KR101161643B1 - Antifouling per-fluoro polyether compounds, coating compositions and their films containing same - Google Patents

Abstract

The present invention relates to an antifouling perfluorinated polyether-modified compound, a coating composition comprising the same, and a membrane to which the same is applied. The surface coated on the surface of the plastic product relates to a perfluorinated polyether modified compound exhibiting excellent water repellency, oil repellency, antifouling property and decontamination while maintaining the transparency of the product itself.

Description

Antifouling perfluorinated polyether-modified compound and coating composition including same and film using the same

The present invention relates to an antifouling perfluorinated polyether-modified compound, a coating composition comprising the same, and a film to which the same is applied, and more particularly, to a transparent glass article including a substrate of a perfluorinated polyether-based structure and a hydrocarbon-based molecular structure in the same molecule. Or it relates to a perfluorinated polyether modified compound coated on the surface of the plastic product exhibits excellent water and oil repellency, antifouling properties while maintaining the transparency of the product itself.

Fluorine-based functional materials are attracting attention as one of the next generation core material technologies in the semiconductor, optical communication, and computer fields, and have recently been applied and applied to electronic products, especially displays. In particular, in the case of display products such as LCD, PDP, OLED, the liquid crystal or polarization functional layer used on the surface, the hard coating layer for protecting and flattening the liquid crystal, the anti-reflection layer for providing clear image quality by canceling external light interference, And the outermost antifouling layer is coated to prevent contamination. Among these, surface contamination prevention and removal functions are important factors that determine the appearance and performance of products, and the industrial demand for solving them is very high. Therefore, there is a need for a surface coating material having high durability and antifouling properties. Silicone materials, fluorine compounds, and the like are widely used as raw materials for surface coating agents for surface protection.

Fluorine has a strong electron density, a small atomic radius after hydrogen atoms, and strong electronegativity, forming a strong carbon-fluorine bond. Due to the fluorine-based properties, the monomer containing a perfluorinated alkyl group exhibits extremely small hydrophobicity of about 6-8 dynes / cm, and has a very low surface energy, which repels both water and oil. As a result, fluorine-based compounds are relatively expensive and are used for high value-added resins, films, lubricants, and paints because of their excellent chemical stability, heat resistance, and weather resistance.They have non-tackiness, low surface energy, water repellency, and low refractive index. The area of use is expanding to the necessary antifouling agents, optical materials, functional dyes and electronic materials.

However, coating agents using fluorine compounds alone have poor decontamination properties, and coating agents using only silicon compounds alone have poor reaction durability and poor friction durability, or insufficient crosslinking. Accordingly, the silane compound having a perfluorine group containing both of them was used as a surface modifier, but they also do not have sufficient water and oil repellency, antifouling properties and decontamination properties.

Recently, various studies have been conducted on coating compositions having excellent decontamination properties, including perfluorinated ether compounds, which are one of fluorine compounds. Perfluorinated ether compounds are of interest as surface coatings because they have excellent flexibility derived from molecular structure, fluidity over a wide temperature range, decontamination resulting from lubrication and lubricity. Republic of Korea Patent Publication No. 10-2009-0056913 (LG CHEM.) Has a fluorine-based UV-curable functional group containing a perfluorinated polyether as a coating agent also serves as a hard coating layer including nanoparticles, in order to obtain a compound having both wear resistance and pollution resistance The containing compound is shown. However, in the case of a material in which a perfluorinated ether and a UV-curable functional group are combined around a cyclic structure including an amine, it is difficult to control the number of combined functional groups or perfluorinated ethers, and thus, there is a difficulty in synthesizing a new type of structure.

Accordingly, the present inventors copolymerize anti-fouling perfluorinated ether compounds and hydrocarbon compounds having high compatibility with substrates such as polymers and plastics, and thus, the number of UV-curable functional groups and the number of perfluorinated ether compounds according to the molecular weight of the hydrocarbon compound. Synthesized oligomeric perfluorinated ether modified compound that can be easily controlled, according to the molecular weight and binding composition of the compound can be added at the time of polymer molding or forming the polymer thin film to form a transparent coating film, synthesized perfluorinated ether modified The present invention includes an antifouling coating liquid composition comprising a compound, a solvent, a photoinitiator, and the like, and a film using the composition.

The present invention improves the difficulty of controlling the number of conventional UV-curable functional groups and the number of perfluorinated ether compounds to efficiently synthesize an antifouling perfluorinated polyether-modified compound, and provides a coating composition comprising the compound and a film to which the same is applied. There is.

In order to achieve the above object, the present invention provides a perfluorinated polyether modified compound represented by the following formula (1).

[Formula 1]

(In Formula 1,
Rf represents a perfluorinated ether group selected from the following Chemical Formulas 2 to 5,
R represents an alkyl group of C _1-18 ,
X represents hydrogen or a C _1-6 alkyl group or phenyl group,
m is an integer from 2 to 100, n and l are each an integer from 1 to 10.)

[Formula 2]

CF ₃ CF ₂ CF _2- [OCF (CF ₃ ) CF ₂ ] _a -OCF (CF ₃ ) COF

(3)

Y- [CF ₂ O] _b- [CF ₂ CF (CF ₃ ) O] _c- [CF (CF ₃ ) O] _d- [CF ₂ CF ₂ O] _e -Z-COF

[Formula 4]

FOC-Z- [CF ₂ O] _b- [CF ₂ CF (CF ₃ ) O] _c- [CF (CF ₃ ) O] _d- [CF ₂ CF ₂ O] _e -Z-COF

[Chemical Formula 5]

CF ₃ CF ₂ CF ₂ O- [CF ₂ -CF ₂ -CF ₂ -O] _f -COF

(In Chemical Formulas 2 to 5,
Y and Z is a perfluoro alkyl group of C _1-5,
a, b, c, d, e And f are each an integer of 2 to 100.)

The perfluorinated polyether-modified compound according to the present invention can be added to a functional hard coating liquid or used individually as an ultraviolet curable transparent coating agent, and can be usefully used for surface processing of various parts requiring antifouling properties, and for the textile industry and the paint industry. It can be used for various purposes in various industries such as adhesive industry, fine chemical industry, biological, biochemical industry, electric and electronic industry, automobile industry and metal industry.

Figure 1 shows a ¹⁹ F-NMR graph of the perfluorinated polyether compound of the present invention by nuclear magnetic resonance (NMR) analysis,
Figure 2 shows a ¹ H-NMR graph analyzed by nuclear magnetic resonance (NMR) of the hydrocarbon-based oligomer of the present invention,
Figure 3 shows a ¹ H-NMR graph of the perfluorinated polyether modified compound of the present invention by nuclear magnetic resonance (NMR) analysis,
Figure 4 shows a ¹⁹ F-NMR graph of the perfluorinated polyether modified compound of the present invention by nuclear magnetic resonance (NMR) analysis,
5 is a graph of Fourier infrared spectroscopy (FT-IR) of the perfluorinated polyether-modified compound of the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention includes a perfluorinated polyether compound and a hydrocarbon compound represented by the following formula 2 to 5 in the same molecule, the form of the entire molecule represents a graft copolymer form, including a double bond capable of ultraviolet polymerization It provides a perfluorinated polyether modified compound represented by the formula (1).

[Formula 1]

(In Formula 1,
Rf represents a perfluorinated ether group selected from the following Chemical Formulas 2 to 5,
R represents an alkyl group of C _1-18 ,
X represents hydrogen or a C _1-6 alkyl group or phenyl group,
m is an integer from 2 to 100, n and l are each an integer from 1 to 10.)

[Formula 2]

CF ₃ CF ₂ CF _2- [OCF (CF ₃ ) CF ₂ ] _a -OCF (CF ₃ ) COF

(3)

Y- [CF ₂ O] _b- [CF ₂ CF (CF ₃ ) O] _c- [CF (CF ₃ ) O] _d- [CF ₂ CF ₂ O] _e -Z-COF

[Formula 4]

FOC-Z- [CF ₂ O] _b- [CF ₂ CF (CF ₃ ) O] _c- [CF (CF ₃ ) O] _d- [CF ₂ CF ₂ O] _e -Z-COF

[Chemical Formula 5]

CF ₃ CF ₂ CF ₂ O- [CF ₂ -CF ₂ -CF ₂ -O] _f -COF

(In Chemical Formulas 2 to 5,
Y and Z is a perfluoro alkyl group of C _1-5,
a, b, c, d, e And f are each an integer of 2 to 100.)

The perfluorinated polyether modified compound of Chemical Formula 1 is added to a monomer or a polymer and a solvent so that the perfluorinated polyether compound is positioned on its surface when coated to have excellent antifouling properties and decontamination characteristics of the perfluorinated compound. In addition, the compound may be added to the substrate to form a coating film of various thicknesses easily transparent by UV curing after coating, there is an advantage that can be used without changing the additional process by adopting a conventional coating method and a universal UV curing method. .

At this time, the amount of m, n, l in the formula (1) can be easily adjusted according to the amount of the precursor to be added, it is possible to easily adjust the amount of the UV curing functional group required to improve the durability.

The perfluorinated polyether compound for imparting water repellency, oil repellency, antifouling property and decontamination property to the perfluorinated polyether modified compound of the present invention should be prepared by selecting the compound and molecular weight among the compounds of Formulas 2 to 5 according to the intended use. do.

The present invention also provides a method for preparing the perfluorinated polyether modified compound, which is as shown below.

The present invention comprises the steps of synthesizing a perfluorinated polyether compound (step 1); Synthesizing an oligomer using an unsaturated hydrocarbon compound composed of two or more hydrocarbon monomers including an esterifiable end group and a polymerizable double bond (step 2); Reacting and esterifying the perfluorinated polyether compound synthesized in Step 1 with the oligomer synthesized in Step 2 (Step 3); And it provides a method for producing the antifouling perfluorinated polyether-modified compound according to the invention, comprising the step (step 4) of introducing a polymerizable double bond to the oligomer.

Hereinafter, the present invention will be described in detail for each step.

Step 1 of the present invention is a step of synthesizing a perfluorinated polyether compound.

In step 1, the perfluorinated polyether compound can be synthesized according to a known method as described in JAMES T. HILL, J. Macromol. Sci. Chem. , A8, (3), p 499 (1974)].

That is, a method of mixing hexafluoropropylene oxide (HFPO) and cesium fluoride in a solvent is used, in which the solvent is not particularly limited to those commonly used in the art, for example, triglyme, tetraglycol, and the like. Solvents selected from meth, butyl diglyme and ethyl diglyme can be used. The degree of polymerization (molecular weight) of the perfluorinated polyether compound synthesized by the above method can be controlled by the rate of introduction of HFPO and the reaction temperature.

Step 2 of the present invention is a step of synthesizing an oligomer using an unsaturated hydrocarbon compound composed of two or more hydrocarbon monomers including an esterifiable end group and a polymerizable double bond.

In the step 2, the polymerizable hydrocarbon monomer is preferably a monomer compatible with the substrate, and the hydrocarbon monomer is synthesized by the polymer polymerization method unsaturated hydrocarbon compound.

At this time, the synthesized hydrocarbon-based compound is adjusted to have an appropriate molecular weight using a thiol compound to form a micro emulsion when mixed with the substrate.

The synthesized hydrocarbon compound may be sequentially subjected to purification, vacuum and drying processes to obtain an oligomer having a hydrocarbon compound having compatibility with the substrate.

In this case, the hydrocarbon monomer is (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (Meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, N-methylol (meth) acrylamide, N-methylol acrylamide butyl ether and 2-hydroxypropyl (meth) It is preferable to select one or two or more from the group consisting of acrylates, and through this, it is possible to impart compatibility with the substrate to the hydrocarbon-based compound.

Step 3 of the present invention is a step of esterifying the perfluorinated polyether compound synthesized in Step 1 and the oligomer synthesized in Step 2.

In step 3, the perfluorinated polyether compound synthesized in step 1 may be esterified by stirring in an appropriate solvent with the oligomer to which the hydrocarbon compound synthesized in step 2 is bonded. The degree of polymerization of the product produced through the esterification is an important variable for determining antifouling properties, compatibility with hydrocarbon-based compounds constituting the substrate, surface migration due to a phase separation effect, and persistence of antifouling properties.

At this time, the perfluorinated polyether compound of the step 3 and the hydrocarbon-based oligomer can be used in a mixture of 95: 5 to 5: 95% by weight, if outside the above range it is not possible to obtain the effect of the present invention. If the content of the unsaturated hydrocarbon is less than the above range there is a problem that the compatibility with the substrate is lowered, if the content exceeds the range there is a problem that the surface movement and surface properties are lowered.

As a polymerization method for preparing the two compounds as the macromonomer, general polymer polymerization may be used, and in the present invention, the macromonomer is prepared using the radical polymerization method.

In addition, the reaction temperature of step 3 is preferably maintained at a temperature of 60 to 70 ℃ in consideration of the viscosity of the perfluorinated polyether compound and the characteristics of the boiling point of the solvent. In this case, the solvent is generally used in the art, but is not particularly limited, trifluorobenzene, 1,3-bistrifluorobenzene, 1,4, which can dissolve the perfluorinated polyether compound and the hydrocarbon compound in common. It can be used as a solvent selected from the group consisting of bis trifluoro benzene and benzotrifluoride.

Step 4 of the present invention is a step of introducing a polymerizable double bond into the oligomer of step 3.

In step 4, the oligomer synthesized in step 3 is acylated with an acyl chloride compound, and purification, vacuum and drying processes are sequentially performed. This makes it possible to synthesize a perfluorinated polyether modified compound having compatibility with the substrate and having a double bond polymerizable to the terminal group.

The present invention also provides another method for preparing the perfluorinated polyether modified compound, which is shown below.

The present invention comprises the steps of synthesizing a perfluorinated polyether compound (step 1); Oligomer synthesis reaction step (step 2) using an unsaturated hydrocarbon compound composed of two or more hydrocarbon monomers having an esterifiable end group and a polymerizable double bond; Introducing a polymerizable double bond into the hydrocarbon-based oligomer synthesized in step 2 (step 3); And reacting and esterifying the perfluorinated polyether compound synthesized in step 1 with the hydrocarbon-based oligomer having a double bond introduced in step 3 (step 4). Provided is a method for preparing a bovine polyether modified compound.

The production method is substantially the same as the first production method except that a double bond is first introduced into the hydrocarbon-based oligomer and then esterified with the perfluorinated polyether compound.

The perfluorinated polyether-modified compound comprising a perfluorinated polyether group, a hydrocarbon group and a polymerizable functional group in a single molecule according to the above-described manufacturing methods of the present invention forms a microdomain when it is mixed with a resin and a substrate to form a surface. It has excellent performance, excellent low energy surface modification effect, and anti-pollution and easy removal of pollutants. In particular, it is excellent in antifouling, water repellent, oil repelling and decontamination performance, so it can be applied to pollution prevention of display frame, water and oil repellent for industrial and textile, large structure for outdoor use, stain-resistant paint, mold release agent for precision molding, exterior protective coating and the like.

The present invention is an antifouling transparent compound comprising a perfluorinated polyether-modified compound and a solvent by mixing the perfluorinated polyether-modified compound synthesized through the above production method alone into a substrate, or dissolved in a solvent containing a photocuring initiator. It provides a coating composition.

At this time, it is preferable to include 50 to 90% by weight of the perfluorinated polyether modified compound and 10 to 50% by weight of the solvent.

Compositions prepared in proportions exceeding the above ranges have a problem in that they cannot exhibit antifouling characteristics of the antifouling transparent coating composition provided by the present invention.

Meanwhile, the solvent of the composition is preferably a fluorine-based solvent or a polar solvent having a hydroxy group or a carbonyl group in consideration of a coating method, stability of the composition, wettability to a substrate, and volatilization rate, and more preferably perfluorine heptane, Perfluorine hexane, m-xylene hexafluoroide, benzotrifluoride, methyl perfluorine butyl ether, ethyl perfluorine butyl ether, perfluorine (2-butyl tetrahydrofuran), petroleum benzene, mineral spirits, isoparaffin, Toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, diacetone alcohol, 2-ethoxyethanol, 2-methoxyethanol and 2- A single compound or a mixture of two or more selected from the group consisting of butoxyethanol can be used.

In another aspect, the present invention provides a membrane formed by coating the antifouling transparent coating composition.

The method of applying the film formed by coating the antifouling transparent coating composition is not particularly limited to a method generally used in the art, and may be a spin coating method, a dip coating method, a curtain coating method, a spray coating method, a sol gel method, and a vacuum deposition method. The known method of can be used.

The film thus coated is preferably 0.005 to 10 μm thick. In this case, if the thickness is less than 0.005 μm, there may be a problem that the antifouling property against water or oil cannot be expressed reliably. If the thickness is more than 10 μm, the thickness is non-uniform, resulting in deterioration or interference pattern of reflection characteristics. It is good to keep the thickness in the above range because problems may occur.

The film formed by coating the antifouling transparent coating composition thereon is not only a frame of various displays, but also flats such as lenses, windows, liquid crystals, flat panel display devices (PDP), organic light emitting devices (EL), and field emission displays (FED). It can be applied as an antireflection film or an optical filter for a panel display.

In addition, the membrane formed by coating the antifouling transparent coating composition of the present invention has an excellent effect of antifouling, decontamination, etc., without deteriorating its inherent transparency on the surface of the transparent glass or plastic product. Therefore, it is applicable to all fields that require the above effects, such as glass or plastic articles, specifically, lenses such as glasses, cameras, liquid crystal surfaces of various electronic products, general household, industrial glass, architectural exterior materials and art It can be used for articles and the like.

Hereinafter, the present invention has been described in more detail based on the following examples, but the present invention is not limited to the following examples.

Perfluorine Polyether  Synthesis of modified compounds 1

Step 1: Synthesis of Perfluorinated Polyether Compound

2.49 g of tetraglyme, 1.69 g of cesium fluoride, 87.75 g of hexafluoropropylene (HFP) and 420 g of hexafluoropropylene oxide were charged into a stainless high pressure reactor equipped with a stirrer, a cooling jacket, a thermometer, and a pressure gauge. Reaction was performed for a time to obtain a hexafluoro propylene oxide (HFPO) oligomer.

Step 2: oligomer synthesis step using hydrocarbon compound

To 100 g of methyl methacrylate (MMA), 39 g of 2-hydroxy ethyl methacrylate (HEMA) and 18.98 g of octanethiol were added to 157.98 g of tetrahydrofuran (THF) and stirred at 60 ° C for 6 hours. After the reaction was completed, the resulting reaction product was added to hexane to precipitate the macromonomer using the precipitation method, and dried under vacuum at room temperature. The oligomer in which the hydroxyl group was formed in the terminal was obtained through this.

Step 3: esterification step of perfluorinated polyether compound with hydrocarbon oligomer

5.00 g (0.0019 mol) of the hydrocarbon-based oligomer obtained in Step 2 and 56.8 g of benzotrifluoride were added to the reactor, and completely dissolved at 70 ° C., followed by 8.43 g of hexafluoro propylene oxide (HPFO) oligomer obtained in Step 1 above. 0.0019 mol) was added and stirred for 24 hours to esterify.

Step 4: introducing a double bond

A small amount of methylhydroquinone to prevent polymerization with the oligomer synthesized in step 3 was dissolved in benzotrifluoride as a solvent, and then 1.730 g (0.018 mol) of acryloyl chloride was added and stirred for 5 hours to acylate. The terminated reactant was added to hexane to precipitate the macromonomer by precipitation, and vacuum dried at room temperature to synthesize a perfluorinated polyether-modified compound having a double bond having the structure as shown in Formula 1 below.

[Formula 1]

(In Formula 1,
Rf is a perfluorinated ether group Y- [CF ₂ O] _b- [CF ₂ CF (CF ₃ ) O] _c- [CF (CF ₃ ) O] _d- [CF ₂ CF ₂ O] _e -Z-COF R represents a methyl group, m is 17, n is 1 and l is 5.

Perfluorine Polyether  Synthesis of Denatured Compound 2

The perfluorinated polyether modified compound was synthesized in the same manner as in Example 1, except that 165 g of HFPO was added in Step 1 of Example 1 to synthesize HFPO oligomer.

Perfluorine Polyether  Synthesis of Denatured Compound 3

A perfluorinated polyether modified compound was synthesized in the same manner as in Example 1, except that 682 g of HFPO was added in Step 1 of Example 1 to synthesize HFPO oligomer.

Perfluorine Polyether  Synthesis of Denatured Compound 4

The same method as in Example 1 except that 10.0 g, 26 g, and 25 g of perfluoropolyether compound, methmethyl acrylate (MMA), and 2-hydroxy ethyl methacrylate (HEMA) were added and esterified. The perfluorinated polyether modified compound was synthesized.

Perfluorine Polyether  Synthesis of Denatured Compound 5

A perfluoropolyether modified compound was synthesized in the same manner as in Example 4, except that 32.5 g and 100 g of methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) were each added and esterified. It was.

Perfluorine Polyether  Synthesis of Denatured Compound 6

Perfluoropolyether-modified compounds were synthesized in the same manner as in Example 4, except that 52 g and 125 g of methyl acrylate (MMA) and 2-hydroxy ethyl methacrylate (HEMA) were added and esterified, respectively. .

Experimental Example 1

Analysis by Gel Permeation Chromatography

In the above examples, the molecular weight of the hydrocarbon-based oligomer and the molecular weight of the perfluorinated polyether compound were analyzed by gel permeation chromatography, and the results are shown in Table 1 below.

As shown in Table 1, the molecular weights of the hydrocarbon oligomers of Examples 1 to 3 were 2609, and the molecular weights of the hydrocarbon oligomers of Examples 4 to 6 were 1050, 2570, and 3305, respectively. In addition, the molecular weight of the hexafluoro propylene oxide (HFPO) oligomer of Examples 1 to 3 was 4400, 1700, 6500, respectively, and the molecular weight of the hexafluoro propylene oxide (HFPO) oligomer of Examples 4 to 6 was 4400.

Through this it was confirmed that the synthesis of the oligomer through the hydrocarbon monomer was properly made.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 PFPE-COF (Mw) 4400 1700 6500 4400 4400 4400 PFPE-COF (g) 8.4 5.0 10.0 10.0 10.0 10.0 HEMA (g) 39 39 39 26 32.5 52 MMA (g) 100 100 100 25 100 125 OT (g) 19 19 19 19 19 19 MMAHEMA (Mw) 2609 2609 2609 1050 2570 3305 MMAHEMA (g) 5.02 7.71 4.12 5.52 6.02 6.50 AC (g) 1.73 1.40 0.71 0.85 0.85 1.31

Experimental Example 2

Perfluoroether  Denatured compound Nuclear magnetic  Analysis by Resonance Method 1

The hexafluoro propylene oxide (HFPO) oligomer synthesized in step 1 of Example 1 was analyzed by nuclear magnetic resonance, and the results are shown in FIG. 1.

As shown in FIG. 1, hexafluoro propylene oxide (HFPO) oligomer was measured by ¹⁹ F-NMR. FIG CF at 83.8ppm in the 1 ₃ CF _2, were able to identify the fluorine group of hexafluoropropylene oxide (HFPO) oligomer through the peak of CF ₃ CF _2, OCFCF ₃ etc. in 146.2PPM in 131.3PPM, the Through analysis, it was confirmed that the hexafluoropropylene oxide (HFPO) oligomer was properly synthesized.

<Experimental Example 3>

Perfluoroether  Denatured compound Nuclear magnetic  Resonance Analysis 2

The hydrocarbon oligomer synthesized in Example 1 was analyzed by ¹ H-NMR nuclear magnetic resonance, and the results are shown in FIG. 2.

Nuclear magnetic resonance analysis was confirmed that the methyl methacrylate (MMA) is about 17-mer, 2-hydroxy ethyl methacrylate (HEMA) is about hexamer. Through this, it was confirmed that the synthesis of the hydrocarbon oligomer through the two hydrocarbon monomers.

<Experimental Example 4>

Perfluoroether  Denatured compound Nuclear magnetic  Analysis by Resonance Method 3

The perfluorinated polyether-modified compound synthesized in Example 1 was analyzed by nuclear magnetic resonance of ¹ H-NMR and ¹⁹ F-NMR, and the results are shown in FIGS. 3 and 4, respectively.

As shown in FIG. 3, a peak corresponding to methylproton of methacrylate was detected at about 4.2 PPM, and the methyl group peak of 2-hydroxy ethyl methacrylate adjacent to the perfluorinated alkyl group was at about 4.8 PPM. Three complex peaks corresponding to are found at about 6.4 to 7.2 PPM.

In addition, as shown in FIG. 4, the fluorine groups of the perfluorinated polyether-modified compound were detected at about -130 PPM and about -145 PPM.

Through the above results it was confirmed that the perfluorinated polyether modified compound synthesized in Example 1 was properly synthesized.

Experimental Example 5

Perfluoroether  Denatured compound Fourier  Infrared Spectroscopy (FT-IR)

The perfluorinated polyether modified compound synthesized in Example 1 was subjected to Fourier infrared spectroscopy (FT-IR), and the results are shown in FIG. 5.

As shown in Fig. 5 2780 ~ 3000cm ^{- 1} in CH, 1730cm ^- from C = O, 1650cm ^-1 in ^{1 C = C, 1100 ~ 1340} cm - to check the CF peak at ^1, through which It was confirmed that the perfluorinated polyether modified compound has a double bond and has hydrogen, oxygen, and fluorine as substituents.

Therefore, it was confirmed that the perfluorinated polyether modified compound was properly synthesized.

<Experimental Example 6>

Evaluation of Dispersibility of Antifouling Coating Composition

1 g of the perfluoroether-modified compound synthesized in Examples 1 to 6 was added to 9 g of trimethyllopropane triacrylate (TMPTA) and 0.6 g of photoinitiator Irgacure 184 into 9.4 g of acetone, and the resultant was dispersed by sonication for 30 minutes. Except for the perfluorinated polyether modified compound of the invention was confirmed the dispersibility of the coating solution and the results are shown in Table 2 below.

<Dispersibility Check>

Milky white translucent: ○

Milky white opaque: △

Layer Separation Insoluble: ×

As shown in Table 2, in the sample of the perfluoroether-modified compound synthesized through the examples of the present invention, it was confirmed that the semi-transparent or opaque composition having a milky white color was dispersed without delamination.

Experimental Example 7

Of the membrane formed by coating the antifouling coating composition. Contact angle  Measure

The composition in which the perfluoroether modified compound used in Experimental Example 6 was dispersed was coated on a slide glass (2.6 × 3.8 × 0.1cm) by spin coating. Spin coating was carried out for 20 seconds under the condition of 2,000 rpm, the thickness of the coating surface was 1 to 2 ㎛. After coating the coating surface using a RC-250B Pulse UV / Vis curing system of Xenon Co., Ltd. was cured for 1 to 2 minutes at 2.5 J / cm ² conditions to form a film.

At this time, the formed film was measured the contact angle of water, diodomethane (DIM) using KR DSA100. The liquid droplet amount was 7 microliters at normal temperature. The higher the contact angle, the lower the surface energy, and the results of the experiment are shown in Table 2 below.

As shown in Table 2, it can be seen that the coating surface of the composition in which the perfluoroether-modified compound is dispersed through the examples of the present invention has a high contact angle compared with the composition which does not contain the perfluoroether-modified compound. Through this embodiment of the present invention it can be seen that the film coated with a composition in which the synthesized perfluoroether modified compound is dispersed has a low surface energy.

<Experimental Example 8>

Contamination of the membrane formed by coating the antifouling coating composition Preventive  Rating 1

Lines were drawn on the coating surface formed in Experimental Example 7 using commercially available red and black name pens (monami), and the dirts attached thereto were determined by visual inspection and the results are shown in Table 2 below.

<Oil Ink Pollution Prevention Criteria>

(Circle): Ink hardly adheres to a coating surface.

(Triangle | delta): Some ink adheres to a coating surface.

X: Ink adheres well to a coating surface.

As shown in Table 2, it can be seen that the coated surface of the composition in which the perfluoroether-modified compound dispersed through the embodiment of the present invention is dispersed has superior antifouling properties as compared to the composition containing no perfluoroether-modified compound. have.

Experimental Example 9

Contamination of the membrane formed by coating the antifouling coating composition Preventive  Evaluation 2

The oily ink attached in Experimental Example 8 was reciprocated five times with a force of 1 kgf / cm ² using a Kim wipe to wipe off the surface dirt. This was visually determined by wiping off the dirt and the results are shown in Table 2 below.

<Quality judgment standard wiping off pollutants>

(Circle): All the dirt can be wiped off.

(Triangle | delta): Although a dirt can be wiped off substantially, trace remains slightly.

X: A dirt remains and a trace remains clearly.

As shown in Table 2, the coating surface of the composition in which the perfluoroether-modified compound dispersed through the embodiment of the present invention is dispersed can be easily removed even when contaminants are attached as compared to the composition containing no perfluoroether-modified compound. As can be seen, excellent antifouling properties of the perfluorinated ether modified compound provided by the present invention can be seen through this.

Experimental Example 10

Contamination of the membrane formed by coating the antifouling coating composition Preventive  Evaluation 3

The coating state of the coated surface formed in Experimental Example 7 was visually observed and the results are shown in Table 2 below.

<Transmittance judgment standard>

○: The coating film was formed transparent.

(Triangle | delta): The coating film was formed slightly whiteish and slightly opaque.

X: The coating film was formed opaquely.

As shown in Table 2, it can be seen that the coated surface of the composition in which the perfluoroether-modified compound synthesized through the embodiment of the present invention is dispersed has a transparent property, thereby providing the perfluoroether-modified compound provided by the present invention. It can be seen that the composition containing can be effectively used as a coating agent such as a display, an optical product.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Coating solution except compound Contact angle (water) 121 115 115 118 120 116 72 Contact angle (DIM) 94 85 86 87 90 86 54 Pollution Prevention (Oil Ink) ○ ○ △ ○ ○ △ × Wiping nature
(Oil based ink) ○ ○ ○ ~ △ △ ○ ~ △ ○ ~ △ × Dispersibility Check △ △ △ ○ ~ △ △ ○ ~ △ - Permeability Check ○ ○ △ △ ○ △ ○

Claims (13)

Perfluorinated polyether modified compound represented by the following formula (1):
[Formula 1]

(In Formula 1,
Rf represents a perfluorinated ether group selected from the following Chemical Formulas 2 to 5,
R represents an alkyl group of C _1-18 ,
X represents hydrogen or a C _1-6 alkyl group or phenyl group,
m is an integer from 2 to 100, n and l are each an integer from 1 to 10.)

(2)
CF ₃ CF ₂ CF _2- [OCF (CF ₃ ) CF ₂ ] _a -OCF (CF ₃ ) COF
(3)
Y- [CF ₂ O] _b- [CF ₂ CF (CF ₃ ) O] _c- [CF (CF ₃ ) O] _d- [CF ₂ CF ₂ O] _e -Z-COF
[Chemical Formula 4]
FOC-Z- [CF ₂ O] _b- [CF ₂ CF (CF ₃ ) O] _c- [CF (CF ₃ ) O] _d- [CF ₂ CF ₂ O] _e -Z-COF
[Chemical Formula 5]
CF ₃ CF ₂ CF ₂ O- [CF ₂ -CF ₂ -CF ₂ -O] _f -COF
(In Chemical Formulas 2 to 5,
Y and Z is a perfluoro alkyl group of C _1-5,
a, b, c, d, e and f are each an integer of 2 to 100).
Synthesizing a perfluorinated polyether compound (step 1); Synthesizing an oligomer using an unsaturated hydrocarbon compound composed of two or more hydrocarbon monomers including an esterifiable end group and a polymerizable double bond (step 2); Reacting and esterifying the perfluorinated polyether compound synthesized in Step 1 with the oligomer synthesized in Step 2 (Step 3); And a step (step 4) of introducing a polymerizable double bond into the oligomer.
Synthesizing a perfluorinated polyether compound (step 1); Oligomer synthesis reaction step (step 2) using an unsaturated hydrocarbon compound composed of two or more hydrocarbon monomers having an esterifiable end group and a polymerizable double bond; Introducing a polymerizable double bond into the hydrocarbon-based oligomer synthesized in step 2 (step 3); And reacting and esterifying the perfluorinated polyether compound synthesized in step 1 with the hydrocarbon-based oligomer having a double bond introduced in step 3 (step 4). Method for producing bovine polyether modified compound.
According to claim 2 or 3, wherein the hydrocarbon monomer of step 2 is (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate , Dodecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, N-methylol (meth) acrylamide, N-methylol acrylamide A method for producing an antifouling perfluorinated polyether-modified compound according to claim 1, which is one or two or more selected from the group consisting of butyl ether and 2-hydroxypropyl (meth) acrylate.
The method of claim 2 or 3, wherein the perfluorinated polyether compound and the hydrocarbon-based oligomer are mixed at a ratio of 5 to 95% by weight of the perfluorinated polyether compound and 5 to 95% by weight of the hydrocarbon-based oligomer. Method for producing an antifouling perfluorinated polyether modified compound according to claim.
An antifouling transparent coating composition comprising the perfluorinated polyether modified compound of claim 1 and a solvent.
The antifouling transparent coating composition according to claim 6, wherein the weight ratio of the perfluorinated polyether modified compound and the solvent is 50 to 90 wt% of the perfluorinated polyether modified compound and 10 to 50 wt% of the solvent.
The antifouling transparent coating composition according to claim 6, wherein the solvent is a polar solvent having a fluorine solvent or a hydroxyl group or a carbonyl group.
The method of claim 8, wherein the polar solvent is perfluoro heptane, perfluorine hexane, m-xylene hexafluoride, benzotrifluoride, methyl perfluorine butyl ether, ethyl perfluorine butyl ether, perfluorine (2-butyl Tetrahydrofuran), petroleum benzene, mineral spirits, isoparaffin, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, diacetone alcohol, An antifouling transparent coating composition, characterized in that it is a single compound or a mixture of two or more selected from the group consisting of 2-ethoxyethanol, 2-methoxyethanol and 2-butoxyethanol.
A film formed by coating the antifouling transparent coating composition of claim 6.
The membrane of claim 10, wherein the membrane has a thickness of 0.005 to 10 μm.
The method of claim 10, wherein the film is used in at least one field selected from the group consisting of a functional coating film for display, an optical filter, a frame or surface coating of an electronic product, a fiber water repellent coating, an optical product coating and a paint. membrane.
The film of claim 12, wherein the display is at least one selected from the group consisting of liquid crystal, flat panel display (PDP), organic light emitting display (EL), and field emission display (FED).

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