A fluorescent composition, fluorescent inkjet ink, method of preparation and use, fluorescent marking

Abstract

The present application relates to the technical field of anti-counterfeiting ink, and discloses a fluorescent composition, fluorescent inkjet ink, a preparation method and application, and a fluorescent mark. The fluorescent composition comprises the following raw material components in parts by weight: 0.01-10 parts of fluorescent dye, 1-90 parts of resin monomer, 1-90 parts of epoxy acrylate oligomer, and 1-18 parts of cationic initiator; the resin monomer is a resin monomer containing a group capable of participating in curing in a molecule; the group capable of participating in curing includes at least one of an epoxy group and a vinyl ether group. The fluorescent inkjet ink prepared from the fluorescent composition can simultaneously meet the dual harsh requirements of high adhesion and resistance to organic solvent scrubbing.

Description

Technical Field

[0001] This invention relates to the field of anti-counterfeiting ink technology, specifically to a fluorescent composition, fluorescent inkjet ink, preparation method and application, and fluorescent marking. Background Technology

[0002] With the rapid development of digital printing technology, inkjet inks are increasingly widely used in anti-counterfeiting fields such as high-end product packaging, securities, and certificates. These application scenarios place higher demands on anti-counterfeiting inks: they not only need to have good fluorescent anti-counterfeiting properties, but also need to have excellent adhesion and durability on a variety of non-absorbent substrates (such as polycarbonate (PC), plastic banknote paper, etc.) to prevent illegal tampering through methods such as adhesive tape tearing or organic solvent wiping.

[0003] Currently, UV / UV-LED curable fluorescent inkjet inks are a research hotspot in the anti-counterfeiting field. However, most existing technologies have the following significant shortcomings: insufficient adhesion: most existing inks have poor adhesion to special substrates such as plastics. The root cause is that the volume shrinkage generated during the ink curing process leads to huge internal stress. When the internal stress exceeds the adhesion between the ink film and the substrate, the ink layer is prone to warping and peeling, and can be easily peeled off with tape, failing to pass the strict cross-cut test (such as GB / T9286), leaving loopholes for counterfeiting. For example, the fluorescent inkjet inks disclosed in patents such as CN103232750B and CN103242700B, although using epoxy resin, only focus on the basic printability of the ink such as pH value and viscosity, without addressing the control of curing shrinkage rate, and therefore cannot solve the adhesion problem on polymer plastic substrates; at the same time, the solvent resistance of existing inks is poor: most UV fluorescent inks on the market use a free radical curing mechanism. This mechanism has a fast curing speed, but it suffers from oxygen inhibition of polymerization, and the cross-linked network formed after curing has a relatively low density. This results in poor resistance of the ink layer to organic solvents such as ethanol and ethyl acetate, making the printed sample easy to erase and compromising the durability of the anti-counterfeiting label. This is evidenced by the free radical system anti-counterfeiting ink disclosed in Chinese invention patent CN117925011A, whose technical solution does not mention excellent solvent-resistant washability. In addition, existing inks have limited anti-counterfeiting functions: existing technologies focus on achieving the fluorescence effect itself, but fail to organically combine fluorescent anti-counterfeiting with physical anti-tampering (high adhesion) and chemical anti-tampering (solvent resistance) functions, resulting in a low level of anti-counterfeiting and insufficient security.

[0004] Therefore, there is an urgent need in the field for a fluorescent inkjet ink that can simultaneously meet the stringent requirements of high adhesion and resistance to organic solvent scrubbing. Summary of the Invention

[0005] This invention provides a fluorescent composition, a fluorescent inkjet ink, a preparation method and uses, and a fluorescent label, to solve the problem that the fluorescent anti-counterfeiting of existing inkjet inks cannot be combined with physical anti-tampering (high adhesion) and chemical anti-tampering (solvent resistance).

[0006] In a first aspect, the present invention provides a fluorescent composition comprising the following raw material components in parts by weight: fluorescent dye: 0.01-10 parts, resin monomer: 1-90 parts, epoxy acrylate oligomer: 1-90 parts, cationic initiator: 1-18 parts; wherein the resin monomer is a resin monomer containing groups in its molecule that can participate in curing.

[0007] Optionally, the curable groups include at least one of epoxy groups and vinyl ether groups.

[0008] In one optional embodiment, the resin monomer comprises: a monofunctional resin monomer; The resin monomer further includes at least one of a difunctional resin monomer and a polyfunctional resin monomer; The monofunctional resin monomer is a resin monomer containing only one group that can participate in curing in its molecule; the difunctional resin monomer is a resin monomer containing two groups that can participate in curing in its molecule; and the polyfunctional resin monomer is a resin monomer containing three or more groups that can participate in curing in its molecule. Optionally, the monofunctional resin monomer is 1-90 parts by weight; The difunctional resin monomer is 1-90 parts by weight; and / or, the polyfunctional resin monomer is 1-30 parts by weight. The total amount of the monofunctional resin monomer, the difunctional resin monomer, and the polyfunctional resin monomer does not exceed 90 parts by weight; and / or, And / or, the epoxy acrylate oligomer is 10-40 parts by weight.

[0009] In one optional embodiment, the monofunctional resin monomer is 10-60 parts by weight; The difunctional resin monomer is 20-70 parts by weight and / or the polyfunctional resin monomer is 5-30 parts by weight.

[0010] In one optional embodiment, the monofunctional resin monomer includes at least one of a monofunctional epoxy resin monomer and a monofunctional vinyl ether resin monomer. Optionally, the monofunctional epoxy resin monomer is selected from: 1,2-epoxy-4-vinylcyclohexane, 1-methyl-4-(2-methylepoxyethylene)-7-oxabicyclo[4.1.0]heptane, glycidyl 12-14 alkyl ether, and 3,4-epoxycyclohexyl methyl isobutylene ester; and / or The monofunctional vinyl ether resin monomer is ethyl 2-ethyleneoxyethoxyacrylate; The difunctional resin monomer is a difunctional epoxy resin monomer, optionally selected from: dicyclopentadiene epoxide, 1,4-cyclohexanediethanol bis(3,4-epoxycyclohexanecarboxylic acid) ester, tetrahydrophthalic acid diglycidyl ester, cyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, bis(7-oxabicyclo[4.1.0]3-heptylmethyl) adipate and 3,4-epoxycyclohexylcarboxylic acid 3,4-epoxycyclohexylmethyl ester; and / or The multifunctional resin monomer is a trifunctional or tetrafunctional epoxy resin monomer, optionally selected from: triglycidyl-p-aminophenol, 4,4'-methylenebis(N,N-diglycidylaniline), and trimethylolpropane triglycidyl ether; and / or The epoxy acrylate oligomer is selected from the polymerization products of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarbamate and caprolactone, poly[(2-epoxyethylene)-1,2-cyclohexanediol]2-ethyl-2-(hydroxymethyl)-1,3-propylene glycol ether; and / or The cationic initiator is selected from 4-(phenylthio)phenyldiphenylthionium hexafluorophosphate, bis(4-(diphenylthionium)phenyl)sulfide-bis(hexafluorophosphate) and 4,4'-dimethyldiphenyliodothionium hexafluorophosphate; Optionally, the polymer product of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarbamate and caprolactone is designated as TTA2081; the poly[(2-epoxyethylene)-1,2-cyclohexanediol]2-ethyl-2-(hydroxymethyl)-1,3-propylene glycol ether is designated as TTA3150.

[0011] In one optional embodiment, the fluorescent dye is selected from red fluorescent dyes, green fluorescent dyes, and blue fluorescent dyes; or Optionally, the red fluorescent dye is a europium(III) complex that, when excited by 365 nm ultraviolet light, emits red fluorescence with a main peak at 610-620 nm; and / or The green fluorescent dye is a mesoscopic polymeric fluorescent material, which is a polymeric material with a molecular weight of 4,000-700,000; optionally, the mesoscopic polymeric fluorescent material is a polymeric material with a molecular weight of 4,118-661,000. The blue fluorescent dye is a small-molecule organic compound containing a fused aromatic ring system in its molecular structure and capable of emitting blue fluorescence under ultraviolet light excitation; the small-molecule organic compound has a molecular weight of less than 1000; and / or Further optionally, the blue fluorescent dye is selected from benzoxazole organic fluorescent dyes and stilbene organic fluorescent dyes; Further optionally, the benzoxazole-based organic fluorescent dye is selected from: 1,2-bis(5-methylbenzo[d]oxazol-2-yl)ethylene and 1,2-bis(5-methyl-2-benzoxazolyl)-ethylene, and the stilbene-based organic fluorescent dye is 4,4'-bis[2-methoxystyryl]-1,1'-biphenyl; and / or The europium(III) complex is selected from tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione]europium(III), with the structural formula shown in Formula 1:

[0012] Formula 1; Tris(1,1,1,5,5,5-hexafluoro-2,4-pentanedione) europium(III), with the structural formula shown in Formula 2:

[0013] Equation 2; and Tris(1,3-diphenyl-propanedione)europium(III), with the structural formula shown in Formula 3:

[0014] Formula 3; and / or The linear mesoscopic polymeric fluorescent dye is selected from green fluorescent dye 1, and its structural formula is shown in Formula 4:

[0015] Equation 4, Where n is an integer selected from 10 to 1000; Optionally, n=41; and Green fluorescent dye 2, with the structural formula shown in Formula 5: Equation 5, Where n is an integer selected from 10 to 1000; Optional, n=76.

[0016] Secondly, the present invention also provides a fluorescent inkjet ink, the raw materials of which comprise the above-described composition; Optionally, it also contains 0.01-5 parts by weight of a leveling agent; Further optionally, the leveling agent is selected from polyether-modified polysiloxane organic compounds, polyester-modified polysiloxane organic compounds, and acrylate organic compounds; Further optionally, the polyether-modified polysiloxane organic compound is designated BYK307 or Glide410, the polyester-modified polysiloxane organic compound is designated BYK331, and the acrylate organic compound is designated BYK-358N.

[0017] In one optional embodiment, the solubility of the fluorescent dye in an organic solvent is 0.01-200 g / kg; Optionally, the raw material components of the fluorescent inkjet ink are selected from any of the following: 0.5 parts of tri[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione]europium(III); 40 parts of ethyl 2-ethyleneoxyethoxyacrylate; 20 parts of a difunctional resin monomer mixture consisting of methyl 3,4-epoxycyclohexylcarboxylate and diglycidyl cyclohexane-1,2-dicarboxylic acid in a mass ratio of 1:1; 30 parts of trimethylolpropane triglycidyl ether; 15 parts of TTA2081; 1 part of a cationic initiator mixture consisting of 4-(phenylthio)phenyldiphenylthionyl hexafluorophosphate and bis(4-(diphenylthionyl)phenyl)sulfide-bishexafluorophosphate in a mass ratio of 2:1; and 2 parts of leveling agent BYK-307; or The composition includes 10 parts of green fluorescent dye 1, 20 parts of a monofunctional epoxy resin monomer mixture consisting of 1,2-epoxy-4-vinylcyclohexane and glycidyl 12-14 alkyl ether in a 1:1 mass ratio, 50 parts of a difunctional epoxy resin monomer mixture consisting of dicyclopentadiene epoxide and 1,4-cyclohexanediethanol bis(3,4-epoxycyclohexanecarboxylic acid) ester in a 1:1 mass ratio, 17 parts of a polyfunctional epoxy resin monomer mixture consisting of triglycidyl-p-aminophenol and trimethylolpropane triglycidyl ether in a 1:1 mass ratio, 10 parts of TTA2081, 18 parts of a cationic initiator mixture consisting of bis(4-(diphenylthionyl)phenyl)sulfide-bis(hexafluorophosphate) and 4-4'-dimethyldiphenyliodothionyl hexafluorophosphate in a 2:1 mass ratio, and 0.01 parts of leveling agent BYK-331; or The fluorescent dye composed of 4,4'-bis[2-methoxystyryl]-1,1'-biphenyl and 1,2-bis(5-methyl-2-benzoxazolyl)-ethylene in a mass ratio of 1:2 was 0.01 parts; 1-methyl-4-(2-methylepoxyethylene)-7-oxabicyclo[4.1.0]heptane was 60 parts; and tetrahydrophthalic acid diglycidyl ester and 4,5-epoxycyclohexane in a mass ratio of 1:1 were used. The mixture comprises 20 parts of a difunctional epoxy resin monomer mixture composed of diglycidyl 1,2-dicarboxylic acid diglycidyl ester, 5 parts of triglycidyl-p-aminophenol, 25 parts of TTA3150, 15 parts of a cationic initiator mixture composed of 4-(phenylthio)phenyldiphenylthionyl hexafluorophosphate and 4-4'-dimethyldiphenyliodothionyl hexafluorophosphate in a mass ratio of 3:1, and 0.5 parts of leveling agent BYK-358N; or The mixture consists of 5 parts of 4,4'-bis[2-methoxystyryl]-1,1'-biphenyl, 10 parts of 1,2-epoxy-4-vinylcyclohexane, 70 parts of a difunctional epoxy resin monomer mixture composed of 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and bis(7-oxabicyclo[4.1.0]3-heptylmethyl) adipate in a mass ratio of 1:1:1, 40 parts of 4,4'-methylene bis(N,N-diglycidylaniline), 40 parts of TTA3150, 10 parts of bis(4-(diphenylthionyl)phenyl)sulfide-bis(hexafluorophosphate), and 4.5 parts of leveling agent Glide-410; or 0.01 parts of tris(1,1,1,5,5,5-hexafluoro-2,4-pentanedione)europium(III), 60 parts of 1-methyl-4-(2-methylepoxyethylene)-7-oxabicyclo[4.1.0]heptane, 20 parts of a difunctional epoxy resin monomer mixture consisting of diglycidyl tetrahydrophthalate and diglycidyl 4,5-epoxycyclohexane-1,2-dicarboxylic acid in a 1:1 mass ratio, 5 parts of triglycidyl-p-aminophenol, 25 parts of TTA3150, 15 parts of a cationic initiator mixture consisting of 4-(phenylthio)phenyldiphenylthionyl hexafluorophosphate and 4-4'-dimethyldiphenyliodothionyl hexafluorophosphate in a 3:1 mass ratio, and 0.5 parts of leveling agent BYK-358N; or 5 parts of tris(1,3-diphenyl-propanedione)europium(III), 10 parts of 1,2-epoxy-4-vinylcyclohexane, 70 parts of a difunctional epoxy resin monomer mixture consisting of 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and bis(7-oxabicyclo[4.1.0]3-heptylmethyl) adipate in a mass ratio of 1:1:1, 4,4'-methylenebis(N,N-diglycidylaniline), 40 parts of TTA3150, 10 parts of bis(4-(diphenylthionyl)phenyl)sulfide-bis(hexafluorophosphate), and 4.5 parts of leveling agent Glide-410; or 0.5 parts of 4,4'-bis[2-methoxystyryl]-1,1'-biphenyl, 40 parts of ethyl 2-ethyleneoxyethoxyacrylate, 30 parts of trimethylolpropane triglycidyl ether, 15 parts of TTA2081, and 1 part of a cationic initiator mixture consisting of 4-(phenylthio)phenyldiphenylthionium hexafluorophosphate and bis(4-(diphenylthionium)phenyl)thionium-bishexafluorophosphate in a mass ratio of 1:1; or 8 parts of 1,2-bis(5-methylbenzo[d]oxazol-2-yl)ethylene; 20 parts of a monofunctional resin monomer mixture consisting of 1,2-epoxy-4-vinylcyclohexane and glycidyl 12-14 alkyl ether in a 1:1 mass ratio; 50 parts of a difunctional epoxy resin monomer mixture consisting of dicyclopentadiene epoxide and 1,4-cyclohexanediethanol bis(3,4-epoxycyclohexanecarboxylic acid) ester in a 1:1 mass ratio; 10 parts of TTA2081; 15 parts of a cationic initiator mixture consisting of bis(4-(diphenylthionyl)phenyl)sulfide-bis(hexafluorophosphate) and 4-4'-dimethyldiphenyliodothionyl hexafluorophosphate in a 2:1 mass ratio; and 0.01 parts of leveling agent BYK-331; or The composition includes 10 parts of green fluorescent dye 2, 20 parts of a monofunctional epoxy resin monomer mixture consisting of 1,2-epoxy-4-vinylcyclohexane and glycidyl 12-14 alkyl ether in a 1:1 mass ratio, 50 parts of a difunctional epoxy resin monomer mixture consisting of dicyclopentadiene epoxide and 1,4-cyclohexanediethanol bis(3,4-epoxycyclohexanecarboxylic acid) ester in a 1:1 mass ratio, 17 parts of a polyfunctional epoxy resin monomer mixture consisting of triglycidyl p-aminophenol and trimethylolpropane triglycidyl ether in a 1:1 mass ratio, 10 parts of TTA2081, 18 parts of a cationic initiator mixture consisting of bis(4-(diphenylthionyl)phenyl)sulfide-bis(hexafluorophosphate) and 4-4'-dimethyldiphenyliodonium hexafluorophosphate in a 2:1 mass ratio, and 0.01 parts of leveling agent BYK-331.

[0018] Thirdly, the present invention also provides a method for preparing the above-mentioned fluorescent inkjet ink, which uses fluorescent dyes, cationic initiators, resin monomers, epoxy acrylate oligomers and leveling agents to prepare ink. In one alternative implementation, the following steps are included: a) Under light-protected conditions, fluorescent dye, resin monomer, epoxy acrylate oligomer, cationic initiator, and leveling agent are mixed in proportion to obtain a mixture solution; b) Filter the mixture solution obtained in step a) to obtain the fluorescent inkjet ink.

[0019] Fourthly, the present invention also provides a fluorescent label, which is prepared by curing the above-mentioned fluorescent inkjet ink with UV / UV-LED. Optionally, the fluorescent inkjet ink is red, blue, and / or green, and the fluorescent marker is a single primary color, a two-primary color, or a three-primary color.

[0020] Fifthly, the present invention also provides the use of the above-mentioned fluorescent inkjet ink in the field of anti-counterfeiting, optionally in the fields of anti-counterfeiting of commodity packaging, securities, certificates, and / or polymer banknotes; Alternatively, the fluorescent inkjet ink is adhered to a polycarbonate or plastic banknote paper substrate.

[0021] The technical solution of this invention has the following advantages: 1. The fluorescent composition provided by the present invention comprises the following raw material components in parts by weight: fluorescent dye: 0.01-10 parts, resin monomer: 1-90 parts, epoxy acrylate oligomer: 1-90 parts, cationic initiator: 1-18 parts; wherein the resin monomer is a resin monomer containing a group that can participate in curing in its molecule; optionally, the group that can participate in curing is selected from epoxy groups and vinyl ether groups; the ratio range of the resin monomer and epoxy acrylate oligomer in the above scheme, under cationic initiation, forms a dense cross-linked network with low internal stress and strong adhesion to the substrate. The product prepared by this composition not only has fluorescent anti-counterfeiting function, but also has excellent adhesion and solvent resistance.

[0022] 2. The resin monomer in the fluorescent composition provided by the present invention includes: a monofunctional resin monomer; the resin monomer further includes at least one of a difunctional resin monomer and a polyfunctional resin monomer. The different functional group resin monomers used in the above scheme lay the foundation for the subsequent precise "adjustment" of the cured network performance. Monofunctional resin monomers, as "flexible segments" and "diluents," can reduce shrinkage and stress; difunctional and / or multifunctional resin monomers, as "crosslinking points," provide rigidity and toughness. In the preferred scheme, the monofunctional resin monomer is 1-90 parts by weight; the difunctional resin monomer is 1-90 parts by weight and / or the multifunctional resin monomer is 1-30 parts by weight; and the epoxy acrylate oligomer is 10-40 parts by weight. This scheme provides a formulation with different contents of resin monomers of three functional groups and epoxy acrylate oligomers working synergistically. The fluorescent inkjet ink prepared by this formulation has low curing shrinkage and low internal stress. After being printed on a flexible plastic substrate and cured using the fluorescent inkjet ink, the flexible plastic substrate remains flat and without curling. The fluorescent inkjet ink can obtain better adhesion on special substrates that are difficult to adhere to, such as polycarbonate (PC) and plastic banknote paper.

[0023] 3. In the fluorescent composition provided by this invention, the monofunctional resin monomer is 10-60 parts by weight; the difunctional resin monomer is 20-70 parts by weight and / or the polyfunctional resin monomer is 5-30 parts by weight; the total amount of the monofunctional resin monomer, the difunctional resin monomer, and the polyfunctional resin monomer does not exceed 90 parts by weight. The above scheme provides the dosage range of the three functional resin monomers and epoxy acrylate in the raw materials, which is the material ratio determined through a large number of experiments to achieve the "performance synergy effect". For example, the dosage of polyfunctional resin monomer (5-30 parts) can avoid the network becoming too rigid due to excessive use, thus damaging the adhesion; at the same time, it provides durability. The preferred range given in the above scheme enables the fluorescent inkjet ink prepared by this scheme to remain flat and free of curling after being printed on a flexible plastic substrate and cured, and to obtain further excellent adhesion on difficult-to-adhere substrates such as PC and plastic banknotes.

[0024] 4. The fluorescent composition provided by this invention employs specific resin monomers, oligomers, and cationic initiators; the listed compounds (such as 3,4-epoxycyclohexylcarboxylic acid methyl ester, dicyclopentadiene epoxide, trimethylolpropane triglycidyl ether, etc.) are all carefully selected substances with low shrinkage and good compatibility; the epoxy acrylate oligomers are specifically limited to small molecules or oligomers with specific structures, such as TTA2081 and / or TTA3150. These substances can act as "adhesion promoters" and "network modifiers" to further optimize the interaction with resin monomers and network toughness. The selection of cationic initiators enables the fluorescent inkjet ink prepared from this composition to be efficiently cured under UV-LED light sources.

[0025] 5. The fluorescent composition provided by this invention employs fluorescent dyes of specific colors and chemical categories and structures. The fluorescent dyes are selected from three colors: red (europium complex), green (mesoscopic polymer), and blue (benzoxazole and stilbene). The fluorescent inkjet ink prepared from this composition can produce a variety of highly concealed and highly recognizable fluorescent anti-counterfeiting patterns, enhancing the anti-counterfeiting level. At the same time, this scheme limits the dye solubility range, ensuring stable dispersion of the dye in the formulation and avoiding aggregation or precipitation. The specific dyes provided by this scheme have good compatibility with the cationic curing system and can withstand the curing process. This scheme further limits the specific compound structural formulas of the blue, red, and green fluorescent dyes. For example, europium complexes have a unique "antenna effect" and a sharp red emission peak, exhibiting extremely strong anti-counterfeiting features. Benzoxazole dyes (such as 4,4'-bis[2-methoxystyryl]-1,1'-biphenyl) have high fluorescence quantum yield and stability.

[0026] 6. The fluorescent inkjet ink raw material provided by this invention comprises the above-mentioned composition and also comprises 0.01-5 parts by weight of a leveling agent. The scheme further specifies the type and specific compound category of the leveling agent. The leveling agent can be Glide-410. The leveling agent Glide-410 solves the problem of ink spreading and leveling on special substrates. On low surface energy plastic substrates (such as PC), the wettability of ink is the key to affecting adhesion and appearance. The polyether modified polysiloxane leveling agent Glide-410 can significantly reduce surface tension, promote uniform ink spreading, eliminate pinholes, and obtain a smooth ink film, thereby indirectly improving adhesion and product aesthetics. After curing, the fluorescent inkjet ink of this scheme is almost invisible under sunlight and difficult to detect, but it can show bright red, green, and blue under 365nm ultraviolet light, which are single-color, two-color, and three-color fluorescence, with strong anti-counterfeiting identification and aesthetics.

[0027] 7. The fluorescent inkjet ink provided by this invention employs a specific soluble fluorescent dye and a series of optimized, readily implementable specific formulations for fluorescent inkjet inks. By synergistically compounding different types and quantities of functional group resin monomers with epoxy acrylate oligomers, the core technical challenges of high crosslinking density inks, such as large shrinkage, poor adhesion, and poor solvent resistance, are fundamentally solved. At the same time, by matching dedicated leveling agents and initiators, the ink possesses excellent inkjet printing suitability and UV curing characteristics, further obtaining a high-performance anti-counterfeiting ink that combines excellent adhesion, good hardness, high flatness, stable fluorescence performance, and reliable processability.

[0028] 8. In the preparation method of the fluorescent inkjet ink provided by the present invention, anti-counterfeiting fluorescent dyes, cationic initiators, resin monomers, epoxy acrylate oligomers, and leveling agents are used to prepare the ink. The above scheme is based on the cationic curing mechanism. Therefore, the ink prepared by this scheme forms a dense three-dimensional cross-linked network structure after curing. The cross-linking density is high, and it has a strong resistance to common organic solvents such as ethanol and ethyl acetate. After 50 vigorous scrubbings, the fluorescent pattern remains intact, and the brightness decay is less than 5%. Thus, the anti-counterfeiting function of the ink prepared by this scheme is durable and tamper-proof. At the same time, the process of this scheme is extremely simple (mixing and filtering), and the conditions are mild (light-proof, room temperature or low temperature), which is suitable for large-scale production. At the same time, the "light-proof" operation protects the photosensitive components (initiator and some dyes). The "filtration" step can remove particulate matter that may clog the precision printhead, improve the purity of the ink and inkjet printing suitability.

[0029] 9. The fluorescent label provided by this invention is prepared using UV / UV-LED cured fluorescent inkjet ink as raw material. It is monochrome, two-color, or three-color, and has "high-tech anti-counterfeiting performance", "excellent durability" and "efficient and flexible production characteristics". It solves the pain points of traditional anti-counterfeiting technology such as poor durability, low production efficiency, easy counterfeiting or lack of environmental protection.

[0030] 10. This invention provides the use of the above-mentioned fluorescent inkjet ink in the field of anti-counterfeiting, optionally in the fields of anti-counterfeiting of commodity packaging, securities, certificates, and / or polymer banknotes; and optionally, the fluorescent inkjet ink is adhered to a polycarbonate or polymer banknote paper substrate. The above solution is applicable to applications requiring extremely high anti-counterfeiting and security durability, protecting the use of special inks possessing the triple characteristics of "high adhesion + solvent resistance + high-intensity fluorescence". Detailed Implementation

[0031] The following embodiments are provided to better understand the present invention, but the following embodiments do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the scope of protection of the present invention.

[0032] Unless otherwise specified, all experimental steps or conditions in the examples were performed according to conventional experimental procedures and conditions in the art. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0033] The reagents used in this invention are as follows: 3,4-Epoxycyclohexylcarboxylic acid methyl 3,4-epoxycyclohexylcarboxylic acid (CAS: 2386-87-0) 1,2-Epoxy-4-vinylcyclohexane (CAS: 106-86-5) 1-Methyl-4-(2-methylepoxyethylene)-7-oxabicyclo[4.1.0]heptane (CAS: 96-08-2), Dicyclopentadiene epoxide (CAS: 81-21-0), 1,4-cyclohexanediethanol bis(3,4-epoxycyclohexanecarboxylic acid) ester (CAS: 20249-12-1), 2-(3,4-epoxycyclohexyl)-5,5-spiro(3,4-epoxycyclohexyl)-1,3-dioxane homopolymer (CAS: 64034-70-4), diglycidyl tetrahydrophthalate (CAS: 21544-03-6), diglycidyl cyclohexane-1,2-dicarboxylic acid (CAS: 5493-45-8) 4,5-Epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester (CAS: 25293-64-5), triglycidyl p-aminophenol (CAS: 5026-74-4), 4,4'-methylenebis(N,N-diglycidylaniline) (CAS: 28768-32-3), and a mixture of 12-14 alkyl ethers of glycidyl ester (CAS: 68609-97-2) are generic numbers, purchased from Aladdin Chemical Company, with the grades D133554 and 1,4 -Butylene glycol diglycidyl ether (CAS: 2425-79-8), neopentyl glycol diglycidyl ether (CAS: 17557-23-2), trimethylolpropane triglycidyl ether (CAS: 30499-70-8), bis(7-oxabicyclo[4.1.0]3-heptylmethyl) adipate (CAS: 3130-19-6), 3,4-epoxycyclohexylmethyl isobutylene ester (CAS: 82428-30-6), poly[(2-epoxyethylene] [1,2-Cyclohexanediol] 2-Ethyl-2-(hydroxymethyl)-1,3-propanediol ether (3:1) (CAS: 244772-00-7), ethyl 2-ethyleneoxyethoxyacrylate (CAS: 86273-46-3), 4-(phenylthio)phenyl diphenylthionyl hexafluorophosphate (CAS: 75482-18-7); bis(4-(diphenylthionyl)phenyl)sulfide-bis(hexafluorophosphate) (CAS: 74227-35-3), 4-4'-di... Methyl diphenyliodonium hexafluorophosphate (CAS: 60565-88-0); Polymer of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarbamate and caprolactone (CAS: 151629-49-1), grade: TTA2081; Poly[(2-epoxyethylene)-1,2-cyclohexanediol]2-ethyl-2-(hydroxymethyl)-1,3-propylene glycol ether (3:1) (CAS: 244772-00-7), grade: TTA3150.

[0034] Blue fluorescent dyes: 1,2-bis(5-methylbenzo[d]oxazol-2-yl)ethylene (CAS: 1041-00-5); 4,4'-bis[2-methoxystyryl]-1,1'-biphenyl (CAS: 79448-61-6); green fluorescent dyes were prepared in the laboratory.

[0035] The leveling agent, polyester-modified polysiloxane, was purchased from BYK Company, brand name BYK331; the leveling agent, polyether-modified polydimethylsiloxane, was purchased from BYK Company, brand name BYK307; and the polyether-modified polysiloxane leveling agent was purchased from Tego Company, brand name TEGO® Glide410; the acrylate leveling agent was purchased from BYK Company, brand name BYK-358N.

[0036] Example 1: Preparation of Red Fluorescent Ink raw material: Red fluorescent dye: tri[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione]europium(III), resin monomer, epoxy acrylate oligomer, cationic initiator, leveling agent (BYK-307), specific ratios are shown in Table 1 and Table 2.

[0037] 1) The entire preparation process must be conducted in the dark; 2) Mix the red fluorescent dye europium complex and other raw materials in proportion, stir at 500 rpm for 2 hours, and filter with a 1 μm filter to obtain red fluorescent inkjet ink.

[0038] 3) Performance Testing: The fluorescent inkjet ink prepared above was printed onto a polycarbonate (PC) substrate using a UV inkjet printer and then cured with UV / UV-LED (the curing equipment used a 395nm LED UV light source with a power of 2W / cm²). 2 According to the national standard GB / T9286-1992 "Cross-cut Test for Paint and Varnish Films", the cross-cut area was observed under a 365nm UV lamp, and the test result was grade 0. Before wiping with solvent, the sample area was observed under a 365nm UV lamp, and the fluorescence emission spectrum of the sample area was tested and the intensity of the fluorescence emission peak was recorded. Then, the sample area was vigorously wiped 25 times with a cotton swab soaked in alcohol, and then vigorously wiped 25 times with a cloth soaked in ethyl acetate. The sample area was then observed under a 365nm UV lamp, and the fluorescence emission spectrum of the sample area was tested and the intensity of the fluorescence emission peak was recorded. Comparing the changes in the intensity of the fluorescence emission peak before and after wiping, the intensity of the fluorescence emission peak decreased by 2.5% after wiping.

[0039] The ink is printed onto a flexible plastic substrate, and after curing, the substrate remains flat and does not curl.

[0040] Example 2: Preparation of Green Fluorescent Ink (1) Preparation of green fluorescent dye 1 1. Synthesis steps of green fluorescent dye 1

[0041] In the reaction formula, SPhos is 2-bicyclohexylphosphine-2',6'-dimethoxybiphenyl, commercially available, CAS: 657408-07-6; (Pd2(dba)3 is tris(dibenzylacetone)dipalladium(0), commercially available, CAS: 52409-22-0; Aliquat336 is methyltrioctylammonium chloride, commercially available, CAS number: 5137-55-3; group C6H 13 - represents n-hexyl, and Tol represents toluene.

[0042] 2. Accurately weigh 208.8 mg of A, 3.6 mg of B, and 217.3 mg of C into a polymer bottle that has been soaked in hydrochloric acid. Add 1-2 drops of G; under light-protected conditions, quickly add 0.93 mg of D and 1.66 mg of E, with Ar gas protection, to obtain an Ar-protected reaction system.

[0043] 3. Take 10 ml of analytical grade toluene and 3 ml of 2M F solution and introduce them into the above reaction system.

[0044] 4. Heat to 110℃ and reflux for 24 hours.

[0045] 5. Palladium removal: Preparation of chelating agent aqueous solution: Weigh 10 g of thiourea (CAS No.: 62-56-6), dilute to 100 mL with deionized water, and then add 1-2 mL of concentrated hydrochloric acid to adjust the pH to 1-2 to obtain a 100 mg / mL chelating agent aqueous solution for later use; Take an equal volume of the chelating agent aqueous solution to the solution in the above reaction system and introduce it into the above reaction system; React overnight at 6.80℃ for 12 hours.

[0046] Post-processing: Extraction; after the above reaction system returned to room temperature and separated into layers, the organic phase was significantly viscous. Refined toluene was added to the reaction system, and the mixture was transferred to a 250 ml separatory funnel and washed three times with water. Concentration; vacuum distillation until the solution was significantly viscous. Precipitation; the solution was added dropwise to 200 ml of refined methanol using a glass dropper, stirred, filtered, and dried to finally obtain green fluorescent dye 1. The detection data for green fluorescent dye 1 are as follows: Elemental analysis data for green fluorescent dye: (C 50 H 64 ) 0.98 (C 45 H 42 ) 0.02 C, 90.35; H, 9.65.

[0047] Test results: C, 90.29; H, 9.61; Gel permeation chromatography data for green fluorescent dye 1: (GPC, 1,2,4-trichlorobenzene, polystyrene as standard, 150℃) analysis results are as follows: Mn=27100, PDI=1.75, degree of polymerization n=41; NMR analysis data for green fluorescent dye 1: 1H NMR (500MHz, CDC) l3 )δ8.01-7.70(m,8H),7.65-7.50(m,4H),1.95-1.78(m,8H),1.40-1.21(m,32H),1.05–0.90(m,12H).

[0048] (2) Preparation of green fluorescent ink raw material: The green fluorescent dye 1 prepared in step (1), resin monomers with different functional groups, epoxy acrylate oligomers, cationic initiators, and leveling agents (BYK-331) are used. The specific proportions are shown in Table 1 and Table 2.

[0049] 1) The entire preparation process must be conducted in the dark; 2) Mix green fluorescent dye 1 and other raw materials in proportion, stir at 500 rpm for 2 hours, and filter with a 1 μm filter to obtain green fluorescent inkjet ink.

[0050] 3) Performance Testing: The method is the same as in Example 1. The fluorescent inkjet ink prepared above was printed onto a plastic banknote paper substrate using a UV inkjet printer. After UV / UV-LED curing, it was tested according to the national standard "Cross-cut Test for Paint and Varnish Films" GB / T9286-1992, and the test result was Grade 1. The intensity of the fluorescence emission peak before and after solvent wiping was recorded, and the change in the intensity of the fluorescence emission peak before and after wiping was compared. The intensity of the fluorescence emission peak decreased by 3.1% after wiping. When the ink was printed onto a flexible plastic substrate, after curing, the substrate remained flat and without curling.

[0051] Example 3: Preparation of Blue Fluorescent Ink raw material: Blue fluorescent dye: a blue fluorescent dye complex composed of 4,4'-bis[2-methoxystyryl]-1,1'-biphenyl and 1,2-bis(5-methyl-2-benzoxazolyl)-ethylene in a weight ratio of 1:2, resin monomers with different functional groups, epoxy acrylate oligomers, cationic initiators, and leveling agents (Tego-410 from Tego). The specific proportions are shown in Tables 1 and 2.

[0052] (1) The entire preparation process must be conducted in the dark; (2) Mix the blue fluorescent dye DELI-S5 and other raw materials in proportion, stir at 500 rpm for 2 hours, and filter with a 1 μm filter to obtain blue fluorescent inkjet ink.

[0053] (3) Performance testing: The method is the same as in Example 1, and the result of the cross-cut adhesion test is grade 0. The intensity change of the fluorescence emission peak before and after solvent wiping is compared. The intensity of the fluorescence emission peak decreases by 4% after wiping. After printing on a flexible plastic substrate and curing, the substrate remains flat and without curling.

[0054] Example 4: Preparation of Blue Fluorescent Ink raw material: Blue fluorescent dye: 4,4'-bis[2-methoxystyryl]-1,1'-biphenyl, resin monomers with different functional groups, epoxy acrylate oligomers, cationic initiator, leveling agent (Tego-410 from Tego), specific ratios are shown in Table 1 and Table 2.

[0055] (1) The entire preparation process must be conducted in the dark; (2) Mix the blue fluorescent dye 9,10-diphenylanthracene and other raw materials in proportion, stir at 500 rpm for 2 hours, and filter with a 1 μm filter to obtain blue fluorescent inkjet ink.

[0056] (3) Performance testing: The method is the same as in Example 1, and the result of the cross-cut adhesion test is grade 0. The intensity change of the fluorescence emission peak before and after solvent wiping is compared. The intensity of the fluorescence emission peak decreases by 2.2% after wiping. After printing on a flexible plastic substrate and curing, the substrate remains flat and without curling.

[0057] Examples 5-9 The preparation methods of all embodiments are the same, with Examples 3 and 5, and Examples 4 and 6 having the same components and the same amount, and the performance testing methods are also completely the same. The difference lies in the type of fluorescent dye used.

[0058] In Examples 1 and 7, except for the different types of fluorescent dyes, Example 7 does not contain difunctional epoxy resin monomers and leveling agents; everything else is the same.

[0059] In Examples 2 and 8, except for the type of fluorescent dye, Example 8 does not contain a multifunctional epoxy resin monomer, and everything else is the same.

[0060] Examples 2 and 9 are identical except for the fluorescent dye.

[0061] The fluorescent dye used in Example 5 was tris(1,1,1,5,5,5-hexafluoro-2,4-pentanedione) europium(III); The fluorescent dye used in Example 6 was tris(1,3-diphenyl-propanedione)europium(III); The fluorescent dye used in Example 7 was 4,4'-bis[2-methoxystyryl]-1,1'-biphenyl; The fluorescent dye used in Example 8 was 1,2-bis(5-methyl-2-benzoxazolyl)-ethylene; The fluorescent dye used in Example 9 was a laboratory-made green fluorescent dye 2; The synthesis steps of green fluorescent dye 2 in Example 9:

[0062] In the reaction formula, (Pd2(dba)3, Aliquat336, C6H group) 13 -, Tol, same as in Example 2.

[0063] 1. Accurately weigh 1.8 mg of A, 1.1 mg of B, and 17.3 mg of C into a polymer bottle that has been soaked in hydrochloric acid. Then add 1 drop of F and 1 mg of D. Under light-protected conditions and with Ar gas protection, form an Ar-protected reaction system.

[0064] 2. Take 5 mL of analytical grade toluene and 1.3 mL of K2CO3 aqueous solution and introduce them into the above reaction system.

[0065] 3. Increase the temperature to 110℃ and react for 24 hours.

[0066] 4. Palladium removal: Prepare a 100 mg / ml chelating agent aqueous solution as in Example 2. Add 5 mL of the chelating agent aqueous solution to the above reaction system and react at 80°C for 5 hours.

[0067] 5. Post-processing: Same as in Example 2, the detection data of green fluorescent dye 2 are as follows: Elemental analysis data for green fluorescent dye 2: (C 31 H 36 ) 0.99 (C 45 H 42 ) 0.01 C, 91.14; H, 8.86. Test results: C, 91.10; H, 8.85. Gel permeation chromatography data of green fluorescent dye 2: (GPC, 1,2,4-trichlorobenzene, polystyrene as standard, 150℃) analysis results are as follows: Mn=31300, PDI=1.83, degree of polymerization n=76. NMR analysis data of green fluorescent dye 2: 1H NMR (500MHz, CDC) l3 )δ7.99-7.72(m,4H),7.63-7.49(m,6H),1.93-1.77(m,4H),1.43-1.25(m,16H),1.03–0.91(m,6H).

[0068] The raw materials and specific proportions of the above embodiments are shown in Table 1 and Table 2.

[0069] The content was printed on a flexible plastic substrate using the fluorescent inks of Examples 5-9. After curing, the substrates remained flat and without curling. Adhesion tests all showed a grade of 0. Solvent resistance rubbing tests showed that the intensity of the fluorescence emission peaks after wiping with the fluorescent inks of Examples 5-9 decreased by 3%, 2.8%, 2.6%, 3.3%, and 3.1%, respectively, with all samples showing a noticeable fading to the naked eye.

[0070] Comparative Example 1 This comparative example uses an acrylate monomer system and a free radical photoinitiator. The substrate resin and cationic initiator in Example 1 were replaced with equal amounts of acrylate monomer and free radical photoinitiator (such as TPO), and the preparation method was the same as in Example 1.

[0071] The raw materials and formulation of Comparative Example 1 are as follows: Tetrahydrofurfuryl acrylate (CAS: 2399-48-6); 1,4-Butanediol diglycidyl ether (CAS: 2425-79-8); 2-Isopropylthioxanthone (CAS: 5495-84-1); 2,4,6-Trimethylbenzoylbenzene-diphenylphosphine oxide (CAS: 75980-60-8).

[0072] Fluorescent dye: 0.5 parts by weight of tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione]europium(III); Acrylate monomer: 90 parts by weight of tetrahydrofurfuryl acrylate; acrylate oligomer: 15 parts by weight of 1,4-butanediol diglycidyl ether; Free radical initiator: 1 part by weight of 2,4,6-trimethylbenzoylbenzene-diphenylphosphine oxide.

[0073] Performance testing: The method was the same as in Example 1, and the result of the cross-cut adhesion test was level 2. After vigorously rubbing the printed area with an alcohol-soaked cloth 50 times, the printed area was observed under a 365nm ultraviolet lamp. The printed area was visibly lighter, and the brightness of the fluorescent pattern decreased by 23%.

[0074] Comparative Example 2 In this comparative example, the types and quantities of the resin monomers used are the same as those used in Example 2 for the difunctional and polyfunctional resin monomers, but it does not contain monofunctional resin monomers. Everything else is the same as in Example 2.

[0075] Performance testing: The method was the same as in Example 1, and the result of the cross-cut adhesion test was level 2. After vigorously rubbing the sample area 10 times with a cotton swab soaked in ethyl acetate, the sample area was observed under a 365nm ultraviolet lamp. The sample was visibly and significantly lighter, and the brightness of the fluorescent pattern decreased by 25%.

[0076] In this comparative example, the resin monomers are difunctional and multifunctional resin monomers, but do not contain monofunctional resin monomers. When the ink prepared in this comparative example is printed on a flexible plastic substrate, the substrate curls severely after curing, indicating a significant decrease in adhesion.

[0077] Comparative Example 3 In this comparative example, all resin monomers used are monofunctional resin monomers, and the types and quantities of monofunctional resin monomers used are exactly the same as in Example 2, while the others are the same as in Example 2.

[0078] Performance testing: The method was the same as in Example 1, and the result of the cross-cut adhesion test was level 2. After vigorously rubbing the sample area 50 times with an alcohol-soaked cloth, the sample area was observed under a 365nm ultraviolet lamp. The sample was visibly and significantly lighter, and the brightness of the fluorescent pattern decreased by 22%.

[0079] In this comparative example, the functional group ratio of the resin monomers was different, and the shrinkage rate of the ink was too high at 15%, indicating a significant decrease in adhesion.

[0080] Table 1: Weight distribution ratio of each functional component in Examples 1-6

[0081] Table 2: Weight distribution ratio of functional components in Examples 7 and 8

[0082] Table 3: Raw material composition and proportions (wt) for Examples 1-6

[0083] Table 4: Raw material composition and proportions (wt) for Examples 7 and 8

[0084] Data shows that when the fluorescent inkjet ink prepared in the embodiments of the present invention is printed on a flexible plastic substrate, the substrate remains flat and without curling after curing, and the curing shrinkage rate is good. It can simultaneously achieve "0-1 level adhesion" and "brightness decay of <5% after 50 washes".

[0085] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A fluorescent composition, characterized in that, The raw material components include the following parts by weight: fluorescent dye: 0.01-10 parts, resin monomer: 1-90 parts, epoxy acrylate oligomer: 1-90 parts, cationic initiator: 1-18 parts; The resin monomer is a resin monomer whose molecule contains groups that can participate in curing; The groups that can participate in curing include at least one of epoxy groups and vinyl ether groups.

2. The fluorescent composition according to claim 1, characterized in that, The resin monomer includes: a monofunctional resin monomer; The resin monomer further includes at least one of a difunctional resin monomer and a polyfunctional resin monomer; The monofunctional resin monomer is a resin monomer that contains only one group that can participate in curing in its molecule; the difunctional resin monomer is a resin monomer that contains two groups that can participate in curing in its molecule; and the polyfunctional resin monomer is a resin monomer that contains three or more groups that can participate in curing in its molecule. Optionally, the monofunctional resin monomer is 1-90 parts by weight; The difunctional resin monomer is 1-90 parts by weight; and / or, the polyfunctional resin monomer is 1-30 parts by weight. The total amount of the monofunctional resin monomer, the difunctional resin monomer, and the polyfunctional resin monomer does not exceed 90 parts by weight. And / or, the epoxy acrylate oligomer is 10-40 parts by weight.

3. The fluorescent composition according to claim 2, characterized in that, The monofunctional resin monomer is 10-60 parts by weight; The difunctional resin monomer is 20-70 parts by weight; and / or, the polyfunctional resin monomer is 5-30 parts by weight.

4. The fluorescent composition according to claim 3, characterized in that, The monofunctional resin monomer includes at least one of monofunctional epoxy resin monomer and monofunctional vinyl ether resin monomer. Optionally, the monofunctional epoxy resin monomer is selected from: 1,2-epoxy-4-vinylcyclohexane, 1-methyl-4-(2-methylepoxyethoxy)-7-oxabicyclo[4.1.0]heptane, glycidyl 12-14 alkyl ether, and 3,4-epoxycyclohexyl methyl isobutylene ester; and / or, the monofunctional vinyl ether-based resin monomer is ethyl 2-ethyleneoxyethoxyacrylate; and / or, The difunctional resin monomer is a difunctional epoxy resin monomer, optionally selected from: dicyclopentadiene epoxide, 1,4-cyclohexanediethanol bis(3,4-epoxycyclohexanecarboxylic acid) ester, tetrahydrophthalic acid diglycidyl ester, cyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, bis(7-oxabicyclo[4.1.0]3-heptylmethyl) adipate and 3,4-epoxycyclohexylcarboxylic acid 3,4-epoxycyclohexylmethyl ester; and / or The multifunctional resin monomer is a trifunctional or tetrafunctional epoxy resin monomer, optionally selected from: triglycidyl-p-aminophenol, 4,4'-methylenebis(N,N-diglycidylaniline), and trimethylolpropane triglycidyl ether; and / or The epoxy acrylate oligomer is selected from the polymer products of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarbamate and caprolactone, poly[(2-epoxyethylene)-1,2-cyclohexanediol]2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether; and / or The cationic initiator is selected from 4-(phenylthio)phenyldiphenylthionium hexafluorophosphate, bis(4-(diphenylthionium)phenyl)sulfide-bis(hexafluorophosphate) and 4,4'-dimethyldiphenyliodothionium hexafluorophosphate; Optionally, the polymer product of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarbamate and caprolactone is designated as TTA2081; the poly[(2-epoxyethylene)-1,2-cyclohexanediol]2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether is designated as TTA3150.

5. The fluorescent composition according to claim 4, characterized in that, The fluorescent dye is selected from red fluorescent dyes, green fluorescent dyes, and blue fluorescent dyes; Optionally, the red fluorescent dye is a europium(III) complex that, when excited by 365 nm ultraviolet light, emits red fluorescence with a main peak at 610-620 nm; and / or The green fluorescent dye is a mesoscopic polymeric fluorescent material, which is a polymeric material with a molecular weight of 4,000-700,000; optionally, the mesoscopic polymeric fluorescent material is a polymeric material with a molecular weight of 4,118-661,000. The blue fluorescent dye is a small-molecule organic compound containing a fused aromatic ring system in its molecular structure and capable of emitting blue fluorescence under ultraviolet light excitation; the small-molecule organic compound has a molecular weight of less than 1000; and / or Further optionally, the blue fluorescent dye is selected from benzoxazole organic fluorescent dyes and stilbene organic fluorescent dyes; Further optionally, the benzoxazole-based organic fluorescent dye is selected from: 1,2-bis(5-methylbenzo[d]oxazol-2-yl)ethylene, 1,2-bis(5-methyl-2-benzoxazolyl)-ethylene, and the stilbene-based organic fluorescent dye is 4,4'-bis[2-methoxystyryl]-1,1'-biphenyl; and / or The europium(III) complex is selected from tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione]europium(III), with the structural formula shown in Formula 1: Formula 1; Tris(1,1,1,5,5,5-hexafluoro-2,4-pentanedione) europium(III), with the structural formula shown in Formula 2: Formula 2; and Tris(1,3-diphenyl-propanedione)europium(III), with the structural formula shown in Formula 3: Formula 3; and / or The linear mesoscopic polymeric fluorescent dye is selected from green fluorescent dye 1, and its structural formula is shown in Formula 4: Equation 4, Where n is an integer selected from 10 to 1000; Optionally, n=41; and Green fluorescent dye 2, with the structural formula shown in Formula 5: Equation 5, Where n is an integer selected from 10 to 1000; Optional, n=76.

6. A fluorescent inkjet ink, characterized in that, Its raw materials include the composition according to any one of claims 1-5; Optionally, it also contains 0.01-5 parts by weight of a leveling agent; Further optionally, the leveling agent is selected from polyether-modified polysiloxane organic compounds, polyester-modified polysiloxane organic compounds, and acrylate organic compounds; Further optionally, the polyether-modified polysiloxane organic compound is designated BYK307 or Glide410, the polyester-modified polysiloxane organic compound is designated BYK331, and / or the acrylate organic compound is designated BYK-358N.

7. The fluorescent inkjet ink according to claim 6, characterized in that, The solubility of the fluorescent dye in organic solvents is 0.01-200 g / kg; Optionally, the raw material components of the fluorescent inkjet ink are selected from any of the following: 0.5 parts of tri[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione]europium(III); 40 parts of ethyl 2-ethyleneoxyethoxyacrylate; 20 parts of a difunctional resin monomer mixture consisting of methyl 3,4-epoxycyclohexylcarboxylate and diglycidyl cyclohexane-1,2-dicarboxylic acid in a mass ratio of 1:1; 30 parts of trimethylolpropane triglycidyl ether; 15 parts of TTA2081; 1 part of a cationic initiator mixture consisting of 4-(phenylthio)phenyldiphenylthionyl hexafluorophosphate and bis(4-(diphenylthionyl)phenyl)sulfide-bishexafluorophosphate in a mass ratio of 2:1; and 2 parts of leveling agent BYK-307. The composition consists of 10 parts of green fluorescent dye 1, 20 parts of a monofunctional resin monomer mixture composed of 1,2-epoxy-4-vinylcyclohexane and glycidyl 12-14 alkyl ether in a 1:1 mass ratio, 50 parts of a difunctional epoxy resin monomer mixture composed of dicyclopentadiene epoxide and 1,4-cyclohexanediethanol bis(3,4-epoxycyclohexanecarboxylic acid) ester in a 1:1 mass ratio, 17 parts of a polyfunctional epoxy resin monomer mixture composed of triglycidyl p-aminophenol and trimethylolpropane triglycidyl ether in a 1:1 mass ratio, 10 parts of TTA2081, 18 parts of a cationic initiator mixture composed of bis(4-(diphenylthionyl)phenyl)sulfide-bis(hexafluorophosphate) and 4-4'-dimethyldiphenyliodothionyl hexafluorophosphate in a 2:1 mass ratio, and 0.01 parts of leveling agent BYK-331. The fluorescent dye composed of 4,4'-bis[2-methoxystyryl]-1,1'-biphenyl and 1,2-bis(5-methyl-2-benzoxazolyl)-ethylene in a mass ratio of 1:2 was 0.01 parts; 1-methyl-4-(2-methylepoxyethylene)-7-oxabicyclo[4.1.0]heptane was 60 parts; and tetrahydrophthalic acid diglycidyl ester and 4,5-epoxycyclohexane in a mass ratio of 1:1 were used. The mixture consists of 20 parts of a difunctional epoxy resin monomer mixture composed of diglycidyl 1,2-dicarboxylic acid diglycidyl ester, 5 parts of triglycidyl p-aminophenol, 25 parts of TTA3150, 15 parts of a cationic initiator mixture composed of 4-(phenylthio)phenyldiphenylthionyl hexafluorophosphate and 4-4'-dimethyldiphenyliodothionyl hexafluorophosphate in a mass ratio of 3:1, and 0.5 parts of leveling agent BYK-358N. 5 parts of 4,4'-bis[2-methoxystyryl]-1,1'-biphenyl, 10 parts of 1,2-epoxy-4-vinylcyclohexane, 70 parts of a difunctional epoxy resin monomer mixture consisting of 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and bis(7-oxabicyclo[4.1.0]3-heptylmethyl) adipate in a mass ratio of 1:1:1, 40 parts of 4,4'-methylene bis(N,N-diglycidylaniline), 40 parts of TTA3150, 10 parts of bis(4-(diphenylthionyl)phenyl)sulfide-bis(hexafluorophosphate), and 4.5 parts of leveling agent Glide-410; The following components are listed: 0.01 parts of tris(1,1,1,5,5,5-hexafluoro-2,4-pentanedione) europium(III), 60 parts of 1-methyl-4-(2-methylepoxyethylene)-7-oxabicyclo[4.1.0]heptane, 20 parts of a difunctional epoxy resin monomer mixture consisting of diglycidyl tetrahydrophthalate and diglycidyl 4,5-epoxycyclohexane-1,2-dicarboxylic acid in a 1:1 mass ratio, 5 parts of triglycidyl p-aminophenol, 25 parts of TTA3150, 15 parts of a cationic initiator mixture consisting of 4-(phenylthio)phenyldiphenylthionyl hexafluorophosphate and 4-4'-dimethyldiphenyliodothionyl hexafluorophosphate in a 3:1 mass ratio, and 0.5 parts of leveling agent BYK-358N. The mixture consists of 5 parts tris(1,3-diphenyl-propanedione)europium(III), 10 parts 1,2-epoxy-4-vinylcyclohexane, 70 parts a difunctional epoxy resin monomer mixture composed of 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether and bis(7-oxabicyclo[4.1.0]3-heptylmethyl) adipate in a mass ratio of 1:1:1, 4,4'-methylene bis(N,N-diglycidylaniline), 40 parts TTA3150, 10 parts bis(4-(diphenylthionyl)phenyl)sulfide-bis(hexafluorophosphate), and 4.5 parts leveling agent Glide-410. 0.5 parts of 4,4'-bis[2-methoxystyryl]-1,1'-biphenyl, 40 parts of ethyl 2-ethyleneoxyethoxyacrylate, 30 parts of trimethylolpropane triglycidyl ether, 15 parts of TTA2081, and 1 part of a cationic initiator mixture consisting of 4-(phenylthio)phenyldiphenylthionium hexafluorophosphate and bis(4-(diphenylthionium)phenyl)thionium-bishexafluorophosphate in a mass ratio of 1:1; The mixture comprises 8 parts of 1,2-bis(5-methylbenzo[d]oxazol-2-yl)ethylene; 20 parts of a monofunctional resin monomer mixture consisting of 1,2-epoxy-4-vinylcyclohexane and glycidyl 12-14 alkyl ether in a mass ratio of 1:1; 50 parts of a difunctional epoxy resin monomer mixture consisting of dicyclopentadiene epoxide and 1,4-cyclohexanediethanol bis(3,4-epoxycyclohexanecarboxylic acid) ester in a mass ratio of 1:1; 10 parts of TTA2081; 15 parts of a cationic initiator mixture consisting of bis(4-(diphenylthionyl)phenyl)sulfide-bis(hexafluorophosphate) and 4-4'-dimethyldiphenyliodothionyl hexafluorophosphate in a mass ratio of 2:1; and 0.01 parts of leveling agent BYK-331. The composition includes 10 parts of green fluorescent dye 2, 20 parts of a monofunctional epoxy resin monomer mixture consisting of 1,2-epoxy-4-vinylcyclohexane and glycidyl 12-14 alkyl ether in a 1:1 mass ratio, 50 parts of a difunctional epoxy resin monomer mixture consisting of dicyclopentadiene epoxide and 1,4-cyclohexanediethanol bis(3,4-epoxycyclohexanecarboxylic acid) ester in a 1:1 mass ratio, 17 parts of a polyfunctional epoxy resin monomer mixture consisting of triglycidyl p-aminophenol and trimethylolpropane triglycidyl ether in a 1:1 mass ratio, 10 parts of TTA2081, 18 parts of a cationic initiator mixture consisting of bis(4-(diphenylthionyl)phenyl)sulfide-bis(hexafluorophosphate) and 4-4'-dimethyldiphenyliodonium hexafluorophosphate in a 2:1 mass ratio, and 0.01 parts of leveling agent BYK-331.

8. The method for preparing the fluorescent inkjet ink according to claim 6 or 7, characterized in that, Ink is prepared using fluorescent dyes, cationic initiators, resin monomers, epoxy acrylate oligomers, and leveling agents; Optionally, the following steps are included: a) Under light-protected conditions, fluorescent dye, resin monomer, epoxy acrylate oligomer, cationic initiator, and leveling agent are mixed in proportion to obtain a mixture solution; b) Filter the mixture solution obtained in step a) to obtain the fluorescent inkjet ink.

9. A fluorescent label, characterized in that, Prepared by curing the fluorescent inkjet ink as described in claim 6 or 7 using UV / UV-LED. Optionally, the fluorescent inkjet ink is red, blue, and / or green, and the fluorescent marker is a single primary color, a two-primary color, or a three-primary color.

10. Use of the fluorescent inkjet ink of claim 6 or 7 in the field of anti-counterfeiting, optionally in the field of anti-counterfeiting of commodity packaging, securities, certificates, and / or polymer banknotes; and optionally, the fluorescent inkjet ink is adhered to a substrate of polycarbonate or polymer banknote paper.

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