阅读说明：本技术 一种水溶性红色有机荧光染料及其制备方法以及一种水性隐形红色荧光防伪油墨和使用方法 (Water-soluble red organic fluorescent dye and preparation method thereof, and water-based invisible red fluorescent anti-counterfeiting ink and use method thereof ) 是由 张国庆 张学鹏 廖凡 于 2018-07-05 设计创作，主要内容包括：本发明提供了一类水性隐形红色荧光防伪油墨及其制备方法以及使用方法,其用到的染料水溶液中的荧光分子在可见光区没有吸收,所以油墨在普通日光条件下而无色透明,完全隐形,只有在紫外照射时才显示鲜艳荧光,进而提高了对比度和防伪安全性；同时本发明提供的水性隐形荧光防伪油墨体系用水作溶解载体,与以往的油性染料相比安全无毒、无挥发性有机气体产生,无污染,减少资源消耗和降低环保成本,无燃爆风险,提高了作业环境的安全性；另外,本发明提供的水性隐形荧光防伪油墨的荧光颜色克服了目前荧光防伪染料往往颜色单一的问题。(The invention provides a water-based invisible red fluorescent anti-counterfeiting ink and a preparation method and a use method thereof, fluorescent molecules in a dye aqueous solution used in the ink are not absorbed in a visible light area, so the ink is colorless and transparent under the condition of common sunlight and is completely invisible, and bright fluorescence can be displayed only when the ink is irradiated by ultraviolet light, thereby the contrast and the anti-counterfeiting safety are improved; meanwhile, the water-based invisible fluorescent anti-counterfeiting ink system provided by the invention takes water as a dissolving carrier, is safe and nontoxic, does not generate volatile organic gas, is pollution-free, reduces resource consumption and environmental protection cost, has no burning and explosion risks, and improves the safety of the operating environment compared with the conventional oily dye; in addition, the fluorescent color of the water-based invisible fluorescent anti-counterfeiting ink provided by the invention overcomes the problem that the existing fluorescent anti-counterfeiting dye is single in color.)

1. A water-soluble red organic fluorescent dye, which is characterized by having a structure shown in formula (I):

R₁，R₂independently selected from hydrophilic aryl, n-3 or 4.

2. The water-soluble organic fluorescent dye according to claim 1, wherein R is₁，R₂Independently selected from pyridyl, a group obtained by losing hydrogen on one terminal hydroxyl group of polyethylene glycol, a benzene ring modified by hydroxyl, amino or carboxyl, a group obtained by losing hydrogen on one terminal hydroxyl group of polyethylene glycol, and a naphthalene ring modified by hydroxyl, amino or carboxyl.

3. The water-soluble organic fluorescent dye according to claim 1, selected from

4. A method for preparing the water-soluble organic fluorescent dye according to claim 1, comprising the steps of:

A) mixing carboxylic ester compounds and ketone compounds, and carrying out claisen condensation reaction under the catalysis of strong base to obtain beta-diketone compounds;

B) mixing and heating the beta-diketone compound and europium nitrate, and reacting to obtain the water-soluble organic fluorescent dye with the structure shown in the formula (I):

R₁，R₂independently selected from hydrophilic aryl, n-3 or 4.

5. The preparation method according to claim 4, wherein the carboxylic ester compound is selected from one or more of methyl nicotinate, ethyl nicotinate, methyl benzoate, ethyl p-methoxybenzoate and ethyl p-hydroxybenzoate;

the ketone compound is selected from one or more of 3-acetylpyridine, acetophenone, p-methoxyacetophenone and p-hydroxyacetophenone;

the strong base is selected from sodium hydroxide, potassium tert-butoxide, sodium tert-butoxide or sodium hydride;

the temperature of the condensation reaction is 35-40 ℃; the condensation reaction time is 2-10 h;

in the step B), the reaction is a heating reflux reaction; the reaction time is 1-1.5 h.

6. The water-based invisible red fluorescent anti-counterfeiting ink is characterized by comprising the following components in parts by weight: the material is prepared by mixing the following raw materials in percentage by mass:

10-50 wt% of water-soluble organic fluorescent dye aqueous solution with the structure shown in the formula (I), wherein the mass concentration of the water-soluble organic fluorescent dye in the water-soluble organic fluorescent dye aqueous solution with the structure shown in the formula (I) is 0.5-50 g/L;

50-89 wt% of water-based resin

1 to 3 weight percent of surfactant.

7. The aqueous invisible red fluorescent anti-counterfeiting ink according to claim 1, wherein the aqueous resin is selected from aqueous acrylic resin, aqueous epoxy resin, aqueous polyurethane resin, aqueous modified polybutadiene resin, aqueous alkyd resin, aqueous amino resin, aqueous polyester resin and aqueous phenolic resin; the surfactant is selected from polyvinylpyrrolidone or sodium dodecyl benzene sulfonate.

8. The preparation method of the water-based invisible red fluorescent anti-counterfeiting ink according to any one of claims 6 to 7, characterized by comprising the following steps:

mixing aqueous resin, a surfactant and an aqueous solution of a water-soluble organic fluorescent dye with a structure shown in a formula (I), and then carrying out ultrasonic treatment to obtain the aqueous invisible red fluorescent anti-counterfeiting ink.

9. The use method of the water-based invisible red fluorescent anti-counterfeiting ink according to any one of claims 6 to 7, characterized by comprising the following steps:

coating or printing the water-based invisible red fluorescent anti-counterfeiting ink as claimed in any one of claims 6 to 7 on the surface of a product, and drying to obtain an anti-counterfeiting product;

the trace and the color of the water-based invisible fluorescent anti-counterfeiting ink on the surface of the anti-counterfeiting product can not be seen under sunlight, and the area coated or printed with the water-based invisible fluorescent anti-counterfeiting ink on the surface of the product can show fluorescence under the irradiation of an ultraviolet lamp.

Technical Field

The invention belongs to the technical field of printing ink, and particularly relates to a water-soluble red organic fluorescent dye and a preparation method thereof, as well as a water-based invisible red fluorescent anti-counterfeiting printing ink and a use method thereof.

Background

Currently, anti-counterfeiting ink can be divided into non-fluorescent anti-counterfeiting ink and fluorescent anti-counterfeiting ink according to the anti-counterfeiting function. The non-fluorescent anti-counterfeiting ink comprises thermochromic ink (such as a thermal response polymer-polyethylene diyne material), photochromic ink (such as azobenzene material and spiropyran material), magnetic color-changing ink (such as ferrocene material), humidity-sensitive color-changing ink (such as siloxane material) and chemical reaction color-changing ink (such as color-changing ink induced by acid-base and indicator reaction, oxidation reduction or enzyme reaction), and the ink is very complex in synthesis, high in cost, poor in stability, short in service life and inconvenient to detect. The second type is fluorescent anti-counterfeiting ink which is prepared from fluorescent dye, namely, corresponding fluorescent compound is added into common ink, and visible fluorescence is displayed under the irradiation of ultraviolet rays. Compared with non-fluorescent ink, the anti-counterfeiting ink has the advantages of convenience and sensitivity in inspection, good safety, good stability and the like, is more concerned in anti-counterfeiting technology, has wider application field, and has been applied to anti-counterfeiting fields of paper money, securities, certificates and the like at home and abroad. The main disadvantages of the fluorescent anti-counterfeiting ink developed at present are as follows: firstly, the materials are absorbed in a visible light area, so that the materials can show a certain color under sunlight, and the anti-counterfeiting effect is reduced; secondly, the fluorescent molecules used in the existing ink are all oil-soluble, only volatile and toxic organic solvents (such as dichloromethane, chloroform, tetrahydrofuran, acetonitrile and the like) can be used in the production and preparation processes, the solvents are not only easy to be absorbed into the body by research and development and workers, causing harm to health, but also easy to diffuse into the atmosphere and polluting the environment, and are all flammable and explosive products, so that great potential safety hazards exist in industrial production (the current frequent chemical plant explosion accidents are mostly caused by the organic solvents and the gases thereof).

Disclosure of Invention

In view of the above, the technical problem to be solved by the present invention is to provide an aqueous invisible fluorescent anti-counterfeiting ink, a preparation method and a use method thereof, the aqueous invisible red fluorescent anti-counterfeiting ink obtained from the water-soluble red organic fluorescent dye provided by the present invention is colorless and transparent under ordinary sunlight conditions, is completely invisible, shows bright fluorescence only under ultraviolet irradiation, and is safe, non-toxic and pollution-free by using water as a dissolution carrier.

The invention provides a water-soluble red organic fluorescent dye, which has a structure shown in a formula (I):

R₁，R₂independently selected from hydrophilic aryl, n-3 or 4.

Preferably, said R is₁，R₂Independently selected from pyridyl, a group obtained by losing hydrogen on one terminal hydroxyl group of polyethylene glycol, a benzene ring modified by hydroxyl, amino or carboxyl, a group obtained by losing hydrogen on one terminal hydroxyl group of polyethylene glycol, and a naphthalene ring modified by hydroxyl, amino or carboxyl.

Preferably, selected from

Wherein m is 1 to 100.

The invention also provides a preparation method of the water-soluble organic fluorescent dye, which comprises the following steps:

A) mixing carboxylic ester compounds and ketone compounds, and carrying out claisen condensation reaction under the catalysis of strong base to obtain beta-diketone compounds;

B) mixing and heating the beta-diketone compound and europium nitrate, and reacting to obtain the water-soluble organic fluorescent dye with the structure shown in the formula (I):

R₁，R₂independently selected from hydrophilic aryl, n-3 or 4.

Preferably, the carboxylate compound is selected from one or more of methyl nicotinate, ethyl nicotinate, methyl benzoate, ethyl p-methoxybenzoate and ethyl p-hydroxybenzoate;

the ketone compound is selected from one or more of 3-acetylpyridine, acetophenone, p-methoxyacetophenone and p-hydroxyacetophenone;

the strong base is selected from sodium hydroxide, potassium tert-butoxide, sodium tert-butoxide or sodium hydride;

the temperature of the condensation reaction is 35-40 ℃; the condensation reaction time is 2-10 h;

in the step B), the reaction is a heating reflux reaction; the reaction time is 1-1.5 h.

The invention also provides water-based invisible red fluorescent anti-counterfeiting ink which is prepared by mixing the following raw materials in percentage by mass:

10-50 wt% of water-soluble organic fluorescent dye aqueous solution with the structure shown in the formula (I), wherein the mass concentration of the water-soluble organic fluorescent dye in the water-soluble organic fluorescent dye aqueous solution with the structure shown in the formula (I) is 0.5-50 g/L;

50-89 wt% of water-based resin

1 to 3 weight percent of surfactant.

Preferably, the aqueous resin is selected from aqueous acrylic resin, aqueous epoxy resin, aqueous polyurethane resin, aqueous modified polybutadiene resin, aqueous alkyd resin, aqueous amino resin, aqueous polyester resin and aqueous phenolic resin; the surfactant is selected from polyvinylpyrrolidone or sodium dodecyl benzene sulfonate.

The invention also provides a preparation method of the water-based invisible red fluorescent anti-counterfeiting ink, which comprises the following steps:

mixing aqueous resin, a surfactant and an aqueous solution of a water-soluble organic fluorescent dye with a structure shown in a formula (I), and then carrying out ultrasonic treatment to obtain the aqueous invisible red fluorescent anti-counterfeiting ink.

The invention also provides a using method of the water-based invisible red fluorescent anti-counterfeiting ink, which comprises the following steps:

coating or printing the water-based invisible red fluorescent anti-counterfeiting ink on the surface of a product and then drying to obtain an anti-counterfeiting product;

the trace and the color of the water-based invisible fluorescent anti-counterfeiting ink on the surface of the anti-counterfeiting product can not be seen under sunlight, and the area coated or printed with the water-based invisible fluorescent anti-counterfeiting ink on the surface of the product can show fluorescence under the irradiation of an ultraviolet lamp.

Compared with the prior art, the invention provides a water-soluble red organic fluorescent dye, which has a structure shown in a formula (I):

R₁，R₂independently selected from hydrophilic aryl, n-3 or 4.

The invention provides a water-soluble red organic fluorescent dye, molecules of which do not absorb in a visible light area, so that the obtained ink is colorless and transparent under the condition of common sunlight and is completely invisible, and the obtained ink can only display bright red fluorescence under ultraviolet irradiation, thereby improving the contrast and the anti-counterfeiting safety; meanwhile, the water-based invisible red fluorescent anti-counterfeiting ink system provided by the invention uses water as a dissolving carrier, and compared with the conventional oily dye, the water-based invisible red fluorescent anti-counterfeiting ink system is safe, non-toxic, free of volatile organic gas generation, pollution-free, capable of reducing resource consumption and environmental protection cost, free of burning and explosion risks, and capable of improving the safety of the operation environment; in addition, the fluorescent color of the water-based invisible fluorescent anti-counterfeiting ink provided by the invention is red, and the water-based invisible fluorescent anti-counterfeiting ink can be randomly combined with inks with different colors into different shapes and color patterns, so that the anti-counterfeiting performance is improved, the ink is not easy to copy, and the problem that the existing fluorescent anti-counterfeiting dye is single in color is solved.

Drawings

FIG. 1 is a photograph of the aqueous invisible red fluorescent anti-counterfeiting ink prepared in example 2 under sunlight (left) and ultraviolet light (right);

FIG. 2 is a fluorescence spectrum of the aqueous invisible red fluorescent anti-counterfeiting ink prepared in example 2;

FIG. 3 is a photograph of the aqueous invisible red fluorescent anti-counterfeiting ink prepared in example 4 under sunlight (left) and ultraviolet light (right);

FIG. 4 is a fluorescence spectrum of the aqueous invisible red fluorescent anti-counterfeiting ink prepared in example 4.

Detailed Description

The invention provides a water-soluble red organic fluorescent dye, which has a structure shown in a formula (I):

R₁，R₂independently selected from hydrophilic aryl, n-3 or 4.

In some embodiments of the invention, R is₁，R₂Independently selected from pyridyl, a group obtained by losing hydrogen on one terminal hydroxyl group of polyethylene glycol, a benzene ring modified by hydroxyl, amino or carboxyl, a group obtained by losing hydrogen on one terminal hydroxyl group of polyethylene glycol, and a naphthalene ring modified by hydroxyl, amino or carboxyl.

In some embodiments of the invention, R is₁，R₂Independently selected from pyridyl, a group obtained by losing hydrogen on one terminal hydroxyl of polyethylene glycol, hydroxyl, amino or carboxyl modified benzene ring.

In some embodiments of the invention, the water-soluble red organic fluorescent dye is selected from

Wherein m is 1-100, preferably, m is 3-50, and further preferably, m is 5-30.

The invention also provides a preparation method of the water-soluble organic fluorescent dye, which comprises the following steps:

A) mixing carboxylic ester compounds and ketone compounds, and carrying out claisen condensation reaction under the catalysis of strong base to obtain beta-diketone compounds;

B) mixing and heating the beta-diketone compound and europium nitrate, and reacting to obtain the water-soluble organic fluorescent dye with the structure shown in the formula (I):

R₁，R₂independently selected from hydrophilic aryl, n-3 or 4.

Specifically, according to the invention, firstly, carboxylic ester compounds and ketone compounds are mixed according to the weight ratio of 1: 1 equivalent was mixed to obtain a mixture. Wherein the carboxylic ester compound is selected from one or more of methyl nicotinate, ethyl nicotinate, methyl benzoate, ethyl p-methoxybenzoate and ethyl p-hydroxybenzoate; the ketone compound is one or more selected from 3-acetylpyridine, acetophenone, p-methoxyacetophenone and p-hydroxyacetophenone.

And then, carrying out a claisen condensation reaction on the mixture under the catalysis of strong alkali to obtain the beta-diketone compound.

Wherein the strong base is selected from sodium hydroxide, potassium tert-butoxide, sodium tert-butoxide or sodium hydride; the temperature of the condensation reaction is 35-40 ℃; the condensation reaction time is 2-10 hours, preferably 4-8 hours;

and then, mixing and heating the beta-diketone compound and europium nitrate for reaction to obtain the water-soluble organic fluorescent dye with the structure shown in the formula (I).

Wherein the reaction is a heating reflux reaction; the reaction time is 1-1.5 h.

The invention also provides water-based invisible red fluorescent anti-counterfeiting ink which is prepared by mixing the following raw materials in percentage by mass:

10-50 wt% of water-soluble organic fluorescent dye aqueous solution with the structure shown in the formula (I), wherein the mass concentration of the water-soluble organic fluorescent dye in the water-soluble organic fluorescent dye aqueous solution with the structure shown in the formula (I) is 0.5-50 g/L;

50-89 wt% of water-based resin

1 to 3 weight percent of surfactant.

The water-based invisible red fluorescent anti-counterfeiting ink provided by the invention comprises 10-50 wt% of water solution of water-soluble organic fluorescent dye with the structure shown in the formula (I), preferably 20-40 wt%, and more preferably 25-35 wt%.

Wherein the mass concentration of the water-soluble organic fluorescent dye in the water solution of the water-soluble organic fluorescent dye with the structure shown in the formula (I) is 0.5-50 g/L, preferably 1.0-30 g/L, and more preferably 5-20 g/L.

The water-based invisible red fluorescent anti-counterfeiting ink provided by the invention also comprises 50 wt% -89 wt% of water-based resin, preferably 55 wt% -80 wt%, and more preferably 60 wt% -70 wt%. The water-based resin is selected from water-based acrylic resin, water-based epoxy resin, water-based polyurethane resin, water-based modified polybutadiene resin, water-based alkyd resin, water-based amino resin, water-based polyester resin and water-based phenolic resin; more preferably an aqueous acrylic resin or an aqueous urethane resin.

The water-based invisible red fluorescent anti-counterfeiting ink provided by the invention also comprises 1 wt% -3 wt% of a surfactant, preferably polyvinylpyrrolidone or sodium dodecyl benzene sulfonate.

The invention also provides a preparation method of the water-based invisible red fluorescent anti-counterfeiting ink, which comprises the following steps:

mixing aqueous resin, a surfactant and an aqueous solution of a water-soluble organic fluorescent dye with a structure shown in a formula (I), and then carrying out ultrasonic treatment to obtain the aqueous invisible red fluorescent anti-counterfeiting ink.

Wherein the time of ultrasonic treatment is 2-5 min, preferably 3 min.

The invention also provides a using method of the water-based red invisible fluorescent anti-counterfeiting ink, which comprises the following steps:

coating or printing the water-based invisible red fluorescent anti-counterfeiting ink on the surface of a product and then drying to obtain an anti-counterfeiting product;

the trace and the color of the water-based invisible red fluorescent anti-counterfeiting ink on the surface of the anti-counterfeiting product can not be seen under sunlight, and the area coated or printed with the water-based invisible fluorescent anti-counterfeiting ink on the surface of the product can show fluorescence under the irradiation of an ultraviolet lamp.

The invention provides water-based invisible red fluorescent anti-counterfeiting ink, wherein fluorescent molecules in a dye aqueous solution used in the ink are not absorbed in a visible light area, so that the ink is colorless and transparent under the condition of common sunlight and is completely invisible, and the ink can display bright fluorescence only under ultraviolet irradiation, thereby improving the contrast and anti-counterfeiting safety; meanwhile, the water-based invisible red fluorescent anti-counterfeiting ink system provided by the invention uses water as a dissolving carrier, and compared with the conventional oily dye, the water-based invisible red fluorescent anti-counterfeiting ink system is safe, non-toxic, free of volatile organic gas generation, pollution-free, capable of reducing resource consumption and environmental protection cost, free of burning and explosion risks, and capable of improving the safety of the operation environment; in addition, the fluorescent color of the water-based invisible fluorescent anti-counterfeiting ink provided by the invention is red, and the water-based invisible fluorescent anti-counterfeiting ink can be randomly combined with inks with different colors into different shapes and color patterns, so that the anti-counterfeiting performance is improved, the ink is not easy to copy, and the problem that the existing fluorescent anti-counterfeiting dye is single in color is solved.

For further understanding of the present invention, the following examples are provided to illustrate the water-soluble red organic fluorescent dye and the preparation method thereof, and the aqueous invisible red fluorescent anti-counterfeiting ink and the using method thereof, and the scope of the present invention is not limited by the following examples.