomer, initiator and catalyst are as follows: 12 to 16 parts of organic ultraviolet fluorescent pigment, 5 to 7 parts of cosolvent, 20 to 30 parts of oil phase solvent, 16 to 28 parts of oil phase crosslinking agent, 40 to 50 parts of deionized water, 7 to 10 parts of emulsifier, 20 to 36 parts of wall material monomer, 2 to 3 parts of initiator and 0.2 to 0.8 parts of catalyst.

5. The method for preparing a waterproof, wear-resistant and high-fidelity anti-counterfeiting ink for labels according to claim 1, characterized in that: The mass ratio of ethanol to isopropanol in the ethanol and isopropanol mixed solution is 3:

1.

6. The method for preparing a waterproof, wear-resistant and high-fidelity anti-counterfeiting ink for labels according to claim 1, characterized in that: The mass ratio of the nano-scale silicon dioxide particles, gamma-glycidyl ether propyl trimethoxysilane and the mixed solution of ethanol and isopropanol is 1:1:

5.

7. The method for preparing a waterproof, wear-resistant and high-fidelity anti-counterfeiting ink for labels according to claim 1, characterized in that: The metal oxide pigment is a mixture of yellow iron oxide, red iron oxide and titanium dioxide, and the mass ratio of the yellow iron oxide, red iron oxide and titanium dioxide is 2:2:1; the cross-linking agent is hexamethylene diisocyanate or toluene diisocyanate.

8. A waterproof, wear-resistant and high-fidelity anti-counterfeiting ink for labels, characterized in that: The invention is obtained by the preparation method of a waterproof, wear-resistant and high-fidelity label anti-counterfeiting ink as described in any one of claims 1 to 7, wherein the waterproof, wear-resistant and high-fidelity label anti-counterfeiting ink is composed of 18 to 25 parts of fluorescent pigment microcapsules, 7 to 10 parts of modified nano-scale silica particles, 30 to 40 parts of water-based polyurethane resin, 5 to 7 parts of metal oxide pigments, 2 to 5 parts of cross-linking agent and 13 to 38 parts of deionized water b in parts by weight.

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