KR20190135749A - Red luminous waterborne emulsion composition and method for preparing the same - Google Patents

Abstract

The present invention relates to a red fluorescent aqueous emulsion composition and a production method thereof and, more specifically, to a red fluorescent aqueous emulsion composition produced by adding an europium compound which emits red light when irradiated with ultraviolet rays during an emulsion polymerization process. The red fluorescent aqueous emulsion composition has excellent fluorescent properties, and is suitable for use in anti-counterfeiting aqueous paints or aqueous inks due to excellent storage stability.

Description

Red fluorescent aqueous emulsion composition and method for preparing the same

The present invention relates to a red fluorescent aqueous emulsion composition and a method for preparing the same, and more particularly, to a high concentration red fluorescent aqueous emulsion composition prepared by adding a Europium compound which exhibits red light when irradiated with ultraviolet rays during an emulsion polymerization process. It is suitable for use in preventing water-based paints or water-based inks.

  Currently, the demand for security and anti-counterfeiting is increasing. As a representative example, black light type UV-fluorescent dyes that do not show color under visible light but express color when irradiated with ultraviolet light are widely applied to anti-counterfeiting ink. have. These UV-fluorescent dyes are commonly used in oil-based ink or paints based on organic solvents such as toluene and the like because they have oil-soluble insoluble in water. However, as the demand for environmentally friendly materials that are harmless to humans is increasing recently, development of water-soluble or ultraviolet curing materials to replace them is being actively conducted.

For example, Korean Patent Publication No. 10-2000-7009466 discloses a technique for preparing and dispersing fluorescent particles, and Korean Patent Publication No. 10-2009-0035258 discloses an inorganic type emitting blue, green yellow, or red light. Disclosed are a fluorescent ink composition prepared by dispersing a mineral in a curable resin. In this case, however, pigments or inorganic phosphors are used. In order to increase dispersion stability after mixing, a dispersant must be added separately, and since the particles are not dissolved in a molecular unit, the luminous efficiency is lowered and storage stability is also reduced. There is a problem.

Meanwhile, US Patent No. 6,846,350 discloses a method for synthesizing a europium compound, which is easy to apply to an alcohol-based ink, and a manufacturing technology for a red light-emitting ink using the same, wherein the solvent is ethanol, ethylene glycol, and polyvinylpi You should use a mixture of ralidone, etc.

As such, until now, a technique for preparing an anti-counterfeiting aqueous fluorescent emulsion composition by adding a fluorescent dye emitting from ultraviolet rays during emulsion polymerization has not been developed, and particularly includes a high concentration of fluorescent dye capable of expressing sufficient luminance. There is no known technique for preparing emulsions.

Korean Patent Publication No. 10-2000-7009466 Korean Patent Publication No. 10-2009-0035258 US Patent No. 6,846,350

The problem to be solved by the present invention is to provide a high concentration red fluorescent aqueous emulsion composition excellent in luminescence properties and excellent storage stability that can be used in an aqueous material such as an anti-counterfeiting aqueous paint or an aqueous ink, and a manufacturing method thereof.

In order to solve the above technical problem, the present invention is prepared by polymerizing (a) Europium fluorescent dye, (b) acrylic monomer or (meth) acrylic acid ester monomer or mixtures thereof and (c) emulsifier It provides a fluorescent aqueous emulsion composition.

At this time, the europium-based fluorescent dye is preferably used by mixing a compound such as Eu (TTA) ₃ Phen, Eu (TTA) ₃ and Eu (TTA) ₂ AA, the content of the europium compound is [Equation 1] and [ It is more preferable to satisfy Formula 2].

[Equation 1]. E = (E ₁ + E ₂ + E ₃ )> 2

[Equation 2]. (E ₁ / E)> 0.5

(In [Formula 1], [Formula 2], E ₁ , E ₂ , E ₃ is the content of Eu (TTA) ₃ Phen, Eu (TTA) ₃ , Eu (TTA) ₂ AA to 100 parts by weight of monomer, respectively. to be)

In another aspect, the present invention comprises the steps of i) preparing a pre-emulsion by mixing europium-based fluorescent dyes, acrylic monomers or (meth) acrylic acid ester monomers or mixtures thereof, emulsifiers and water; And ii) adding a polymerization initiator to the preemulsion to perform an emulsion polymerization reaction.

The red fluorescent aqueous emulsion composition according to the present invention is an environmentally friendly aqueous emulsion composition having excellent luminescence properties and excellent storage stability, and has a total luminance of 2 parts by weight or more relative to the resin solid content, and a fluorescent dye may be used. Since it is dissolved in molecular units, problems such as aggregation do not occur. In addition, only 5 to 10% of the general aqueous resin used may exhibit anti-counterfeiting properties without affecting the physical properties of the existing resin.

1 is a photograph taken when the UV lamp is illuminated after coating the red fluorescent aqueous emulsion composition prepared according to Example 1 and Comparative Example 1 of the present invention on paper.

The present invention will be described in more detail with reference to the following examples.

The red fluorescent aqueous emulsion composition according to the present invention is characterized in that the europium-based compound exhibiting red fluorescence upon ultraviolet irradiation is prepared by the emulsion polymerization process. Specifically, the red fluorescent aqueous emulsion composition according to the present invention is prepared by polymerizing (a) a Europium fluorescent dye, (b) an acrylic monomer or a (meth) acrylic acid ester monomer or a mixture thereof, and (c) an emulsifier. .

Europium based fluorescent dyes in the emulsion composition according to the invention is represented by the following [formula _{1] Eu (TTA) 3 Phen} , [ Formula 2] Eu (TTA) ₃ and [Formula 3] is represented as represented by It is preferable to use a mixture of Eu (TTA) ₂ AA.

[Formula 1]

Eu (TTA) ₃ Phen

[Formula 2]

Eu (TTA) ₃

[Formula 3]

Eu (TTA) ₂ AA

In general, a europium compound has a ligand bound to the center metal to absorb light in the ultraviolet region, and the energy is transferred to the europium metal to express sharp red fluorescence. At this time, TTA (Thenoyltrifluoroacetone) is a ligand that effectively absorbs light in the ultraviolet region, and Phen (1,10-phenanthroline) plays a role of transferring the absorbed energy to europium. However, the compound of [Formula 1] in which TTA molecules and one molecule of Phen are combined shows high luminance, but the solubility in acryl monomer is 1 part by weight or less, which is not sufficient to make a high concentration of fluorescent emulsion. On the other hand, the compound of [Formula 2] bound with 3 molecules of TTA has very low solubility and has excellent solubility in acrylic monomer. The compound of [Formula 3] consisting of 2 molecules of TTA and 1 molecule of AA (acrylic acid) has a lower brightness and solubility, but has a reactor that can participate in the emulsion polymerization reaction, which helps to increase the content of europium compound in the final emulsion. .

In consideration of physical properties such as luminance and solubility of each of the flow path compounds, the content of the europium fluorescent dye in the red fluorescent aqueous emulsion composition according to the present invention preferably satisfies the following [formula 1] and [formula 2].

[Equation 1]. E = (E ₁ + E ₂ + E ₃ )> 2

[Equation 2]. (E ₁ / E)> 0.5

(In [Formula 1], [Formula 2], E ₁ , E ₂ , E ₃ are represented by Eu (TTA) represented by [Formula 1], [Formula 2] and [Formula 3] with respect to 100 parts by weight of monomer, respectively. ₃ Phen, Eu (TTA) ₃ , Eu (TTA) ₂ AA)) In this case, the content of the total europium compound (E) is lower than 2, or the content of the compound represented by [Formula 1] is compared to the total content of the europium compound. If it is less than 50%, the light emission luminance is not sufficient.

As another aspect of the present invention, a method of preparing a red fluorescent aqueous emulsion composition comprises the steps of i) preparing a preemulsion by mixing a europium fluorescent dye, an acrylic monomer or an (meth) acrylic acid ester monomer or a mixture thereof, an emulsifier and water. ; And ii) adding an polymerization initiator to the preemulsion to perform emulsion polymerization. At this time, the emulsion polymerization reaction is preferably carried out at a temperature range of 50 to 95 ℃, more preferably carried out at 60 to 85 ℃. If the reaction temperature is less than 50 ℃ the rate of emulsion polymerization is too slow and the reaction does not proceed well, while if the reaction temperature is too high there is a disadvantage that the molecular weight distribution is wide.

As the monomer used for preparing the red fluorescent aqueous emulsion composition of the present invention, any monomer generally used for acrylic resin polymerization may be used, and an acrylic monomer or a (meth) acrylic acid ester monomer, or a mixture thereof may be mentioned. . Specifically, acrylic acid, 2-ethylhexyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl One or more selected from the group consisting of (meth) acrylate, 2-ethylhexyl (meth) acrylate and isononyl (meth) acrylate can be used, but is not particularly limited thereto.

In addition, as the polymerization initiator usable in the present invention, any of the polymerization initiators commonly used in emulsion polymerization may be used, and is not particularly limited. Specifically, benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone Peroxide compounds such as peroxide and t-butylhydroperoxide; Azo compounds such as 2,2'-azobisisobutylonitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis-2-methylisobutyronitrile, or Mixtures of these are mentioned.

At this time, the content of the polymerization initiator used in the present invention is preferably used in 0.1 to 10 parts by weight based on 100 parts by weight of the monomer. If the content of the polymerization initiator is less than 0.1 parts by weight, there is a disadvantage in that the reaction rate is slow and the molecular weight of the resulting polymer is too high, while if the content of the polymerization initiator is more than 10 parts by weight, it is difficult to obtain a polymer of the polymer.

Emulsifiers usable in the present invention may be any of a radically polymerizable reactive emulsifier and a non-reactive emulsifier. In general, any of emulsifiers used for polymerization may be used. Specifically, for example, as the non-reactive emulsifier, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether may be used, and in the case of the reactive emulsifier, an alkylphenyl ether type having a radical polymerization reactor Or alkylphenyl esters, acrylate sulfate esters, or mixtures thereof.

The amount of the emulsifier is not particularly limited, but is preferably used within the range of 0.5 to 10 parts by weight. If the content of the emulsifier is less than 0.5 parts by weight, the emulsification of the monomer is not sufficient, so that the emulsion polymerization does not proceed well. Due to this, there is a problem in that the storage stability of the resin is rapidly lowered over time.

In addition, in the present invention, in order to improve the mechanical properties of the resin, a crosslinking agent may be used in the polymerization process, but the crosslinking agent that can be used is not particularly limited, but as a specific example, ethylene glycol dimethacrylate divinylbenzene ( divinylbenzene), 1,4-butanediol diacrylate, or a mixture thereof. The crosslinking agent is suitably added in an amount of 1 to 5 parts by weight based on 100 parts by weight of the monomer. When the content of the crosslinking agent is too low, the cohesive properties of the prepared polymer are lowered and the mechanical properties are decreased. On the other hand, when the content of the crosslinking agent is too high, the mechanical properties are increased but the adhesion is poor and the coating layer is too brittle. A problem arises.

In addition, according to the purpose of use of a resin composition, you may add and use a plasticizer, an antifreezing agent, a viscosity modifier, etc.

The present invention will be described in more detail with reference to the following examples. However, the following examples are presented by way of example only for understanding of the present invention, and the scope of the present invention should not be construed as being limited thereto.

Synthesis of Europium Fluorescent Dye Compound

The europium compounds of [Formula 1], [Formula 2] and [Formula 3] were synthesized by a known method, and references for each are as follows. Eu (TTA) ₃ Phen represented by [Formula 1] is J. Non-Cryst. Solids, 2000, Vol 275, pp. Synthesis was carried out according to the method described in 52, Eu (TTA) ₃ represented by the formula [2] is J. Inorg. Nucl. Chem., 1965, Vol 27. pp. It was synthesized according to the method described in 255, and Eu (TTA) ₂ AA represented by [Formula 3] is Chem. Mater., 2000, Vol 12, pp. It synthesized according to the method described in 2212.

Preparation of Fluorescent Aqueous Emulsion Composition

<Example 1>

53 parts by weight of ion-exchanged water and 3 parts by weight of Hitenol BC (Daiichi Kogyo Seiyaku Co., Ltd.) were added to an reactor equipped with a stirrer, a thermometer, and a refluxing machine, and the temperature was raised to 80 ° C while stirring. 34.5 parts by weight of ion-exchanged water, 4 parts by weight of Hitenol BC and 50 parts by weight of methyl methacrylate, 2 parts by weight of acrylic acid, 48 parts by weight of 2-ethylhexyl acrylate and 1 part by weight of Eu (TTA) ₃ Phen, Eu (TTA) _A preemulsion was prepared by mixing ₃ 0.5 parts by weight and 0.5 parts by weight of Eu (TTA) ₂ AA, and 5% of the obtained preemulsion was added to the reactor. 0.3 parts by weight of benzoyl peroxide was added as a polymerization initiator to confirm that the reaction was started, and then the emulsion was polymerized by adding the preemulsion equally for 4 hours. After the reaction was completed, the temperature was cooled to 65 ° C., then 0.004 parts by weight of benzoyl peroxide was added and stirred for 30 minutes to terminate the reaction. 3.9 parts by weight of 25% aqueous ammonia was added to obtain a fluorescent aqueous emulsion having a pH of 8 and 50% by weight of solids.

<Example 2>

Except that in Example 1 1 part by weight of Eu (TTA) ₃ Phen and 1 part by weight of Eu (TTA) ₃ while not adding Eu (TTA) ₂ AA is the same as in Example 1.

<Example 3>

In Examples 1 to inject Eu (TTA) ₃ Phen 1 part by weight, and Eu (TTA) ₂ AA 1 part by weight of the other hand, except that it does not supply the Eu (TTA) ₃ is the same as in Example 1.

<Comparative Example 1>

In Example 1, except that only 1 part by weight of Eu (TTA) ₃ Phen is not added, Eu (TTA) ₃ and Eu (TTA) ₂ AA is the same as in Example 1.

<Comparative Example 2>

In Example 1, except that 0.5 parts by weight of Eu (TTA) ₃ Phen, 1 part by weight of Eu (TTA) ₃ , and 1 part by weight of Eu (TTA) ₂ AA was the same as in Example 1.

<Comparative Example 3>

Examples Example 1 In the first Eu (TTA) ₃ Phen only added 2 parts by weight, and it is the same as in Example 1 except that it does not supply the Eu (TTA) ₃ and Eu (TTA) ₂ AA.

Dye solubility and luminance measurement

The solubility of 100 mL of methylmethacrylate was measured using the europium fluorescent dye compounds Eu (TTA) ₃ Phen, Eu (TTA) ₃ and Eu (TTA) ₂ AA prepared according to the synthesis example. In addition, 25 mg of each compound was dissolved in 100 mL of ethanol, and then luminescence was measured using a fluorescence spectrometer (QM-4 / 2005SE, manufactured by PIT, USA). The results are summarized in Table 1 below.

The properties of the fluorescent aqueous emulsion compositions prepared in Examples and Comparative Examples according to the present invention were evaluated through the following experiment and the results are shown in [Table 2].

Emulsion stability

After leaving the fluorescent resin composition prepared in the above Examples and Comparative Examples for 30 days at room temperature, the state of the resin was visually observed. When particles are not observed, such as agglomeration of the dye O, when suspended matter such as particles are summarized in the following [Table 2].

Emission characteristics

The emission compositions of the emulsion compositions prepared by the above Examples and Comparative Examples were measured using a fluorescence spectrometer (QM-4 / 2005SE, manufactured by PIT, USA), and the results are summarized in the following [Table 2]. And after coating the emulsion of Comparative Example 1 on a paper, a photograph when the UV lamp is illuminated in Figure 1 is shown.

As shown in Table 1, Table 2 and Figure 1, the red fluorescent aqueous emulsion composition according to the present invention has storage stability, and in order to exhibit optimal emission luminance, It was confirmed that the emulsion must be prepared by mixing the europium compound having excellent solubility in the monomer in an appropriate ratio according to the above [formula 1] and [formula 2].

Claims (15)

A red fluorescent aqueous emulsion composition prepared by polymerizing (a) a Europium fluorescent dye, (b) an acrylic monomer or a (meth) acrylic acid ester monomer or a mixture thereof and (c) an emulsifier. The method of claim 1,
The europium-based fluorescent dye is red fluorescence characterized in that it comprises Eu (TTA) ₃ Phen of [Formula 1], Eu (TTA) ₃ of [Formula 2], Eu (TTA) ₂ AA of [Formula 3] Aqueous emulsion composition:
[Formula 1] [Formula 2] [Formula 3]

Eu (TTA) ₃ Phen Eu (TTA) ₃ Eu (TTA) ₂ AA The method of claim 2,
Red fluorescent aqueous emulsion composition, characterized in that the content of the europium-based fluorescent dye satisfies the following [formula 1] and [formula 2]:
[Equation 1]. E = (E ₁ + E ₂ + E ₃ )> 2
[Equation 2]. (E ₁ / E)> 0.5
(In [Formula 1], [Formula 2], E ₁ , E ₂ , E ₃ is the content of Eu (TTA) ₃ Phen, Eu (TTA) ₃ , Eu (TTA) ₂ AA to 100 parts by weight of monomer, respectively. to be) The method of claim 1,
The acrylic monomers or (meth) acrylic acid ester monomers are acrylic acid, 2-ethylhexyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, n Red fluorescent aqueous emulsion, characterized in that at least one selected from the group consisting of octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and isononyl (meth) acrylate Composition. The method of claim 1,
The emulsifying agent is a red fluorescent aqueous emulsion composition, characterized in that at least one selected from the group consisting of polyoxyethylene lauryl ether, polyoxyethylene stearyl ether alkylphenyl ether type, alkylphenyl ester type, acrylate sulfate ester type emulsifier . i) preparing a preemulsion by mixing europium fluorescent dyes, acrylic monomers or (meth) acrylic acid ester monomers or mixtures thereof, emulsifiers and water; And
ii) A method of preparing a red fluorescent aqueous emulsion composition comprising the step of performing an emulsion polymerization by adding a polymerization initiator to the preemulsion. The method of claim 6,
The emulsion polymerization reaction is a method of producing a red fluorescent aqueous emulsion composition, characterized in that carried out at a temperature range of 50 to 90 ℃. The method of claim 6,
The europium-based fluorescent dye is Eu (TTA) ₃ Phen, Eu (TTA) ₃ , A process for producing a red fluorescent aqueous emulsion composition comprising Eu (TTA) ₂ AA. The method of claim 8,
The method for producing a red fluorescent aqueous emulsion composition, wherein the content of the europium fluorescent dye satisfies the following [Formula 1] and [Formula 2]:
[Equation 1]. E = (E ₁ + E ₂ + E ₃ )> 2
[Equation 2]. (E ₁ / E)> 0.5
(In [Formula 1], [Formula 2], E ₁ , E ₂ , E ₃ is the content of Eu (TTA) ₃ Phen, Eu (TTA) ₃ , Eu (TTA) ₂ AA to 100 parts by weight of monomer, respectively. to be) The method of claim 6,
The acrylic monomers or (meth) acrylic acid ester monomers are acrylic acid, 2-ethylhexyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, n -Red fluorescent aqueous emulsion, characterized in that at least one selected from the group consisting of octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and isononyl (meth) acrylate Method of Preparation of the Composition. The method of claim 6,
The emulsifying agent is a red fluorescent aqueous emulsion composition, characterized in that at least one selected from the group consisting of polyoxyethylene lauryl ether, polyoxyethylene stearyl ether alkylphenyl ether type, alkylphenyl ester type, acrylate sulfate ester type emulsifier Method of preparation. The method of claim 6,
The content of the emulsifier is 0.5 to 10 parts by weight based on 100 parts by weight of the monomer, the method of producing a fluorescent aqueous enamel composition. The method of claim 6,
The polymerization initiator is benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl hydroperoxide, 2,2'-azobisisobutylonitrile, 2,2'-azobis A process for producing a red fluorescent aqueous emulsion composition, characterized in that at least one member is selected from the group consisting of -2,4-dimethylvaleronitrile and 2,2'-azobis-2-methylisobutyronitrile. The method of claim 6,
The content of the polymerization initiator is 0.1 to 10 parts by weight based on 100 parts by weight of the monomer, the method of producing a fluorescent aqueous enamel composition. An anti-counterfeiting aqueous ink prepared using the red fluorescent aqueous emulsion composition according to claim 1.

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