KR102491823B1 - Pressure discolored fluorescent material and forgery prevention device using the same - Google Patents

Abstract

The present invention relates to a pressure-discolored fluorescent material and a forgery prevention device using the same. Specifically, the present invention relates to a pressure-discolored fluorescent material including a nanoparticled fluorescent dye, a forgery prevention device using the same, and a forgery authentication method using the forgery prevention device. The present invention improves the aggregation effect of the fluorescent dye by increasing the number of branches in the molecular structure of the fluorescent dye and can change an emission wavelength.

Description

Pressure discoloration fluorescent material and anti-counterfeiting device using the same {PRESSURE DISCOLORED FLUORESCENT MATERIAL AND FORGERY PREVENTION DEVICE USING THE SAME}

The present invention utilizes a nanoparticled fluorescent dye for an anti-counterfeiting device, specifically, a pressure-discoloring fluorescent material containing a nanoparticled fluorescent dye, an anti-counterfeiting device using the same, and tampering authentication using the anti-counterfeiting device. It's about how.

Various technologies have been introduced to prevent counterfeiting and falsification of expensive products or products requiring authenticity of contents. Conventionally, technologies using fine patterns, braille, holograms, RFID, etc. have been mainly used to prevent counterfeiting and falsification of products, but these conventional technologies have limitations in that it is not easy for general users to discriminate whether products are counterfeit or falsified. However, there is a problem in that a lot of cost is required to manufacture anti-counterfeiting and tampering devices.

Forgery prevention technology, the technology that can be easily checked by the general consumer (Overt) should be given the highest priority, but as the technology for copying is gradually developing, from the viewpoint of manufacturers/suppliers, the form in which the forgery prevention technology is additionally hidden (Covert) When a forged product is detected by applying it as high, a security technology that can be double-checked is required.

Recently, interest in technologies enabling fluorescence control in a solid phase is increasing. Among them, there is a piezochromic fluorescence technique. As materials are aggregated by pressure or physical force, the secondary binding force between molecules such as π-π interaction, hydrogen bonding, and van der Waals force in the chemical structure of the material changes. It is a phenomenon in which the fluorescence color or intensity changes and returns to the original fluorescence through heat treatment or the like.

Organic materials whose fluorescence emission characteristics are changed while being agglomerated have been researched and developed in various industrial fields such as displays, solar cells, and piezoelectric fluorescence sensors.

Regarding the use of the aggregation phenomenon of molecules, conventionally, molecular aggregation is achieved through association of chemical bonds in organic molecules (intra-molecular interaction) or intermolecular (inter-molecular interaction), and piezoelectric discoloration fluorescence characteristics are obtained. designed to.

In this regard, there are two main types of changes in emission wavelength caused by molecular aggregation. When an aromatic ring exists in a molecule, it has a packing structure between molecules due to resonance or electron transfer between delocalized electrons in the solidification step of a material. This packing structure largely consists of intermolecular interactions ( There is H-Aggregation, which is a structure that is sequentially stacked by inter-chain interaction, and J-Aggregation, which is a structure that is twisted and stacked by Intra-chain interaction (see Figure 1).

This stacking structure may vary depending on the structure of the molecule itself and the method of solidification. In general, the stacking structure through solidification or chemical crystallization can be controlled.

At this time, the standard of external pressure intensity for changing color according to interaction is more than 10MPa, which is generally difficult to utilize, so there is a limit to easily commercializing the molecules in various fields, and fluorescence is difficult to apply to small printed materials such as labels. There are many limitations in selecting an excipient capable of supporting the material.

Here, excipients used in prints are generally called binders, and are fixed using a heat or light curing agent. Since these binders may react with unsaturated bonds included in the structure of the piezoelectric color-changing organic light emitting material, their usability is limited. Therefore, in the case of the excipients proposed in the prior art, there is a disadvantage in that they cannot be used in fields such as small prints.

As a result of diligent efforts to solve the above technical problems, the inventors of the present invention utilize a fluorescent material whose luminous properties change as it is agglomerated, thereby providing ease of the printing process and at the same time easily determining whether it is forged or altered by external stimuli. Therefore, a counterfeiting device with high usability in various fields was obtained and the present invention was reached.

Therefore, the first technical problem to be solved by the present invention is to provide a forgery prevention device that is highly usable in various fields because it can easily determine whether or not it is forgery while the light emitting characteristics are changed while being agglomerated.

In addition, a second technical problem of the present invention is to provide an anti-counterfeiting device for easy printing process.

A third technical problem of the present invention is to provide a forgery authentication method using the forgery prevention device of the present invention.

In order to solve the above technical problem, the present invention

Including a fluorescent dye represented by the following formula,

The fluorescent dye is nanoparticled by an organic polymer,

It provides a pressure changeable fluorescent material containing a nanoparticled fluorescent dye.

[chemical formula]

이고, A is H or

ego,

(-N(C₆H₅)₂), 또는

(-N(C₆H₄R)₂) 이고,B is -R, -OR, -OCOR, -NHCOR, -NR (C ₆ H ₅ )

(-N(C ₆ H ₅ ) ₂ ), or

(-N(C ₆ H ₄ R) ₂ ),

R is -(CH ₂ ) _n CH ₃ , or -O(CH ₂ ) _n CH ₃ ;

n is an integer from 0 to 5;

인 것일 수 있다.In one embodiment of the present invention, at least two or more of the six A's included in the formula

may be

In one embodiment of the present invention, the fluorescent dye having the above chemical formula may include a molecular configuration in which electrons in the bonsai can be de-localized by a pi-pi (π-π) interaction. there is.

In one embodiment of the present invention, the particle size of the nanoparticled fluorescent dye may be 20 ~ 800nm.

In one embodiment of the present invention, the organic polymer is an acrylic copolymer having an ammonium functional group, preferably a copolymer containing at least one of poly(chlorotrimethyl-aminoioethyl methacrylate), poly(ethyl acrylate), and poly(methyl methacrylate) And, most preferably ammonio methacrylate copolymer.

In one embodiment of the present invention, the organic polymer of the nanoparticled fluorescent dye may be destroyed by a physical stimulus to change the emission wavelength of the fluorescent dye.

the present invention

(S1) preparing a first solution containing a first solvent;

(S2) preparing a second solution by dissolving a fluorescent dye of the following chemical formula and an organic polymer in a second solvent;

(S3) preparing a mixed solution by mixing the first solution and the second solution by adding a second solution dropwise to the first solution;

(S4) stirring the mixed solution to proceed with emulsification;

It provides a method for producing a nanoparticled fluorescent dye comprising a.

[chemical formula]

이고, A is H or

ego,

(-N(C₆H₅)₂), 또는

(-N(C₆H₄R)₂) 이고,B is -R, -OR, -OCOR, -NHCOR, -NR (C ₆ H ₅ )

(-N(C ₆ H ₅ ) ₂ ), or

(-N(C ₆ H ₄ R) ₂ ),

R is -(CH ₂ ) _n CH ₃ , or -O(CH ₂ ) _n CH ₃ ;

n is an integer from 0 to 5;

인 것일 수 있다.In one embodiment of the present invention, at least two or more of the six A's included in the formula

may be

In one embodiment of the present invention, the method for producing a nanoparticled fluorescent dye may further include a particleization step through (S5) evaporation.

In one embodiment of the present invention, the first solvent is one or more solvents selected from the group consisting of water, distilled water, and alcohol,

The second solvent may be one or more solvents selected from the group consisting of saturated petroleum solvent (CnH2n+2), Halocarbon oil 0.8, Halocarbon oil 1.8, Isoparaffin oil (C<12), Tetrachloromethane, Tetrahydrofuran, Trichloromethane, and Dichloromethane. there is.

In one embodiment of the present invention, the heating in the step (S5) may be performed for 30 minutes to 2 hours in the range of 30 ℃ to 60 ℃.

On the other hand, anti-counterfeiting device using the fluorescent dye of the present invention is a substrate layer; and a pattern layer disposed on an upper side of the substrate layer and including a pressure-discoloring fluorescent material. Characterized in that it includes, it is possible to provide a forgery prevention device.

On the other hand, in another embodiment of the present invention, the anti-counterfeiting device using the pressure discoloration fluorescent material of the present invention

base layer; a pattern unit disposed on a portion of an upper portion of the substrate layer and including a pressure-discoloring fluorescent material; And among the substrate layer, it is possible to provide a forgery and alteration prevention device, characterized in that the pattern portion is printed on the non-printed portion and consists of a background portion (FIG. 7) for describing a specific background pattern.

In one embodiment of the present invention, the fluorescent dye is 0.01% to 20% by weight, preferably 0.01% to 10% by weight, more preferably 0.01% to 5% by weight based on the total weight of the pattern layer or pattern portion. may be included in weight percent.

The solution to the above problems does not enumerate all the features of the present invention. Various features of the present invention and the advantages and effects thereof will be understood in more detail with reference to the following specific examples.

The present invention increases the number of branches in the molecular structure of the fluorescent dye to improve the aggregation effect of the fluorescent dye, thereby easily inducing nanoparticles and thereby easily changing the emission wavelength by external stimulation. can provide.

In addition, the present invention provides the ease of the printing process by utilizing a fluorescent dye whose luminous properties change as it is agglomerated, and at the same time, it is possible to easily determine whether it is forged or altered by an external stimulus. Forgery prevention device with high utility in various fields can provide.

In addition to the above effects, specific effects of the present invention will be described together while explaining specific details for carrying out the present invention.

1 is a schematic diagram showing the expression of H-aggregation and J-aggregation, which are types of molecular aggregation, and the resulting energy change.
Figure 2 shows the nanoparticled fluorescent dye of the present invention, showing the fluorescent dye forming the core and the organic polymer forming the shell.
Figure 3 is according to an embodiment of the present invention, showing a scanning electron microscope (Scanning Electron Microscope, SEM) image of the nanoparticled fluorescent dye of Example 1.
Figure 4 is according to an embodiment of the present invention, showing a scanning electron microscope (Scanning Electron Microscope, SEM) image of the nanoparticled fluorescent dye of Example 2.
Figure 5 is according to an embodiment of the present invention, showing a scanning electron microscope (Scanning Electron Microscope, SEM) image of the nanoparticled fluorescent dye of Example 3.
Figure 6 shows that the organic polymer is destroyed (particles are destroyed) by a physical stimulus to the nanoparticled fluorescent dye according to an embodiment of the present invention, and the emission wavelength is changed.
7 is a cross-sectional view of an anti-counterfeiting device manufactured according to an embodiment of the present invention.
Figure 8 shows the change in fluorescence emission wavelength when a physical stimulus is applied to the nanoparticled fluorescent dye of Example 1.
Figure 9 shows the change in fluorescence emission wavelength when a physical stimulus is applied to the nanoparticled fluorescent dye of Example 2.
Figure 10 shows the change in fluorescence emission wavelength when a physical stimulus is applied to the nanoparticled fluorescent dye of Example 3.

Hereinafter, the principles of preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings and description. However, the drawings shown below and the description below relate to preferred implementation methods among various methods for effectively explaining the features of the present invention, and the present invention is not limited to only the drawings and description below.

Meanwhile, terms such as first or second may be used to describe various components, but these terms should be interpreted only for the purpose of distinguishing one component from another. For example, a first element may be termed a second element, and similarly, a second element may be termed a first element.

Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "comprise" or "have" are intended to designate that the described feature, number, step, operation, component, part, or combination thereof exists, but one or more other features or numbers, It should be understood that the presence or addition of steps, operations, components, parts, or combinations thereof is not precluded.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in this specification, interpreted in an ideal or excessively formal meaning. It doesn't work.

The term 'forgery' used in this specification may refer to any act of creating a new object that does not exist for the purpose of use by an unauthorized person, or any act of applying changes to an existing object without authorization.

Figure 1 shows the types of molecular aggregation of fluorescent dyes used in anti-counterfeiting devices using polarized light, and shows energy changes of H-aggregation (H-aggregation) and J-aggregation (J-aggregation).

In this way, as the degree of aggregation of the fluorescent dyes changes due to the applied stimulus, a difference occurs in the energy level of the material, and accordingly, various colors and patterns are expressed externally. can be applied

Figure 2 shows the nanoparticled fluorescent dye of the present invention, showing the fluorescent dye forming the core and the organic polymer forming the shell.

Hereinafter, with reference to this, the nanoparticled fluorescent dye used in the anti-counterfeiting device according to an embodiment of the present invention will be described.

In one embodiment of the present invention, the degree of aggregation of the nanoparticled fluorescent dye changes according to an applied external stimulus, so that dichroic fluorescence characteristics can be implemented.

In the present invention, a nanoparticled fluorescent dye composed of a fluorescent dye forming a core and an organic polymer forming a shell of a nano-sized dye having fluorescence characteristics is utilized.

the present invention

Including a fluorescent dye represented by the following formula,

The fluorescent dye is nanoparticled by an organic polymer,

It relates to a pressure discoloration fluorescent material comprising the nanoparticled fluorescent dye.

[chemical formula]

이고, A is H or

ego,

(-N(C₆H₅)₂), 또는

(-N(C₆H₄R)₂) 이고,B is -R, -OR, -OCOR, -NHCOR, -NR (C ₆ H ₅ )

(-N(C ₆ H ₅ ) ₂ ), or

(-N(C ₆ H ₄ R) ₂ ),

R is -(CH ₂ ) _n CH ₃ , or -O(CH ₂ ) _n CH ₃ ;

n is an integer from 0 to 5;

The fluorescent dye having the above chemical formula preferably has a molecular structure in which electrons in the molecule can be de-localized by pi-pi (π-π) interaction.

Here, the particle diameter of the nanoparticled fluorescent dye may be 20 ~ 800nm.

The inventor of the present invention found that when the molecule of the fluorescent dye has a structurally large steric hindrance, specifically, the larger the molecular structure of the functional group, the easier the aggregation reaction of nanoparticles by external stimulation, and accordingly, the emission wavelength It was found that the change appeared to be larger and led to the present invention. Specifically, the present invention improves the aggregation effect of the fluorescent dye by increasing the number of branches in the molecular structure of the fluorescent dye, thereby easily inducing nanoparticles and easily changing the emission wavelength by external stimuli. It is about fluorescent dyes in

According to one embodiment of the present invention, the fluorescent dye may be made into nanoparticles by organic polymers.

When an external stimulus is applied to the nanoparticled fluorescent dye, the organic polymer material is destroyed, and as a result, the degree of aggregation of the fluorescent dye changes while dichroic fluorescence characteristics can be implemented.

An external stimulus applied to the nanoparticled fluorescent dye may be a physical stimulus such as push or scratch.

The organic polymer material may be an acrylic copolymer having an ammonium functional group, and specifically, a copolymer including at least one repeating unit of poly(chlorotrimethyl-aminoioethyl methacrylate), poly(ethyl acrylate), and poly(methyl methacrylate). The most preferred organic polymer is ammonio methacrylate copolymer.

In the present invention, the method of converting fluorescent dyes into nanoparticles using organic polymers uses a method of inducing aggregation of fluorescent dyes in a state in which they are not mixed using the solubility principle.

In one embodiment of the present invention, the method for preparing the nanoparticled fluorescent dye of the present invention

(S1) preparing a first solution containing a first solvent;

(S2) preparing a second solution by dissolving the fluorescent dye and the organic polymer in a second solvent;

(S3) preparing a mixed solution by mixing the first solution and the second solution by adding a second solution dropwise to the first solution;

(S4) stirring the mixed solution to proceed with emulsification;

It provides a method for producing a nanoparticled fluorescent dye comprising a.

In one embodiment of the present invention, the fluorescent dye may have a molecular structure of the following chemical formula.

[chemical formula]

[chemical formula]

이고, A is H or

ego,

(-N(C₆H₅)₂), 또는

(-N(C₆H₄R)₂) 이고,B is -R, -OR, -OCOR, -NHCOR, -NR (C ₆ H ₅ )

(-N(C ₆ H ₅ ) ₂ ), or

(-N(C ₆ H ₄ R) ₂ ),

R is -(CH ₂ ) _n CH ₃ , or -O(CH ₂ ) _n CH ₃ ;

n is an integer from 0 to 5;

In an embodiment of the present invention, it is preferable that the first solvent and the second solvent are solvents that do not mix with each other, that is, have a difference in polarity. Due to the difference in polarity of the two solvents, the second solution containing the fluorescent dye forms droplets on the first solution, and at the same time, heat is applied to volatilize the second solvent, thereby reducing the solubility of the fluorescent dye and organic polymer It is aggregated inside and induces the crystallinity of the organic polymer, so that the granulation proceeds to have a solid phase.

In one embodiment of the present invention, each of the first solvent and the second solvent is one or more solvents selected from the group consisting of water, distilled water, and alcohol, and has a higher polarity than the second solvent, and the second solvent is the first solvent. A solvent with a lower boiling point or polarity is preferred. In a preferred embodiment, the second solvent is selected from the group consisting of saturated petroleum solvent (C _n H _2n+2 ), Halocarbon oil 0.8, Halocarbon oil 1.8, Isoparaffin oil (C<12), Tetrachloromethane, Tetrahydrofuran, Trichloromethane, and Dichloromethane. It is preferable that it is 1 or more types selected.

The fluorescent dye and the organic polymer are contained in an amount of 0.001% to 10% by weight, preferably 0.001% to 5% by weight based on the total weight of the second solution, and the fluorescent dye is 0.0001% by weight based on the total weight of the second solution. to 1% by weight, preferably 0.0005 to 0.4% by weight.

Among the methods for preparing the nanoparticled fluorescent dye of the present invention, the emulsification step (S3) may be performed for 1 to 10 minutes.

The manufacturing method of the nanoparticled fluorescent dye of the present invention may further include a granulation step using solution evaporation through heating (S5) following the above (S4).

At this time, the heating in step (S5) may be performed for 30 minutes to 2 hours in the range of 30 ℃ to 60 ℃. While removing the solvent through heating, in-situ polymerization of organic polymers is induced to proceed with nanoparticle fluorescent dyeing.

After proceeding with nanoparticles through step (S5), distilled water or the like may be added to remove residual impurities, and other agglomerated impurities may be removed using a sieve.

Then, when the nanoparticled fluorescent dye is obtained, it is pulverized using a mortar and pestle to obtain the final nanoparticled fluorescent dye.

The nanoparticled fluorescent dye prepared through the steps (S1) to (S5) is shown in FIG. 2. Fluorescent dye shows nanoparticle shape by organic polymer.

In the nanoparticled fluorescent dye of the present invention, organic polymers are destroyed by physical stimuli, and granulation is destroyed. As a result, the degree of aggregation of the fluorescent dye changes and the emission wavelength of the fluorescent dye changes, thereby showing a different color. can

Specifically, as the fluorescent dye is aggregated into nanoparticles, the emission wavelength shifts to a longer wavelength, and the organic polymer is destroyed and the nanoparticles are broken, resulting in a change in emission characteristics in which the emission wavelength shifts to a shorter wavelength.

7 shows a cross-section of an anti-counterfeiting device according to an embodiment of the present invention manufactured using the nanoparticled fluorescent dye of the present invention. Hereinafter, based on this, a forgery prevention device to which the present invention is applied will be described.

Anti-counterfeiting device according to an embodiment of the present invention includes a base layer; It may include a pattern layer disposed on the upper side of the base layer.

Anti-counterfeiting device according to an embodiment of the present invention includes a base layer; a pattern unit disposed on an upper portion of the substrate layer and including a nanoparticled fluorescent dye; And among the base layer, it may include a background part printed on the remaining part where the pattern part is not located and describing a specific background pattern.

The substrate layer may be located at the lowest layer of the anti-counterfeiting device, and various film layers used to manufacture labels in the art, such as synthetic resin, oil labels, paper and / or metal, may be used.

At this time, the pattern layer/pattern part is printed on the substrate layer in the above-described nanoparticle fluorescent dye state, and may be composed of a pattern distinguished from the background part described later.

The pattern layer/pattern part may have a form including a known binder to have adhesiveness with a substrate, and the binder may be included in an amount of 80% to 99.9% by weight based on the total weight of the pattern layer/pattern part. there is.

The background part is printed on the part where the pattern layer/pattern part is not printed on the substrate layer, and a specific background pattern can be printed.

On the other hand, when a physical stimulus is applied to the anti-counterfeiting device of the present invention, the nanoparticled fluorescent dye capsules included in the pattern layer/pattern part are destroyed, and accordingly, the degree of aggregation of the fluorescent dyes varies, and the emission wavelength (λ) varies. can For example, dichroic fluorescence characteristics are exhibited while the emission wavelength of the fluorescent dye moves to a shorter wavelength by physical stimulation.

On the other hand, it can be used to determine forgery or alteration by utilizing the forgery prevention device of the present invention.

A method for determining whether forgery or falsification using the forgery prevention device of the present invention

A first authentication step of applying a physical stimulus to the pattern unit of the anti-counterfeiting device;

a second authentication step of confirming a change in light emission color of the pattern part; can include

Here, in the second authentication step, it is possible to determine forgery or falsification by a device capable of confirming a change in light emission color with the naked eye or detecting a change in light emission wavelength.

Hereinafter, preferred embodiments are presented to aid understanding of the present invention, but the following examples are merely illustrative of the present invention, and various changes and modifications are possible within the scope and spirit of the present invention. It is obvious to those skilled in the art, It goes without saying that these variations and modifications fall within the scope of the appended claims. Examples and comparative examples of the present invention are described below. Such following examples are only one embodiment of the present invention, but the present invention is not limited to the following examples.

Preparation Example 1. Preparation of Fluorescent Dye of Chemical Formula 1

Triethyl phosphite (15 mL, 87.475 mmol) and dry 1,4-Di(bromomethyl)benzene (2.50 g, 9.546 mmol) were put in a round bottom flask and reacted under argon atmosphere at 150° C. for 18 h under reflux stirring.

Then, after removing triethyl phosphite using a distillation device, 1,4-Di(diethoxyphosphomethyl)benzene as an intermediate is obtained.

Next, 1,4-Di(diethoxyphosphomethyl)benzene (2.00 g, 5.289 mmol) and 4-(Diphenylamino)benzaldehyde (3.3 g, 12.1 mmol) were added to 30ml of THF in a two-necked round bottom flask and incubated at 0°C for 10 minutes. Stir for a minute.

Thereafter, t-BuOK (2.54 g, 22.636 mmol) was added at 0 ° C, stirred at room temperature for 24 hours, washed with distilled water, and the fluorescent dye of Formula 1 ((2,4- Di[2-[4-[N,N-di(ptolyl)amino]phenyl]vinyl]benzene)) is obtained.

[Formula 1]

Preparation Example 2. Preparation of Fluorescent Dye of Chemical Formula 2

Triethyl phosphite (15 mL, 87.475 mmol) and dry 1,3,5-tris(bromomethyl)benzene (2.50 g, 7.005 mmol) were put in a round bottom flask and reacted under argon atmosphere at 150° C. for 18 h under reflux stirring.

Then, after removing triethyl phosphite using a distillation device, 1,3,5-Tris (diethoxyphosphomethyl) benzene as an intermediate is obtained.

Next, 1,3,5-Tris(diethoxyphosphomethyl)benzene (2.00 g, 3.784 mmol) and 4-(Diphenylamino)benzaldehyde (3.3g, 12.1 mmol) were added to 30ml of THF in a two-necked round bottom flask, and 0°C stirred for 10 minutes.

Then, t-BuOK (2.54 g, 22.636 mmol) was added at 0 ° C, stirred at room temperature for 24 hours, washed with distilled water, and then a fluorescent dye of formula 2 ((1,3,5-tris [2-[4-[N,N-di(ptolyl)amino]phenyl]vinyl]benzene)) is obtained.

[Formula 2]

Preparation Example 3. Preparation of Fluorescent Dye of Chemical Formula 3

Triethyl phosphite (15 mL, 87.475 mmol) and dry 1,2,4,5-Tetrakis(bromomethyl)benzene (2.50 g, 5.558 mmol) were put in a round-bottom flask and reacted under argon atmosphere at 150 ° C under reflux stirring for 18 h. let it

Then, after removing triethyl phosphite using a distillation device, 1,2,4,5-Tetrakis (diethoxyphosphomethyl) benzene as an intermediate is obtained.

Next, 1,2,4,5-Tetrakis (diethoxyphosphomethyl) benzene (2.00 g, 2.950 mmol) and 4- (Diphenylamino) benzaldehyde (3.3 g, 12.1 mmol) were added to 30 ml of THF in a two-necked round bottom flask and 0 Stir at °C for 10 minutes.

Thereafter, tBuOK (2.54 g, 22.636 mmol) was added at 0 ° C., stirred at room temperature for 24 hours, washed with distilled water, and a fluorescent dye corresponding to Formula 3 of the present invention ((1,2,4,5 -Tetrakis[2-[4-[N,N-di(ptolyl)amino]phenyl]vinyl]benzene)).

[Formula 3]

Example 1. Preparation of nanoparticled fluorescent dye (Preparation Example 1)

2.75 g of Polyvinyl alcohol (PVA) was added to 247.25 g of distilled water and heated at 80° C. for 5 hr to prepare a first solution (water phase).

0.01g ammonio methacrylate copolymer was added to 10g of tetrahydrofuran, and the fluorescent dye of Preparation Example 1 ((2,4-Di[2-[4-[N,N-di(ptolyl) amino]phenyl]vinyl]benzene)) 0.01g was added and stirred at room temperature for 1 hr to prepare a 22nd solution (oil phase).

250 g of the first solution was transferred to a 1L tall beaker, and 125 g of the second solution phase was added dropwise while mixing at low speed. At this time, the homogenizer was adjusted to 600 rpm.

When all of the second solution was added, the speed of the homogenizer was set to 4,000 rpm, and an emulsification reaction was performed for 5 minutes to prepare an emulsion.

Then, after lowering the speed to 600 rpm, the bubble size was checked through process inspection, and when the target size was reached, about 1.5 g of 10% antifoaming agent was added to remove the remaining bubbles.

After removing bubbles, the emulsion was transferred to a 3L 1-Neck R-B Flask and connected to a concentrator for particleization through evaporation.

After degassing at 790 mbar at room temperature for about 10 minutes, the pressure was slowly reduced to 600 mbar, and after reaching 600 mbar, the temperature was raised to 40 ° C. After reaching 40 ℃, the pressure was slowly reduced to 70 mbar to remove the solvent remaining inside.

After removing the solvent, a dispersion was obtained in which the prepared nanoparticled fluorescent dye was dispersed in water at a concentration of 100 ppm.

Example 2. Preparation of nanoparticled fluorescent dye (Preparation Example 2)

In the preparation method of Example 1, instead of the fluorescent dye of Preparation Example 1, the fluorescent dye of Preparation Example 2 ((1,3,5-Tris[2-[4-[N,N-di(ptolyl) amino]phenyl A nanoparticled fluorescent dye was prepared in the same manner as in Example 1, except that ]vinyl]benzene)) was added and reacted.

Example 3. Preparation of nanoparticled fluorescent dye (Preparation Example 3)

In the preparation method of Example 1, instead of the fluorescent dye of Preparation Example 1, the fluorescent dye of Preparation Example 3 ((1,2,4,5-Tetrakis[2-[4-[N,N-di(ptolyl) amino A nanoparticled fluorescent dye was prepared in the same manner as in Example 1, except that ]phenyl]vinyl]benzene)) was added and reacted.

Experimental Example 1. Particle size analysis of nanoparticled fluorescent dye

Particle size analysis of the fluorescent dye was confirmed through dynamic light scattering method (DLS) and scanning electron microscope (SEM).

In the dynamic light scattering method, the fluorescent dye was dispersed in deionized water (DIW) at a concentration of 10 ppm and measured according to ISO 22412 (Particle size analysis-DLS). dye ((2,4-Di[2-[4-[N,N-di(ptolyl)amino]phenyl]vinyl]benzene)) or the fluorescent dye of Example 2 ((1,3,5-tris[2 -[4-[N,N-di(ptolyl)amino]phenyl]vinyl]benzene)) and the fluorescent dye of Example 3 ((1,2,4,5-Tetrakis[2-[4-[N,N After dissolving -di(ptolyl) amino]phenyl]vinyl]benzene)), it was added to purified water to a concentration of 10 ppm, mixed, and particle size was measured. The results are as follows.

DLS SEM Average particle diameter (nm) Polydispersity index Particle size range (nm) Example 1 108.1 0.092 80 to 100 Example 2 78.1 0.126 50 to 350 Example 3 138 0.164 100 to 800

Experimental Example 2. Evaluation of emission wavelength change of anti-counterfeiting device (label) manufactured using nanoparticled fluorescent dye

An anti-counterfeiting device (label) was prepared using the nanoparticled fluorescent dye of the present invention.

90% by weight of a dispersion of a nanoparticled fluorescent dye diluted to a concentration of 1,000ppm in water and 10% by weight of an acrylic aqueous binder as a binder were mixed and coated on a 155㎛ spreading paper (substrate) using the silk printing method, and 60 It was dried so that water was removed in a dryer at ° C. The coating thickness was about 30 μm. The mesh used for silk printing was 200 mesh.

A physical stimulus was applied to the label prepared as described above. In the case of a push stimulus, a high weight scale was attached to the surface of the label, and after pressing the high weight scale to indicate 10-12 kg, the fluorescence discoloration wavelength was measured. In the case of scratch stimulation, after applying the stimulation by scratching with a fingernail, the fluorescence discoloration wavelength was measured (FIGS. 8 to 10). It was confirmed that the fluorescent dyes were aggregated by the physical stimulation and the fluorescence emission wavelength was also blue shifted (shifted to a shorter wavelength).

Even effects not described in the present specification, in the present invention, each of the above-described components may additionally have other effects, and derive new effects that cannot be seen in the prior art according to the organic coupling relationship between each of the above-described components. can do.

In addition, the embodiments shown in the drawings may be modified and implemented in other forms, and if implemented including the configuration claimed in the claims of the present invention or implemented within the scope of equivalents, it should be regarded as belonging to the scope of the present invention. something to do.

Claims (9)

Including a fluorescent dye represented by the following formula,
The fluorescent dye includes a fluorescent dye nanoparticled by an organic polymer,
Pressure discoloration fluorescent material.
[chemical formula]

A is H or

ego,
B is -NR(C ₆ H ₅ )

(-N(C ₆ H ₅ ) ₂ ), or

(-N(C ₆ H ₄ R) ₂ ),
R is -(CH ₂ ) _n CH ₃ ;
n is an integer from 0 to 5;
According to claim 1,
At least two or more of the six A's included in the above formula

Which is, a pressure discoloration fluorescent material.
According to claim 1,
Fluorescent dyes having the above formula,
Characterized in that the electrons in the bonsai include molecules in which electrons can be de-localized by pi-pi (π-π) interactions,
Pressure discoloration fluorescent material.
According to claim 1,
The organic polymer is an acrylic copolymer having an ammonium functional group, a pressure discoloration fluorescent material.
According to claim 1,
The organic polymer of the nanoparticled fluorescent dye is destroyed by physical stimulation to change the emission wavelength of the fluorescent dye,
Pressure discoloration fluorescent material.
Including a fluorescent dye represented by the following formula,
In the fluorescent dye made of nanoparticles by an organic polymer,
At least 3 or more of 6 A included in the following formula

Which is, a fluorescent dye.
[chemical formula]

A is H or

ego,
B is -NR(C ₆ H ₅ )

(-N(C ₆ H ₅ ) ₂ ), or

(-N(C ₆ H ₄ R) ₂ ),
R is -(CH ₂ ) _n CH ₃ ;
n is an integer from 0 to 5;
base layer; and
a pattern layer disposed on the upper side of the base layer and including the pressure-discoloring fluorescent material according to any one of claims 1 to 5;
Containing, forgery prevention device.
base layer;
a pattern unit disposed on a portion of the upper side of the base layer and including the pressure-discoloring fluorescent material of any one of claims 1 to 5; and
Of the base layer, the pattern portion is printed on the unprinted portion, and includes a background portion for describing a specific background pattern, anti-counterfeiting device.
(S1) preparing a first solution containing a first solvent;
(S2) preparing a second solution by dissolving the fluorescent dye and the organic polymer in a second solvent;
(S3) preparing a mixed solution by mixing the first solution and the second solution by adding a second solution dropwise to the first solution;
(S4) stirring the mixed solution to proceed with emulsification;
In the method for producing a nanoparticled fluorescent dye comprising a,
The fluorescent dye comprises a fluorescent dye represented by the following formula,
Manufacturing method of nanoparticled fluorescent dye.

[chemical formula]

A is H or

ego,
B is -NR(C ₆ H ₅ )

(-N(C ₆ H ₅ ) ₂ ), or

(-N(C ₆ H ₄ R) ₂ ),
R is -(CH ₂ ) _n CH ₃ ;
n is an integer from 0 to 5;

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