CN103242699A - Ultraviolet excited green fluorescent inkjet ink for printing and imaging by additive method and preparation method - Google Patents

Abstract

The invention relates to an ultraviolet-excited green fluorescent ink-jet ink for additive color printing and imaging and a preparation method, belonging to the technical field of anti-counterfeiting printing. The composition and weight ratio of the ink are: 0.1-10 parts of ultraviolet-excited green fluorescent anti-counterfeiting materials, 15-50 parts of ester solvents, 15-30 parts of sulfur-containing solvents, 5-30 parts of synthetic resins, and 15-30 parts of ether solvents. 40 parts, nitrogen-containing solvent 10~30 parts, surfactant 0.5~3 parts, pH regulator 0.5~3 parts. The preparation process of the ink of the present invention is simple, and only needs magnetic stirring and heat treatment to completely dissolve and mix the components evenly. The green fluorescent anti-counterfeiting ink-jet ink of the present invention is suitable for printing invisible one-dimensional barcodes and two-dimensional barcodes on various securities, bills, trademarks and the like. The process is simple in operation, strong in concealment, and can effectively prevent copying and counterfeiting.

Description

Ultraviolet-excited green fluorescent inkjet ink for color additive printing and imaging and its preparation method

technical field

The invention relates to an ultraviolet-excited green fluorescent ink-jet ink for color-additive printing and imaging and a preparation method. The ink is a printing ink-jet ink and belongs to the technical field of anti-counterfeiting printing.

Background technique

With the improvement of living standards and environmental protection awareness, people have put forward higher requirements for anti-counterfeiting of packaging and printing products. At present, there are a variety of counterfeit products in the market, flooding every corner of the market, which has seriously harmed the interests of producers and consumers. People began to pay more attention to the application of anti-counterfeiting technology in printed matter, not only expecting it to achieve the expected anti-counterfeiting effect, but also to meet high-quality printing performance, simple operation, and high anti-counterfeiting performance. This is a topic that many manufacturers and consumers pay more attention to.

Most of the traditional anti-counterfeiting inks use printing processes such as offset printing and screen printing. The process is complicated and cannot meet the needs of modern life.

Contents of the invention

The invention provides a novel UV-excited green fluorescent ink-jet ink formula and a preparation method thereof. The printing method of this fluorescent inkjet ink is inkjet printing, which is simple and feasible, and has excellent anti-counterfeiting performance, simple operation, low cost, good concealment, bright colors, convenient inspection and other characteristics of general anti-counterfeiting inks. The main feature is one of the ingredients used in the formulation of additive color imaging techniques.

In order to achieve the above object, the present invention takes the following technical solutions:

An ultraviolet-excited green fluorescent inkjet ink, used for color-additive printing and imaging, is prepared by mixing commercially available ultraviolet-excited green fluorescent anti-counterfeiting materials (ultraviolet-absorbing green fluorescent anti-counterfeiting materials), synthetic resins, solvents, and additives, including The following composition and weight ratio:

UV-excited green fluorescent anti-counterfeiting material: 0.1~10 parts

Synthetic resin: 5~30 parts

Ester solvent: 15~50 parts

Ether solvent: 15~40 parts

Nitrogen-containing solvents: 10~30 parts

Sulfur-containing solvents: 10~30 parts

Surfactant: 0.5~3 parts

pH adjuster: 0.5~3 parts.

The ultraviolet-excited green fluorescent anti-counterfeiting material in the present invention is an ultraviolet-absorbing material with an excitation (absorption) wavelength of 220-450nm, and emits green light with a wavelength range of 500-600nm. After being put on the object, it is colorless visually, and it shows a gorgeous green color after being irradiated by ultraviolet light. It has strong concealment and can effectively prevent copying and counterfeiting.

The synthetic resin is one or a mixture of two or more of acrylic resin, epoxy resin, polyurethane resin, vinyl resin and phenolic resin.

Described ester solvent is one or both in ethyl acetate, methyl formate, butyl ester, propylene glycol methyl ether acetate, methyl acetate, ethyl butyrate, propylene glycol methyl ether propionate and ethyl benzoate mixture of the above.

The ether solvent is one or a mixture of two or more of propylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol butyl ether and 1,4-dioxane.

The nitrogen-containing solvent is one or a mixture of two or more of N,N-methylformamide, N,N-methylacetamide, N-methylpyrrolidone and formamide.

The sulfur-containing solvent is one or a mixture of dimethyl sulfoxide and sulfolane.

The surfactant is one or a mixture of two or more of silicone surfactants and organic fluorine surfactants.

The pH regulator is one or a mixture of two or more of N,N-dimethylformamide, triethanolamine and triethylamine.

The preparation method of above-mentioned ultraviolet excitation green fluorescent ink-jet ink, comprises the following steps:

(1) Mix the ultraviolet-excited green fluorescent anti-counterfeiting material with sulfur-containing solvents and ester solvents according to the stated ratio, heat and stir at 30-55°C to obtain component A;

(2) Mix the synthetic resin with the ether solvent and the nitrogen-containing solvent according to the stated ratio, and stir evenly to obtain component B;

(3) Mix the components A and B, stir until the solution is completely transparent, then add a surfactant and a pH regulator, and mix and stir evenly to obtain the ink, which can be spray-painted on the substrate.

In step (1), the heating and stirring time of the component A is 45-60 minutes.

In step (2), the stirring time of the B component is 20-40 minutes.

In step (3), the A component and the B component are mixed, and the stirring time is 30-60 min; the surfactant and the pH regulator are added, and the mixing and stirring time is 10-25 min.

The pH of the ultraviolet-excited green fluorescent inkjet ink of the present invention is 6.82-8.97, the surface tension is 22.36-34.66mN/m, the viscosity is 2.43-4.57mPa·S, and the fluorescence intensity of the ink is 532.538-629.320cd, which can be sprayed onto white cards On various substrates such as paper, coated paper, offset paper, aluminum foil paper, photo paper, rice paper, etc., when there is no ultraviolet light source, it is colorless or nearly colorless, and under the irradiation of a specific ultraviolet light source, it appears bright green. Obviously, it can play an anti-counterfeiting effect very well.

The preparation process of the ink of the present invention is simple, and it can be completely dissolved only through magnetic stirring and heat treatment, so that the components can be mixed uniformly.

The ultraviolet-absorbing green fluorescent anti-counterfeiting ink-jet ink of the present invention is prepared and processed from commercially available ultraviolet-absorbing green fluorescent materials, synthetic resins, solvents, auxiliary agents and the like. The green fluorescent anti-counterfeiting ink-jet ink of the present invention is suitable for printing invisible one-dimensional barcodes and two-dimensional barcodes on various securities, bills, trademarks and the like. The process is simple in operation, strong in concealment, and can effectively prevent copying and counterfeiting.

Detailed ways

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, various changes or modifications made by those skilled in the art to the present invention, and these equivalent forms also fall within the scope of protection claimed by the present application. The proportions in the embodiments of the present invention are all by weight.

Example 1

Add 0.5 parts of UV-excited green to 13.5 parts of dimethyl sulfoxide (analytical pure), 31.5 parts of methyl acetate (analytical pure): butyl ester (analytical pure) in a mixed ester solvent of 1:4 (weight ratio) Fluorescent anti-counterfeiting material (hereinafter referred to as green fluorescent material), heated magnetically and stirred evenly at 30°C, stirred for 45 minutes to form component A; added 11 parts of N,N-methyl formazan to 15.5 parts of epoxy resin (commercially available) Amide (analytical pure), 26.5 parts of propylene glycol methyl ether (analytical pure) ether solvent, in which synthetic resin is, after magnetic stirring evenly, component B is formed, components A and B are mixed and stirred for 30 minutes until the solution is completely transparent, add 1 part Organic fluorine surfactant (TEGO), 0.5 parts of pH regulator triethanolamine (analytical pure). Mix and stir for 20 minutes to obtain the ink, which can be spray-painted on the substrate.

Chemical name of green fluorescent material: 6-chloro-2-[5-chloro-2-(4-biphenylsulfonylamino)]phenyl-4-benzoxazinone, absorption wavelength is 300~400nm, emission wavelength is 500~600nm, the specific structure is:

In the following embodiments, this kind of phosphor is used as the green fluorescent material.

Example 2

Add 3.5 parts of green fluorescent material to 17.5 parts of sulfolane (analytical pure) and 34.5 parts of propylene glycol methyl ether acetate (analytical pure), heat and magnetically stir evenly at a temperature of 55 ° C, and stir for 50 minutes to form A component; add 15.5 parts Add 13.5 parts of N,N-methylacetamide (analytical pure) and 17 parts of ethylene glycol ethyl ether (analytical pure) to polyurethane resin (commercially available), and stir magnetically for 30 minutes to form component B, components A and B Mix and stir for 40 minutes until the solution is completely transparent, add 1 part of silicone surfactant (TEGO) and 1 part of pH regulator triethylamine (analytical pure). Mix and stir for 25 minutes to obtain the ink, which can be spray-painted on the substrate.

Example 3

Add 5 parts of green fluorescent material to 20 parts of sulfolane (analytically pure) and 15 parts of propylene glycol methyl ether acetate (analytical pure), heat and magnetically stir evenly at a temperature of 45°C, and stir for 60 minutes to form A component; add 19.5 parts Add 21.5 parts of ethylene glycol ether (analytical grade) and 19 parts of diethylene glycol butyl ether: 1,4-dioxane in a mixed ether solvent of 3:2 (weight ratio) to polyurethane resin (commercially available). After magnetically stirring for 30 minutes to form component B, mix and stir components A and B for 60 minutes until the solution is completely transparent, then add 2 parts of organic fluorine surfactant (TEGO) and 1 part of pH regulator N,N-dimethylformamide (analytical pure). Mix and stir for 10 minutes to obtain the ink, which can be spray-painted on the substrate.

Example 4

To 27.5 parts of sulfolane (analytical pure): dimethyl sulfoxide (analytical pure) with a mixed sulfur-containing solvent of 3:2 (weight ratio), 23.5 parts of methyl acetate (analytical pure): butyl ester (analytical pure) as Add 7.5 parts of green fluorescent material to a 2:1 (weight ratio) mixed ester solvent, heat and magnetically stir evenly (45min), and the temperature is 45°C to form component A; add 25 parts of epoxy resin (commercially available): Add 21 parts of diethylene glycol butyl ether (analytical pure) and 13 parts of propylene glycol methyl ether (analytical pure) to the mixed resin of 3:2 (weight ratio) of vinyl chloride resin (commercially available), and stir magnetically for 35 minutes to form Component B, components A and B were mixed and stirred for 50 minutes until the solution was completely transparent, and 1.5 parts of silicone surfactant (TEGO) and 0.5 parts of pH regulator N,N-dimethylformamide (analytical grade) were added. Mix and stir for 20 minutes to obtain the ink, which can be spray-painted on the substrate.

Example 5

Add 10 parts of green fluorescent material to 30 parts of dimethyl sulfoxide (analytical pure), 50 parts of methyl formate (analytical pure): propylene glycol methyl ether acetate (analytic pure) at a ratio of 4:1 (weight ratio), heat Stir evenly with magnetic force (45min) at a temperature of 55°C to form component A; add 30 parts of N-methylpyrrolidone (analytical pure) to 5 parts of vinyl acetate resin (commercially available): N-N dimethylacetamide (analytical pure ) is a 1:2 (weight ratio) mixed nitrogen-containing solvent and 15 parts of 1,4-dioxane (analytically pure), and after magnetically stirring for 20 minutes to form B component, A and B components are mixed and stirred for 30 minutes to The solution is completely transparent, and 0.5 parts of silicone surfactant (TEGO) and 0.5 parts of pH regulator triethylamine (analytical pure) are added. Mix and stir for 10 minutes to obtain the ink, which can be spray-painted on the substrate.

Example 6

To 10 parts of sulfolane (analytical pure): dimethyl sulfoxide (analytical pure) in a 1:1 (weight ratio) mixed sulfur-containing solvent, 20 parts of propylene glycol methyl ether acetate (analytical pure): ethyl benzoate ( Analytical pure) is 3:1 (weight ratio) mixed ester solvent, add 0.1 part of green fluorescent material, heat magnetic stirring evenly (60min), the temperature is 45 ℃, form A component; add 30 parts of polyurethane resin ( Commercially available), add 15 parts of formamide (analytical pure) and 40 parts of ethylene glycol ethyl ether (analytical pure), stir magnetically for 40 minutes to form component B, mix and stir components A and B for 30 minutes until the solution is completely transparent, add 3 parts of organic fluorine surfactant (TEGO), 3 parts of pH regulator triethylamine (analytical pure). Mix and stir for 25 minutes to obtain the ink, which can be spray-painted on the substrate.

The properties of the ink obtained in Examples 1-6 are shown in Table 1. The properties of the ultraviolet-excited green fluorescent inkjet ink prepared by the invention are as follows: the pH is 6.82-8.97, the surface tension is 22.36-34.66mN/m, the viscosity is 2.43-4.57mPa·S, and the fluorescence intensity of the ink is 532.538-629.320cd. Table 2 is the performance comparison of the ink of the present invention and the imported ink.

Table 1 The performance of embodiment 1-6 gained printing ink

Ink performance pH Surface Tension Viscosity Conductivity The fluorescence intensity Example 1 7.32 24.26 3.27 0 574.218 Example 2 7.84 25.17 4.09 0 532.537 Example 3 6.82 22.36 2.43 0 543.183 Example 4 8.39 27.32 3.38 0 588.392 Example 5 8.97 31.49 4.56 0 629.320 Example 6 7.83 34.66 3.74 0 532.538

The performance contrast of table 2 ink of the present invention and imported ink

Comparing the ink of the present invention with the imported (Yimashi 5553) UV-excited green fluorescent inkjet ink after simultaneous printing, it can be seen that the green ink of the present invention has high brightness, bright colors and good effects, while the Japanese green fluorescent inkjet ink has low brightness , the color is not bright.

In other embodiments of the present invention, each component of the ink can use the specific components listed in the Summary of the Invention that are different from Examples 1-6, and carry out different collocations and combinations, all of which can obtain the performance of the ink of the present invention and apply effects. The ultraviolet-excited green fluorescent ink-jet ink prepared by the present invention can be spray-painted on various substrates such as white cardboard, coated paper, offset paper, aluminum foil paper, photo paper, rice paper, etc., and is colorless or nearly colorless when no ultraviolet light source is irradiated. Under the irradiation of a specific ultraviolet light source, it presents a bright green color, the effect is obvious, and it can play a very good anti-counterfeiting effect.

Claims (10)

1. A UV-excited green fluorescent ink-jet ink for additive color printing imaging, which comprises the following composition and weight ratio: Ultraviolet excited green fluorescent anti-counterfeiting material: 0.1~10 parts Synthetic resin: 5~30 parts Ester solvent: 15~50 parts Ether solvent: 15~40 parts Nitrogen-containing solvents: 10~30 parts Sulfur-containing solvents: 10~30 parts Surfactant: 0.5~3 parts pH adjuster: 0.5~3 parts. 2. The ultraviolet-excited green fluorescent ink-jet ink for additive color printing and imaging according to claim 1, characterized in that: the excitation wavelength of the ultraviolet-excited green fluorescent anti-counterfeiting material is 220-450nm, and the emission wavelength is 500nm ~600nm. 3. the ultraviolet-excited green fluorescent ink-jet ink that is used for color additive printing and imaging according to claim 1, is characterized in that: described synthetic resin is acrylic resin, epoxy resin, polyurethane resin, vinyl chloride resin and phenolic resin One or more of the resins. 4. The UV-excited green fluorescent ink-jet ink for color additive printing and imaging according to claim 1, characterized in that: the ester solvent is ethyl acetate, methyl formate, butyl ester, propylene glycol methyl ether One or more of acetate, methyl acetate, ethyl butyrate, propylene glycol methyl ether propionate, and ethyl benzoate. 5. The ultraviolet-excited green fluorescent ink-jet ink used for color additive printing and imaging according to claim 1, characterized in that: the ether solvent is propylene glycol methyl ether, ethylene glycol ether, diethylene glycol butyl One or more of ether and 1,4-dioxane. 6. The ultraviolet-excited green fluorescent ink-jet ink for color additive printing and imaging according to claim 1, characterized in that: the nitrogen-containing solvent is N, N-dimethylformamide, N, N - one or more of dimethylacetamide, N-methylpyrrolidone and formamide; the sulfur-containing solvent is one or two of dimethyl sulfoxide and sulfolane. 7. The UV-excited green fluorescent inkjet ink for color additive printing and imaging according to claim 1, wherein the surfactant is one of an organic silicon surfactant and an organic fluorine surfactant or two or more. 8. The UV-excited green fluorescent ink-jet ink for color additive printing and imaging according to claim 1, characterized in that: the pH regulator is N,N-dimethylformamide, triethanolamine and triethyl One or more than two kinds of amines. 9. the preparation method of the ultraviolet-excited green fluorescent ink-jet ink that is used for additive color printing imaging described in any one in claim 1-8, comprises the steps: (1) Mix the ultraviolet-excited green fluorescent anti-counterfeiting material with sulfur-containing solvents and ester solvents according to the stated ratio, heat and stir at 30-55°C to obtain component A; (2) Mix the synthetic resin with the ether solvent and the nitrogen-containing solvent according to the stated ratio, and stir evenly to obtain component B; (3) Mix component A and component B, stir until the solution is completely transparent, then add surfactant and pH regulator, and mix and stir evenly. 10. The method for preparing an ultraviolet-excited green fluorescent inkjet ink for additive color printing and imaging according to claim 9, characterized in that: the heating and stirring time of the A component is 45 to 60 min; The stirring time of component B is 20-40min; the mixing of component A and component B is 30-60min; the time of adding surfactant and pH regulator is 10-25min.