KR101915865B1 - Fluorescent waterborne enamel composition and method for preparing the same - Google Patents

Abstract

The present invention relates to a fluorescent water-based enamel composition comprising a non-reactive perylene-based fluorescent dye, a reactive type perylene-based fluorescent dye having a radical reactor, and a reactive emulsifier capable of radical polymerization and a method for producing the same. , Storage stability and water resistance at room temperature, and can provide a fluorescent water-based enamel composition suitable for use in cosmetics such as nail enamel.

Description

FIELD OF THE INVENTION The present invention relates to a fluorescent water-based enamel composition and a method for preparing the same,

More particularly, the present invention relates to a fluorescent water-soluble enamel composition and a method for producing the same, and more particularly, to a fluorescent aqueous enamel composition and a method for producing the fluorescent water- The present invention relates to a fluorescent water-based enamel composition suitable for use in cosmetics such as nail enamel, and a method for producing the same.

With the rapid growth of the cosmetics market, stability and various functionalities for basic raw materials for cosmetics are required. Especially, there is an increasing need to develop water-soluble colored binders for cosmetics, which are harmless to human body and excellent in color. In particular, color cosmetics have a large market size, which accounts for 17% of the total cosmetics market. Most color cosmetics use a pigment dispersion based on oily binders. Due to the characteristics of oily binders, It is a potential risk to skin side effects for the elderly and women. On the other hand, in the case of special fields such as face paint, there are various problems such as detection of heavy metals, although aqueous products are being marketed.

Korean Patent Publication No. 10-2006-0066744 discloses an aqueous dispersion for nail enamel and an aqueous nail enamel composition having an average molecular weight of 10,000 to 40,000 and a glass transition temperature of 50 to 80 ° C, Patent No. 10-2012-0039080 discloses an aqueous manicure composition characterized by a glass transition temperature of -5 to 30 ° C. However, at present, most of the methods are limited to the resin for cosmetics, and a color toner, in which a color pigment is dispersed in a water-based resin made by such a technique, is simply mixed to produce a final product. In this case, it is necessary not only to decrease the color of the original dye but also to add an additional dispersing agent to improve the dispersibility of the colored pigment. Also, as time elapses, aggregation of colored pigments occurs and storage stability of the final product is remarkably deteriorated.

On the other hand, a conventional aqueous resin is prepared by using emulsion polymerization, in which a surfactant is used. Emulsion polymerization is a method in which micelles of a size of several hundred nanometers are emulsified in water and polymerization proceeds inside each micelle. These emulsifiers stabilize micelles, but if they are dried after coating with water resin, Remains. When these coatings are exposed to high temperature and high humidity conditions, they invite moisture penetration in the atmosphere, which greatly decreases the stability of the final coating layer and causes a whitening phenomenon.

Meanwhile, US Patent No. 5,131,916 describes a color emulsion for a marker pen prepared by injecting a fluorescent dye during emulsion polymerization, but does not mention the stability of the dyes used and applicability to nail enamel . In general, fluorescent dyes are superior in color development to general dyes, while light stability (light fastness) is very poor. Light-colored cosmetics are very important because they are often exposed to sunlight and ultraviolet rays outdoors. In addition, when the fluorescent dye is added during the emulsion polymerization, the solubility of the dye in the resin is remarkably lowered as the polymerization progresses even if the solubility in the initial monomer is excellent, so that the dyes are not completely dissolved in the resin and are again agglomerated to form particles.

Thus, a fluorescent water-based enamel composition suitable for use in nail enamel cosmetics which is excellent in light resistance and storage stability and does not cause opacity even under high temperature and high humidity conditions is not known.

Korean Patent Publication No. 10-2006-0066744 Korean Patent Publication No. 10-2012-0039080 United States Patent No. 5,131,916

The present invention is directed to a fluorescent water-soluble enamel composition which is excellent in light resistance, color clarity, storage stability and water resistance, and is suitable for use in cosmetics such as nail enamel, and a method for producing the same.

In order to solve the above technical problem, the present invention relates to a fluorinated aqueous dispersion comprising (a) a non-reactive type perylene-based fluorescent dye, (b) a reactive type perylene-based fluorescent dye having a radical reactor, and (c) a reactive emulsifier capable of radical polymerization To provide an enamel composition. At this time, it is preferable that the content of the non-reactive perylene-based fluorescent dye (a) and the reactive perylene-based fluorescent dye (b) satisfy the following expressions (1) and (2).

[Equation 1] ... 1 < D (= D ₁ + D ₂ ) < 10

[Equation 2] ... 1 < (D ₁ / D ₂ ) < 10

In the above-mentioned [Formula 1] and [Formula 2], D ₁ is the content of the non-reactive perylene-based fluorescent dye relative to 100 parts by weight of the resin, and D ₂ is the content of the reactive perylene-based fluorescent dye relative to 100 parts by weight of the resin .

The present invention also relates to a process for producing a fluorine-containing polymer, which comprises the steps of: i) mixing an acrylic monomer or a (meth) acrylic acid ester monomer or a mixture thereof with a reactive perylene-based fluorescent dye having a non-reactive perylene-based fluorescent dye, a radical reactor and a reactive emulsifier capable of radical polymerization Preparing a pre-emulsion; And ii) adding a polymerization initiator to the pre-emulsion to carry out a polymerization reaction.

Since the fluorescent water-soluble enamel composition according to the present invention is completely dissolved by injecting the fluorescent dye during the emulsion polymerization, it has not only the characteristics such as cohesion and migration, but also environmental friendliness, It is suitable for use in cosmetics such as nail enamel.

In addition, since the present invention can introduce a perylene-based fluorescent dye having excellent light resistance and a reactor capable of chemical reaction with the polymer main chain, it is possible to increase the content of the dye itself. Also, by using an emulsifier having a reactor during emulsion polymerization, it is possible to provide a fluorescent water-based enamel resin composition excellent in water resistance at room temperature, which can prevent white turbidity caused by remaining emulsifier after emulsion polymerization.

Hereinafter, the present invention will be described in more detail with reference to examples.

The fluorescent water-based enamel composition according to the present invention comprises (a) a non-reactive perylene-based fluorescent dye, (b) a reactive perylene-based fluorescent dye having a radical reactor, and (c) a reactive emulsifier capable of radical polymerization.

Perylene-based fluorescent dyes are widely used in industrial and electronic materials because they are known as fluorescent dyes having the highest light resistance and highest quantum efficiency among fluorescent dyes. However, it is disadvantageous in that it is difficult to prepare a liquid state resin by dissolving a large amount of dye in a relatively low solubility to a solvent or a monomer. In order to improve this, a reactive type fluorescent dye having a reactive group such as an acryl group was prepared and added to the emulsion polymerization process to increase the total dye concentration (D) in the resin.

Specifically, in the fluorescent water-based enamel composition according to the present invention, the dye content (D) in the resin preferably satisfies the following [Equation 1] and [Equation 2].

[Equation 1] ... 1 < D (= D ₁ + D ₂ ) < 10

[Equation 2] ... 1 < (D ₁ / D ₂ ) < 10

D ₁ is the content of the non-reactive perylene-based fluorescent dye relative to 100 parts by weight of the resin, D ₂ is the content of the reactive perylene-based fluorescent dye relative to 100 parts by weight of the resin to be.

In the present invention, a perylene-based fluorescent dye containing a perylene group having a perylene group and a radical dye having a perylene group in a chemical structure can be used, and the kind and structure of the dye are not particularly limited. However, in order to obtain sufficient characteristics, the content of the dye relative to the total weight of the resin is important. When the total dye content (D) is less than 1, the color feeling may decrease. When the total dye content (D) exceeds 10, The stability of the fluorescent water-based resin is remarkably lowered.

Also, the ratio (D ₁ / D ₂ ) of the reactive type perylene monomer to the non-reactive perylene monomer is very important. If the ratio exceeds 10, the content of the non-reactive dye is too high, There is a problem that storage stability such as precipitation occurs with time, and when the ratio is less than 1, the content of the reactive dye to be added increases to increase the manufacturing cost.

There is no particular limitation on the kind of the perylene-based fluorescent dye that can be used in the present invention, but a compound represented by the following formula (1) is one example.

The reactive perylene-based fluorescent dye used in the present invention is characterized by having a radical reactor. Examples of the radical reactor include an acrylic group, a metha (acryl) group, a thiol group, an allyl group and a vinyl group , But is not limited thereto. Specific examples of the reactive type perylene-based fluorescent dyes include compounds represented by the following formula (2).

The reactive emulsifier used in the present invention is an emulsifier containing a reactive group capable of at least one radical polymerization in the molecule, and is preferably an emulsifier containing an acrylic group, a vinyl group, a propenyl group, an isopropenyl group, a vinyl ether group (vinyloxy group) Allyloxy group), and the like, but the present invention is not limited thereto.

Specific examples thereof include compounds represented by the following formula (3).

In the above formula 3, R is alkyl or alkenyl having 6 to 18 carbon atoms, A is ethylene, and M is an alkali metal or ammonium.

In the present invention, the content of the reactive emulsifier is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 10 parts by weight based on 100 parts by weight of the monomer. If the content of the emulsifier is less than 0.1 part by weight, the pre-emulsion state becomes unstable and the emulsion polymerization does not proceed well. On the other hand, if the amount exceeds 30 parts by weight, the size of the emulsion polymer particles becomes too small, There is a disadvantage that it greatly increases. Further, the amount of the emulsifier remaining after the completion of the reaction is excessively large, resulting in deteriorating the physical properties of the final resin.

Also, the method for producing a fluorescent water-based enamel composition according to the present invention comprises the steps of: i) reacting an acrylic monomer or a (meth) acrylate monomer or a mixture thereof with a non-reactive perylene-based fluorescent dye, a reactive perylene- Mixing a reactive emulsifier capable of radical polymerization to prepare a pre-emulsion; And ii) adding a polymerization initiator to the pre-emulsion to perform a polymerization reaction. At this time, the polymerization reaction is performed through an emulsion polymerization reaction.

Further, the polymerization reaction is preferably carried out generally at 50 to 95 ° C, and more preferably at 60 to 85 ° C. If the reaction temperature is lower than 50 ° C, the rate of emulsion polymerization is too slow and the reaction does not proceed well, whereas when the reaction temperature is too high, the molecular weight distribution becomes wider.

As monomers to be used in the production of the fluorescent resin composition of the present invention, monomers which are generally used for acrylic resin polymerization can be used, and examples thereof include acrylic monomers, (meth) acrylic acid ester monomers, and mixtures thereof. Specific examples include acrylic acid, 2-ethylhexyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (Meth) acrylate, 2-ethylhexyl (meth) acrylate and isononyl (meth) acrylate, and mixtures thereof, but is not particularly limited thereto.

As the polymerization initiator usable in the present invention, any polymerization initiator conventionally used in emulsion polymerization can be used without any particular limitation, and specifically, benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone Peroxide compounds such as peroxide and t-butyl hydroperoxide; Azo compounds such as 2,2'-azobisisobutylonitrile, 2,2'-azobis-2,4-dimethylvaleronitrile and 2,2'-azobis-2-methylisobutyronitrile, or And mixtures thereof.

At this time, the content of the polymerization initiator used in the present invention is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the monomer. When the content of the polymerization initiator is less than 0.1 parts by weight, the reaction rate is slowed and the molecular weight of the resulting polymer is excessively increased. On the other hand, when the content of the polymerization initiator exceeds 10 parts by weight, it is difficult to obtain a polymer.

In the present invention, in order to improve the mechanical properties of the resin, a cross-linking agent may be used in the polymerization. The cross-linking agent that can be used is not particularly limited. Specific examples thereof include ethylene glycol dimethacrylate divinylbenzene ( divinylbenzene, 1,4-butanediol diacrylate, and the like. 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 cross-linking agent is too low, the cohesive property of the produced polymer is lowered and the mechanical properties are decreased. On the other hand, when the content of the cross-linking agent is too high, the mechanical properties are increased but the adhesiveness is poor and the coating layer is too brittle A problem arises.

In addition, a plasticizer, a cryoprotectant, a viscosity modifier, and the like may be added in accordance with the intended use of the fluorescent resin composition.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are provided to illustrate the present invention and should not be construed as limiting the scope of the present invention.

Reactive Fluorescence with a Radical Reactor Red  Synthesis of dyes

<Synthesis Example>

1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic acid dianhydride (1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic acid dianhydride) 16.67 g of 2,6-diisopropylaniline and 250 ml of propionic acid were heated to 80 ° C under argon and maintained at this temperature for 17 hours. After cooling to room temperature, crystals were precipitated with water and then filtered to dryness. 5 g of the dried powder was mixed with 8.14 g of 4-hydroxyphenylethyl alcohol and 4.07 g of K ₂ CO ₃ and mixed with 100 ml of DMF. The mixture was heated to 120 ° C and stirred for 12 hours. After the reaction was cooled to room temperature, crystals were precipitated using methanol, followed by filtration and drying. 2.7 g of the dried powder was mixed with 0.72 g of acryloyl chloride and 30 g of dioxane, followed by heating at 100 ° C for 3 hours. The reaction product was cooled to room temperature, and crystals were precipitated using water. The crystals were filtered and dried to obtain a reactive fluorescent red dye expressed by the formula (2).

Preparation of Fluorescent Aqueous Acrylic Resin Composition

&Lt; Example 1 >

A reactor equipped with a stirrer, a thermometer and a reflux condenser was charged with 53 parts by weight of ion-exchanged water and 3 parts by weight of Hitenol BC (Daiichi Kogyo Seiyaku Co., Ltd.) as a reactive emulsifier. 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 Lumogen F Red- ) And 1 part by weight of the reaction type fluorescent red dye synthesized in the above Synthesis Example were mixed to prepare a pre-emulsion, and 5% of the obtained pre-emulsion was added to the reaction vessel. After 0.3 part by weight of benzoyl peroxide was added as a polymerization initiator to confirm that the reaction was started, the pre-emulsion was added uniformly for 4 hours to conduct emulsion polymerization. After completion of the reaction, the temperature was lowered to 65 ° C, and 0.004 part by weight of benzoyl peroxide was added. The reaction was terminated by stirring for 30 minutes. And 3.9 parts by weight of 25% ammonia water were added to obtain a fluorescent water-soluble acrylic resin having pH = 8 and a solid content of 50% by weight.

&Lt; Example 2 >

The same as Example 1 except that 2 parts by weight of non-reactive fluorescent dye was added in Example 1.

&Lt; Example 3 >

Example 1 was the same as Example 1 except that 1 part by weight of non-reactive fluorescent dye was added in Example 1.

&Lt; Comparative Example 1 &

Example 1 was the same as Example 1 except that sodium dodecyl benzene sulfonate, which is a non-reactive emulsifier, was used instead of the reactive emulsifier.

&Lt; Comparative Example 2 &

Except that 0.5 parts by weight of a non-reactive fluorescent dye and 0.5 parts by weight of a reactive fluorescent dye were added in Example 1, respectively.

&Lt; Comparative Example 3 &

Example 1 was the same as Example 1 except that the reaction type fluorescent dye was not added and only 3 parts by weight of non-reactive fluorescent dye was added

&Lt; Comparative Example 4 &

Example 1 was the same as Example 1 except that 3 parts by weight of Bayer Red 540 (BASF), a non-perylene fluorescent dye, was added in place of the perylene-based fluorescent dye

The properties of the fluorophore resin compositions prepared in the examples and comparative examples according to the present invention were evaluated through the following experiment and the results are shown in Table 1.

<Experimental Example>

1) Light resistance

A sheet having a thickness of 100 microns was prepared by solvent casting the fluororesin composition prepared in Examples and Comparative Examples, and a light fastness test (test standard: KS K07000) using Xenon-arc or Carbon-arc was performed And the light fastness rating was determined. When there is no difference in color between the portion exposed to light and the portion not exposed to light after 80 hours, it is indicated as O or higher than that of light-resistant grade 6. On the other hand, if there is a difference in color between the portion exposed to light and the portion not exposed to light after 20 hours, it is indicated as X. In the case where color change is observed within 20 to 80 hours, Respectively.

2) Water temperature

The fluorocarbon resin composition prepared in Examples and Comparative Examples was coated on a glass plate to a thickness of 25 microns, and the glass plate was immersed in hot water of 40 degrees for 1 hour. After 1 hour, the coated glass plate was taken out, and the state of the coating was visually confirmed. When no whitening occurred and the color remained unchanged, the coating was marked with O or X.

3) Color characteristics

The fluorescent water-soluble resin composition prepared in Examples and Comparative Examples was coated on a glass plate to a thickness of 25 microns, and the glass plate was dried at room temperature for 1 hour. After drying, the color of the glass plate was observed. When the fluorescent microscope was strongly expressed, it was labeled O. Otherwise, when the color was poor, X was indicated.

4) Storage characteristics

The fluorescent water-based resin composition prepared through Examples and Comparative Examples was allowed to stand at room temperature for 30 days, and the state of the resin was visually observed. When particles are not observed such as aggregation of dyes, O, when floating matters such as particles are observed, they are marked with X.

As shown in Table 1, when a reactive emulsifier is used and the content of the perylene-based dye satisfies the above-mentioned [Formula 1] and [Formula 2], it is found that an aqueous fluorescent enamel having excellent properties can be obtained have. On the other hand, when the non-reactive emulsifier is used, it is found that the water-temperature resistance property is degraded. When the perylene-based fluorescent resin does not satisfy [Formula 1], [Formula 2] , The color characteristics or the storage characteristics were deteriorated.

Claims (16)

(a) a non-reactive perylene-based fluorescent dye represented by the following formula (1);
(b) a reactive perylene-based fluorescent dye having a radical reactive group represented by the following formula (2);
(c) a reactive emulsifier capable of radical polymerization represented by the following formula (3); And
(d) Fluorescent aqueous enamel composition comprising an acrylic monomer or a (meth) acrylic acid ester monomer or a mixture thereof:
[Formula 3] &lt; EMI ID =

Wherein R is alkyl or alkenyl having 6 to 18 carbon atoms, A is ethylene, and M is an alkali metal or ammonium. The method according to claim 1,
Wherein the content of the non-reactive perylene-based fluorescent dye (a) and the reactive perylene-based fluorescent dye (b) satisfy the following expressions (1) and (2)
[Equation 1] ... 1 < D (= D ₁ + D ₂ ) < 10
[Equation 2] ... 1 < (D ₁ / D ₂ ) < 10
(Wherein D ₁ is the content of the non-reactive perylene-based fluorescent dye relative to 100 parts by weight of the resin, and D ₂ is the content of the reactive perylene-based fluorescent dye relative to 100 parts by weight of the resin Content.) The method according to claim 1,
The acrylic monomer or (meth) acrylate monomer (d) may be at least one selected from the group consisting of acrylic acid, 2-ethylhexyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (Meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and isononyl Composition. delete The method according to claim 1,
Wherein the content of the reactive emulsifier (c) is 0.1 to 30 parts by weight based on 100 parts by weight of the monomer. The method according to claim 1,
Characterized in that it is used in nail enamel cosmetics. i) a non-reactive perylene-based fluorescent dye represented by the following formula (1); A reactive perylene-based fluorescent dye having a radical reactor represented by the following formula (2); A reactive emulsifier capable of radical polymerization represented by the following formula 3; And mixing the acrylic monomer or (meth) acrylic acid ester monomer or a mixture thereof to prepare a pre-emulsion; And
ii) a step of adding a polymerization initiator to the pre-emulsion to carry out a polymerization reaction.
[Formula 3] &lt; EMI ID =

Wherein R is alkyl or alkenyl having 6 to 18 carbon atoms, A is ethylene, and M is an alkali metal or ammonium. 8. The method of claim 7,
Wherein the polymerization reaction is an emulsion polymerization reaction. 8. The method of claim 7,
Wherein the polymerization reaction is carried out at 50 to &lt; RTI ID = 0.0 &gt; 95 C. &lt; / RTI &gt; 8. The method of claim 7,
Wherein the content of the non-reactive perylene-based fluorescent dye and the reactive perylene-based fluorescent dye satisfy the following expressions (1) and (2):
[Equation 1] ... 1 < D (= D ₁ + D ₂ ) < 10
[Equation 2] ... 1 < (D ₁ / D ₂ ) < 10
(Wherein D ₁ is the content of the non-reactive perylene-based fluorescent dye relative to 100 parts by weight of the resin, and D ₂ is the content of the reactive perylene-based fluorescent dye relative to 100 parts by weight of the resin Content.) 8. The method of claim 7,
(Meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, n (meth) acrylate, (Meth) acrylate, isooctyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and isononyl Way. delete delete 8. The method of claim 7,
The polymerization initiator may be selected from the group consisting of benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl hydroperoxide, 2,2'-azobisisobutylonitrile, 2,2'-azobis -2,4-dimethylvaleronitrile, 2,2'-azobis-2-methylisobutyronitrile, or a mixture thereof. 8. The method of claim 7,
Wherein the polymerization reaction further comprises a crosslinking agent. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; 16. The method of claim 15,
Wherein the crosslinking agent is selected from the group consisting of ethylene glycol dimethacrylate, divinylbenzene, 1,4-butanediol diacrylate, and mixtures thereof.