Ink with fluorescent effect and preparation method and application thereof

Abstract

The present invention provides an ink with a fluorescent effect, a preparation method thereof, and an application thereof, and relates to the field of ink technology. The ink of the present invention comprises the following components by weight percentage: 5-10% fluorescent complex, 50-55% resin, 1-2% functional additive, and the remainder solvent; the preparation method of the fluorescent complex comprises: adding piroctone olamine salt to a fluorescent solution dissolved with a fluorescent substance, stirring and mixing to obtain a mixed solution; mixing and dissolving a coating matrix, a light stabilizer, and an antioxidant to obtain an additive solution; and mixing the mixed solution with the additive solution, and then curing and crushing to obtain the fluorescent complex. The present invention can improve the aging resistance of a fluorescent ink cured film.

Description

Technical Field

[0001] The present invention relates to the technical field of inks, and in particular to an ink with a fluorescent effect and a preparation method and application thereof. Background Art

[0002] Fluorescent ink is a special ink that can emit visible light under ultraviolet light or other specific wavelengths of light. It is mainly composed of fluorescent substances, solvents, resins and additives. Among them, fluorescent substances are the core components of fluorescent inks. They can absorb high-energy photons and then re-emit them in the form of lower-energy visible light, so that fluorescent inks exhibit fluorescent properties. Therefore, the properties of fluorescent substances determine the color and luminous effect of fluorescent inks.

[0003] Due to its fluorescent properties, fluorescent inks are widely used in applications requiring anti-counterfeiting measures, such as bills, certificates, and product packaging. Their fluorescence under specific wavelengths allows for authenticity verification. Furthermore, in fields such as advertising, decoration, and art, fluorescent inks offer vibrant and distinct color effects under varying lighting conditions, enabling the creation of richer, more recognizable, and recognizable works.

[0004] Currently, when preparing fluorescent ink, it is mainly necessary to select the fluorescent substance to be used, then choose a suitable solvent to dissolve the fluorescent substance and mix it with other substances. In addition, some functional additives can be added to the ink to improve the ink performance accordingly. However, after the fluorescent ink is cured on the surface of the product, after being exposed to ultraviolet light for a long time, the fluorescent substance in the ink is prone to photodegradation, resulting in a weakening of the fluorescence effect. Therefore, there is an urgent need to provide a solution to improve the above problems. Summary of the Invention

[0005] The purpose of the present invention is to provide an ink with fluorescent effect and a preparation method and application thereof.

[0006] The present invention provides an ink with a fluorescent effect, which comprises the following components by weight percentage: 5-10% of a fluorescent complex, 50-55% of a resin, 1-2% of a functional additive, and the remainder of a solvent. The preparation method of the fluorescent complex comprises: adding piroctone olamine salt into a fluorescent solution containing a fluorescent substance, stirring and mixing to obtain a mixed solution; mixing and dissolving a coating matrix, a light stabilizer, and an antioxidant to obtain an additive solution; and mixing the mixed solution with the additive solution, solidifying, and crushing the mixture to obtain the fluorescent complex.

[0007] Optionally, after the piroctone olamine salt is added to a fluorescent solution in which a fluorescent substance is dissolved, the mass mixing ratio of the piroctone olamine salt to the fluorescent substance is 1:(5-8).

[0008] Optionally, after the coating matrix, the light stabilizer and the antioxidant are mixed and dissolved to prepare the additive solution, the mass ratio of the coating matrix, the light stabilizer and the antioxidant is 1:(0.2-0.3):(0.1-0.3).

[0009] Optionally, after the mixed solution is mixed with the auxiliary agent solution, the mass ratio of the piroctone olamine salt to the coating matrix is 1:(2-2.5).

[0010] Optionally, the fluorescent substance includes at least one of fluorescein, rhodamine, coumarin, acriflavine, and rose bengal B.

[0011] Optionally, the coating matrix includes at least one of PUD-270, Carbomer-934, and Carbomer-941.

[0012] Optionally, the light stabilizer includes at least one of LQ-292, Tinuvin-320, Tinuvin-327, and IRGACURE-651.

[0013] Optionally, the antioxidant includes at least one of 2,6-di-tert-butyl-4-methylphenol, catechol, hydroquinone, and β-naphthol.

[0014] Optionally, the process of adding piroctone olamine salt into a fluorescent solution containing a fluorescent substance and stirring and mixing to prepare a mixed solution includes: dissolving the fluorescent substance to prepare a fluorescent solution; ultrasonically dispersing the modified nano-titanium dioxide into the fluorescent solution to prepare a dispersion; and stirring and dissolving the piroctone olamine salt in the dispersion, and stirring and reacting at 50-55° C. for 3-4 hours to prepare the mixed solution.

[0015] Optionally, the preparation method of the modified nano-titanium dioxide comprises: performing surface hydroxylation modification on the nano-titanium dioxide, and then immersing the nano-titanium dioxide in a phosphoric acid solution for phosphorylation to obtain the modified nano-titanium dioxide.

[0016] Optionally, after the modified nano-titanium dioxide is ultrasonically dispersed into the fluorescent solution, the mass ratio of the modified nano-titanium dioxide to the fluorescent substance is 1:(10-15).

[0017] Optionally, the average particle size of the modified nano-titanium dioxide is 10-100 nm.

[0018] Optionally, the functional additives include a defoaming agent, a leveling agent, and a dispersant.

[0019] Optionally, the defoaming agent includes at least one of BYK-052, HY-141, and BYK-052N.

[0020] Optionally, the leveling agent includes at least one of SH-450, MOK-2044, and BYK-333.

[0021] Optionally, the dispersant includes at least one of ECODIS P90 and ECODIS123K.

[0022] Optionally, the resin includes at least one of polyurethane resin, acrylic resin, epoxy resin, polyester resin, and nitrocellulose resin.

[0023] Optionally, the solvent comprises an ethanol solution with a volume ratio of 50-60%.

[0024] In a second aspect, the present invention provides a method for preparing an ink having a fluorescent effect, comprising the following steps: stirring and dissolving a fluorescent complex and a resin in a solvent to obtain a fluorescent resin, stirring and dispersing a functional additive in the fluorescent resin, and adjusting the solid content using a solvent to obtain an ink having a fluorescent effect.

[0025] In a third aspect, the present invention provides an application with a fluorescent effect. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments.

[0027] The present invention provides an ink with a fluorescent effect, comprising the following components, by weight: 5-10% fluorescent compound, 50-55% resin, 1-2% functional additive, and the balance solvent. The fluorescent compound imparts fluorescent properties to the ink, emitting visible fluorescence under specific lighting conditions. Furthermore, the compound effectively protects the core components within the ink.

[0028] In practice, the preparation method of the fluorescent complex includes:

[0029] S1. adding piroctone olamine salt into a fluorescent solution containing a fluorescent substance, stirring and mixing the solution to obtain a mixed solution;

[0030] S2, mixing and dissolving the coating substrate, light stabilizer and antioxidant to prepare an additive solution;

[0031] S3. The mixed solution is mixed with the auxiliary agent solution, and then solidified and crushed to obtain a fluorescent composite.

[0032] Specifically, after mixing piroctone olamine salt with a fluorescent solution, the functional groups on the salt, such as the amide group, hydroxyl group, and pyrrolidone ring, can interact with the fluorescent substance molecules to form a stable complex, thereby improving the stability and weather resistance of the fluorescent substance. Furthermore, under light and oxidative conditions, the salt can capture and neutralize free radicals generated within the cured ink film, thereby preventing oxidative degradation of the fluorescent substance.

[0033] In some embodiments, when executing step S1, the mass mixing ratio of piroctone olamine salt to the fluorescent substance is 1:(5-8). By adopting this ratio for mixing, it is possible to ensure that the piroctone olamine salt is evenly distributed on the surface of the fluorescent substance, forming a sparse but stable protective layer, thereby avoiding quenching of the fluorescent substance and reducing the luminous intensity of the fluorescent substance.

[0034] In some embodiments, during step S1, the fluorescent substance includes at least one of fluorescein, rhodamine, coumarin, acriflavine, and Rose Bengal B. In practice, by selecting different fluorescent substances, the ink can exhibit different fluorescence effects under light sources of different wavelengths. For example, fluorescein isothiocyanate, which has an excitation wavelength of 495 nm and an emission wavelength of 525 nm, can emit bright yellow-green fluorescence upon excitation.

[0035] In some embodiments, when performing step S1, the piroctone olamine salt used can be a conventional commercial product.

[0036] In some embodiments, when performing step S2, the mass ratio of the coating substrate, the light stabilizer, and the antioxidant is 1:(0.2-0.3):(0.1-0.3). When performing step S3, the mass ratio of piroctone olamine salt to the coating substrate is 1:(2-2.5).

[0037] In fact, the coating matrix used in step S2 can be at least one of PUD-270, carbomer-934, and carbomer-941, the light stabilizer includes at least one of LQ-292, Tinuvin-320, Tinuvin-327, and IRGACURE-651, and the antioxidant includes at least one of 2,6-di-tert-butyl-4-methylphenol, catechol, hydroquinone, and β-naphthol.

[0038] In some embodiments, when executing step S1, the following sub-steps are included:

[0039] S1.1. Dissolve the fluorescent substance to prepare a fluorescent solution;

[0040] S1.2. Ultrasonic dispersion of modified nano-titanium dioxide into the fluorescent solution to prepare a dispersion;

[0041] S1.3. Dissolve piroctone olamine salt in the dispersion solution with stirring, and react at 50-55° C. with stirring for 3-4 hours to obtain a mixed solution.

[0042] In fact, the preparation method of the modified nano-titanium dioxide used in step S1.2 includes: performing surface hydroxylation modification on the nano-titanium dioxide, and then immersing the nano-titanium dioxide in a phosphoric acid solution for phosphorylation to obtain the modified nano-titanium dioxide.

[0043] Specifically, the preparation method of modified nano titanium dioxide comprises the following steps:

[0044] The nano-titanium dioxide is dispersed in a saturated aqueous solution of sodium hydroxide at a solid-liquid ratio of 0.05-0.08 g / mL, and ultrasonically treated at a frequency of 20-40 kHz for 10-20 minutes to obtain hydroxylated titanium dioxide.

[0045] The modified nano-titanium dioxide is prepared by dispersing hydroxylated titanium dioxide with a solid-liquid ratio of 0.05-0.08 g / mL in phosphoric acid at 50-55° C. and ultrasonically treating the mixture at a frequency of 20-40 kHz for 10-20 minutes.

[0046] In some embodiments, when performing step S1.2, the mass ratio of the modified nano-titanium dioxide to the fluorescent substance is 1:(10-15), and the average particle size of the modified nano-titanium dioxide is 10-100 nm.

[0047] In some embodiments, the functional additives include a defoamer, a leveling agent, and a dispersant. Specifically, the defoamer includes at least one of BYK-052, HY-141, and BYK-052N; the leveling agent includes at least one of SH-450, MOK-2044, and BYK-333; and the dispersant includes at least one of ECODIS P90 and ECODIS123K.

[0048] In some embodiments, the resin includes at least one of polyurethane resin, acrylic resin, epoxy resin, polyester resin, and nitrocellulose resin, and the solvent includes an ethanol solution with a volume ratio of 50-60%. In practice, the solvent is a mixture of ethanol and water.

[0049] The present invention also provides a method for preparing an ink with a fluorescent effect, comprising the following steps: stirring and dissolving a fluorescent complex and a resin in a solvent to obtain a fluorescent resin, stirring and dispersing a functional additive in the fluorescent resin, and adjusting the solid content using a solvent to obtain an ink with a fluorescent effect.

[0050] Example 1 to Example 3

[0051] Examples 1 to 3 of the present invention respectively provide an ink having a fluorescent effect. The components and amounts used in each example are shown in Table 1 below.

[0052] Table 1

[0053]

[0054]

[0055] In Examples 1 to 3, the resin used was selected from TBU-C-59-D-53 of BASF, Germany; the defoamer used was purchased from Shanghai Huiyan New Materials Co., Ltd. with the brand name HY-141; the leveling agent used was BYK-333 of BYK Chemical; and the dispersant used was selected from Ecodis P90 of Arkema, France.

[0056] The method for preparing the fluorescent complex used in Examples 1 to 3 comprises the following steps:

[0057] S1. Dissolve fluorescein isothiocyanate (purchased from Hubei Jianchu Biopharmaceutical Co., Ltd., CAS: 3326-32-7) in deionized water to prepare a fluorescent solution; add piroctone olamine salt (purchased from Tesco Chemical Co., Ltd., CAS: 68890-66-4) to the fluorescent solution and stir to dissolve, and then stir and react at 55°C for 4 hours to prepare a mixed solution; wherein the mass ratio of piroctone olamine salt to fluorescein isothiocyanate is 1:7;

[0058] S2. Carbomer-934 (purchased from Wuhan Lanabai Pharmaceutical Chemical Co., Ltd.), Tinuvin-320 (purchased from Chongqing Kaiyin Chemical Co., Ltd.) and hydroquinone (CAS: 123-31-9) were mixed and dissolved in ethanol to prepare an auxiliary agent solution;

[0059] S3. The mixed solution and the auxiliary solution were stirred and reacted at 60° C. for 4 h, then cooled to room temperature at a rate of 4° C. / min to solidify, and then ground and pulverized through a 500-mesh sieve to obtain a fluorescent composite.

[0060] The preparation method of the ink with a fluorescent effect in Examples 1 to 3 includes the following steps: stirring and dissolving the fluorescent complex and resin in a 50 vol.% ethanol aqueous solution to prepare a fluorescent resin; then dispersing the functional additive in the fluorescent resin, adding ethanol aqueous solution to adjust the solid content to 20% to prepare the ink with a fluorescent effect.

[0061] Example 4

[0062] Example 4 of the present invention provides an ink with a fluorescent effect, which differs from Example 2 in that, in step S1 when preparing the fluorescent complex, fluorescein isothiocyanate (purchased from Hubei Jianchu Biotechnology Co., Ltd., CAS: 3326-32-7) is dissolved in deionized water to prepare a fluorescent solution; modified nano-titanium dioxide is ultrasonically dispersed into the fluorescent solution to prepare a dispersion; piroctone olamine salt (purchased from Tesco Chemical Co., Ltd., CAS: 68890-66-4) is added to the fluorescent solution and stirred to dissolve, and then stirred at 55°C for 4 hours to prepare a mixed solution; wherein, the mass ratio of modified nano-titanium dioxide to fluorescein isothiocyanate is 1:12, and the mass ratio of piroctone olamine salt to fluorescein isothiocyanate is 1:7.

[0063] Among them, the preparation method of modified nano titanium dioxide includes the following steps: dispersing nano titanium dioxide (purchased from Hubei Shenglun Chemical Technology Co., Ltd., brand R-258) in a saturated aqueous solution of sodium hydroxide at a solid-liquid ratio of 0.06 g / mL, and ultrasonically treating it at a frequency of 40 kHz for 10 minutes to obtain hydroxylated titanium dioxide; dispersing hydroxylated titanium dioxide and a solid-liquid ratio of 0.07 g / mL in 55°C phosphoric acid, and ultrasonically treating it at a frequency of 40 kHz for 20 minutes to obtain modified nano titanium dioxide.

[0064] Example 5

[0065] Example 5 of the present invention provides an ink with a fluorescent effect, which is different from Example 2 in that, in step S1 when preparing the fluorescent complex, fluorescein isothiocyanate (purchased from Hubei Jianchu Biotechnology Co., Ltd., CAS: 3326-32-7) is dissolved in deionized water to prepare a fluorescent solution; nano-titanium dioxide (purchased from Hubei Shenglun Chemical Technology Co., Ltd., brand R-258) is ultrasonically dispersed into the fluorescent solution to prepare a dispersion; piroctone olamine salt (purchased from Tesco Chemical Co., Ltd., CAS: 68890-66-4) is added to the fluorescent solution and stirred to dissolve, and then stirred at 55°C for 4 hours to prepare a mixed solution; wherein, the mass ratio of nano-titanium dioxide to fluorescein isothiocyanate is 1:12, and the mass ratio of piroctone olamine salt to fluorescein isothiocyanate is 1:7.

[0066] Comparative Example 1

[0067] Comparative Example 1 of the present invention provides an ink with a fluorescent effect, which is different from Example 2 in that Comparative Example 1 does not contain a fluorescent complex, but adds 8% fluorescein isothiocyanate (purchased from Hubei Jianchu Biopharmaceutical Co., Ltd., CAS: 3326-32-7).

[0068] Performance testing

[0069] The fluorescent inks in Examples 1 to 5 and Comparative Example 1 were respectively applied on stainless steel plates, and after curing, the corresponding cured films to be tested were obtained. The following tests were performed:

[0070] Fluorescence performance testing was performed using an FLS-920 fluorescence spectrophotometer produced by Edinburgh Instruments to test the fluorescence performance of the cured film at 510-530 nm. The results are shown in Table 2 below.

[0071] Light aging performance test: After the cured film was aged for 240 hours under UV light and air atmosphere, the fluorescence performance was repeatedly tested. The results are shown in Table 2 below.

[0072] Table 2 Fluorescence performance test data before and after aging

[0073] Fluorescence properties Photoaging performance Example 1 obvious Slightly attenuated Example 2 obvious Slightly attenuated Example 3 obvious Slightly attenuated Example 4 obvious Slightly attenuated Example 5 obvious obvious Comparative Example 1 obvious Obvious attenuation

[0074] While the embodiments of the present invention have been described in detail above, it will be apparent to those skilled in the art that various modifications and variations of these embodiments are possible. However, it should be understood that such modifications and variations are within the scope and spirit of the present invention as set forth in the claims. Furthermore, the invention described herein is susceptible to other embodiments and may be practiced or implemented in a variety of ways.

Claims

1. An ink with a fluorescent effect, characterized in that: The composition comprises the following components by weight percentage: 5-10% fluorescent compound, 50-55% resin, 1-2% functional additive and the balance solvent; The preparation method of the fluorescent complex comprises: adding piroctone olamine salt into a fluorescent solution containing a fluorescent substance, stirring and mixing to obtain a mixed solution; wherein the functional groups amide group, hydroxyl group and pyrrolidone ring on the piroctone olamine salt can interact with the fluorescent substance molecules to form a stable complex; after adding the piroctone olamine salt into the fluorescent solution containing the fluorescent substance, the mass mixing ratio of the piroctone olamine salt to the fluorescent substance is 1:(5-8); mixing and dissolving a coating matrix, a light stabilizer and an antioxidant to obtain an auxiliary agent solution; mixing the mixed solution with the auxiliary agent solution, solidifying and crushing the solution to obtain the fluorescent complex; The coating matrix is carbomer-934; The process of adding piroctone olamine salt into a fluorescent solution containing a fluorescent substance and stirring and mixing to prepare a mixed solution comprises: dissolving the fluorescent substance to prepare a fluorescent solution; ultrasonically dispersing modified nano-titanium dioxide into the fluorescent solution to prepare a dispersion; stirring and dissolving the piroctone olamine salt in the dispersion, and stirring and reacting at 50-55° C. for 3-4 hours to prepare a mixed solution; The preparation method of the modified nano titanium dioxide comprises: dispersing nano titanium dioxide in a saturated sodium hydroxide aqueous solution at a solid-liquid ratio of 0.05-0.08 g / mL, and ultrasonically treating the solution at a frequency of 20-40 kHz for 10-20 minutes to obtain hydroxylated titanium dioxide; and dispersing the hydroxylated titanium dioxide in phosphoric acid at 50-55° C. at a solid-liquid ratio of 0.05-0.08 g / mL, and ultrasonically treating the solution at a frequency of 20-40 kHz for 10-20 minutes to obtain the modified nano titanium dioxide.

2. The ink according to claim 1, characterized in that After mixing and dissolving the coating substrate, the light stabilizer and the antioxidant to prepare an additive solution, the mass ratio of the coating substrate, the light stabilizer and the antioxidant is 1: (0.2-0.3): (0.1-0.3); And / or, after the mixed solution is mixed with the auxiliary agent solution, the mass ratio of the piroctone olamine salt to the coating matrix is 1:(2-2.5).

3. The ink according to claim 1, characterized in that The fluorescent substance includes at least one of fluorescein, rhodamine, coumarin, acriflavine, and rose bengal B; and / or, the light stabilizer comprises at least one of LQ-292, Tinuvin-320, Tinuvin-327, and IRGACURE-651; And / or, the antioxidant includes at least one of 2,6-di-tert-butyl-4-methylphenol, catechol, hydroquinone, and β-naphthol.

4. The ink according to claim 1, characterized in that After ultrasonically dispersing the modified nano-titanium dioxide into the fluorescent solution, the mass ratio of the modified nano-titanium dioxide to the fluorescent substance is 1:(10-15); And / or, the average particle size of the modified nano-titanium dioxide is 10-100 nm.

5. The ink according to claim 1, characterized in that The functional additives include defoaming agents, leveling agents, and dispersants; in: The defoaming agent includes at least one of BYK-052, HY-141, and BYK-052N; And / or, the leveling agent includes at least one of SH-450, MOK-2044, and BYK-333; And / or, the dispersant includes at least one of ECODIS P90 and ECODIS123K.

6. The ink according to claim 1, characterized in that The resin includes at least one of polyurethane resin, acrylic resin, epoxy resin, polyester resin, and nitrocellulose resin; And / or, the solvent comprises an ethanol solution with a volume ratio of 50-60%.

7. A method for preparing the ink according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: stirring and dissolving a fluorescent compound and a resin in a solvent to prepare a fluorescent resin, stirring and dispersing a functional auxiliary agent in the fluorescent resin, and adjusting the solid content with a solvent to prepare an ink with a fluorescent effect.

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