KR101384424B1 - Fingerprint-resistant coating composition and the making method thereof and the method for making the hollow body particles for the fingerprint-resistant coating composition - Google Patents

Abstract

A production method of a fingerprint-resistant coating liquid composition according to the present invention comprises: a) mixing tetraethoxysilane and ethanol in a reaction container to obtain first mixture liquid, and stirring the first mixture liquid for 5-30 minutes; b) adding water and hydrochloric acid to the first mixture liquid while maintaining the temperature of the first mixture liquid at 20-35°C to produce second mixture liquid, and stirring the second mixture liquid for 10 minutes-1 hour; c) adding methyltrimethoxysilane to the second mixture liquid to produce third mixture liquid, and stirring the third mixture liquid for 20 minutes-1 hour; d) adding 3-methacryloxypropyl triethoxysilane to the third mixture liquid to produce fourth mixture liquid, and stirring the fourth mixture liquid for 30 minutes-2 hours; e) dripping hexadecyl trimethoxysilane and polydimethyl siloxane to the fourth mixture liquid to produce fifth mixture liquid, and stirring the fifth mixture liquid for 30 minutes-2 hours; f) adding isopropyl alcohol to the fifth mixture liquid, and stirring the mixture at room temperature for 30 minutes- 2 hours to obtain an inorganic binder; g) aging the inorganic binder for 12-36 hours by resting the inorganic binder at room temperature; h) and mixing and dispersing hollow body particles in the inorganic binder for producing the fingerprint-resistant coating liquid composition. [Reference numerals] (AA) Visible rays; (BB) Fingerprint-resistant effect by the roughness and water-repellent surface treatment

Description

Fingerprint coating composition and method for producing same and manufacturing method of hollow particles for preparing fingerprint coating liquid {fingerprint-resistant coating composition and the making method etc. and the method for making the hollow body particles for the fingerprint-resistant coating composition}

The present invention relates to an anti-fingerprint coating composition, a method for producing the same, and a method for preparing hollow particles for preparing an anti-fingerprint coating liquid, and has a low refractive index, high light transmittance, and high surface roughness, so that contaminants do not easily stick. Anti-fingerprint coating composition, a method for producing the same, and a method for producing a hollow particle material contained in the anti-fingerprint coating liquid.

Various display devices, such as mobile phones, PDAs, PMPs, and smart phones, are finished with glass or plastic materials, and people recognize images on the screen through glass or plastic materials attached to the surface of the display devices.

Although the glass itself is a material with good transmittance, it is an anti-reflective coating or anti-fingerprint that can exert this effect on the glass surface of the display device in order to achieve the protection, strength, anti-reflective and anti-fingerprint effects of the glass rather than by itself. It is coated and used.

In addition, there are many cases where a separate coating film is attached to the glass surface of display devices, and in this case, the coating film is coated with an anti-fingerprint coating or an anti-reflective coating solution on a synthetic resin film such as PET film.

FIG. 1 is a view illustrating a conventional anti-fingerprint technique using a coating liquid containing solid particles. When visible light is emitted onto the organic water-repellent coating 2 coated on the surface of the liquid crystal display 1, most of the visible light is emitted. The solid particles 3 show a phenomenon of causing strong diffuse reflection.

Referring to FIG. 1, conventionally, surface energy is lowered by using fluorine-based additives to organic resin, and silica (SiO ₂ ) or polymethyl methacrylate (PMMA) resin is added to improve the roughness of the coating film. roughness) to reduce the contact area of the contaminants to achieve the anti-fingerprint effect. However, since the conventional anti-fingerprint coating liquid uses solid particles such as silica or polymethyl methacrylate (PMMA), that is, filled particles, the visible light is irradiated to the organic water repellent coating layer (2). The amount of light reflected by the diffused reflection in the other direction was higher than the amount of light passing straight through the coating layer 2 as it was, and as a result, the coating layer 2 was blurred, resulting in haze. When attaching a film having such a coating layer on the device, visibility is often lowered and it becomes a barrier to viewing a clear screen.

In addition, the conventional anti-fingerprint coating solution using solid particles has a large amount of volatile organic compounds (VOC) generated by using an organic solvent as a binder, which is a threat to environmental pollution and health of the user, the hardness and scratch resistance of the coating layer itself When the film product coated with the coating solution is poor in performance, there is a problem in that the surface is easily damaged and the aesthetic appearance is not beautiful.

That is, in the conventional anti-fingerprint coating solution, the haze phenomenon is aggravated by using silica and polymethyl methacrylate (PMMA) resin particles as solid particles, and the sparkling is severe due to the crystallinity of the solid particles. There was a problem that visibility is reduced.

For this reason, it was necessary to develop a new type of anti-fingerprint coating solution that can improve visibility by increasing hollowness of the anti-fingerprint coating solution and improving transmittance by using hollow hollow particles instead of the existing solid particles. .

In addition, in the binder for the anti-fingerprint coating solution, it was necessary to develop an environment-friendly binder that does not generate any volatile organic compounds (VOCs) by manufacturing the binder using only inorganic materials without using any conventional organic binder.

1. Republic of Korea Patent Registration 10-1141955 (2012. 5. 4. notice) 2. Republic of Korea Patent Publication No. 10-2008-0071608 (August 4. 2008 publication)

An object of the present invention is to provide an anti-fingerprint coating composition and a method for producing the same, which can achieve low refractive index, high transmittance and antireflection effect by using hollow particles in order to solve the above problems.

In addition, the present invention develops an inorganic binder as a binder for mixing the hollow particles, thereby greatly improving the hardness, durability, and scratch resistance of the coating layer without generating volatile organic compounds harmful to humans and the environment. It is an object to provide an inorganic binder composition and a method for producing the same.

In addition, it is an object of the present invention to provide a binder composition for an anti-fingerprint coating liquid and a method of manufacturing the same which can form an environmentally friendly inorganic coating having high hardness and high scratch resistance using a sol gel process. .

In addition, the present invention does not use any metal fluoride used in the preparation of the hollow particles in the prior art, but instead forms a hematite core by hydrothermal reaction, and then condenses silica around the core to shell An object of the present invention is to provide a method for preparing a hollow particle material for an anti-fingerprint coating liquid by forming a core-shell particle and then removing the core to obtain only hollow shell particles.

In order to achieve the above object, a method for preparing hollow particles for preparing an anti-fingerprint coating solution provided by the present invention includes a) ferric chloride hexahydrate (FeCl _{3 ·} 6H ₂ O), sodium hydroxide (NaOH), and polyvinylpyrrolidone ( a first step of mixing polyvinyl pyrrolidone (PVP) with water and stirring in the reactor; b) a second step of proceeding the hydrothermal synthesis reaction while stirring the mixed solution stirred in the first step for 15-25 hours at a temperature of 150 ℃ to 250 ℃ in a hydrothermal synthesis reactor; c) a third step of obtaining the synthesized hematite (Fe ₂ O ₃ ) core particles by performing cooling, washing and drying after completion of the reaction of the second step; d) a fourth step of mixing the synthesized hematite core particles with water and adding a sodium hydroxide (NaOH) aqueous solution to form a buffer solution (buffer solution); e) a fifth step of mixing and aging an aqueous solution of sodium silicate (Na ₂ SiO ₃ ) and an aqueous solution of sodium sulfate in the buffer solution; f) a sixth step of washing the synthesis solution synthesized in the fifth step with distilled water and then filtering to obtain core-shell particles in which a shell is covered around the hematite core particles; And g) mixing the core-shell particles with water, and then removing the core in the core-shell particles using hydrochloric acid to leave only the shell to form hollow particles.

In addition, in order to achieve the above object, the method for preparing hollow particles for preparing an anti-fingerprint coating liquid provided by the present invention comprises: h) mixing the hollow body particles obtained in the seventh step with water and then adding hydrochloric acid to maintain the acidic atmosphere. Eighth step of adding and stirring fluoroalkylsilane in the state; And i) performing a hydrothermal reaction for 30 minutes to 2 hours at a temperature of 120 to 200 ° C. in the hydrothermal synthesis reactor in the hydrothermal synthesis reactor, and after completion of the hydrothermal synthesis reaction, cooling, washing, filtering and drying operations are performed. The ninth step of performing a surface-modified hollow particles by performing a fluoro alkyl silane; characterized in that it further comprises.

And in order to achieve the above object, the method for producing hollow particles for preparing an anti-fingerprint coating liquid provided by the present invention is characterized in that the diameter of the hollow particles is 100 to 1000 nm, and the shell thickness of the hollow particles is 20 to 300 nm. . More preferably, the diameter of the hollow particle may be 300 to 600 nm, and the shell thickness of the hollow particle may be 100 to 200 nm.

On the other hand, the anti-fingerprint coating composition provided by the present invention in order to achieve the above object is made by mixing a hollow material with an inorganic binder, wherein the inorganic binder is 12 to 25% by weight of tetra ethoxy silane (tetra ethoxy silane) , 3 to 13% by weight of methyl trimethoxy silane, 6 to 18% by weight of 3-methacryloxypropyl triethoxysilane, 8 to 16% by weight of ethanol, isopropyl alcohol ( isopropyl alcohol) 25 to 36% by weight, 10 to 20% by weight of water, 0.5 to 4% by weight of hexadecyltrimethoxy silane, 0.05 to 3% by weight of hydrochloric acid and 0.1 to 3 poly dimethyl siloxane It comprises a weight percent.

And in order to achieve the above object, the method for preparing a fingerprint-protective coating liquid composition provided by the present invention comprises: a) a first step of mixing tetraethoxysilane and ethanol in a reaction vessel to form a first mixture and stirring for 5 to 30 minutes; b) a second step of mixing the first mixture with water and hydrochloric acid in the state of maintaining the first mixture at 20-35 ° C. to form a second mixture and stirring the second mixture for 10 minutes to 1 hour; c) a third step of preparing a third mixture by mixing methyltrimethoxysilane with respect to the second mixture and stirring the third mixture for 20 minutes to 1 hour; d) preparing a fourth mixture by mixing 3-methacryloxypropyl triethoxysilane to the third mixture, and stirring the fourth mixture at a temperature of 30 to 45 ° C. for 30 minutes to 2 hours; e) a fifth step of adding dropwise hexadecyltrimethoxy silane and polydimethyl siloxane to the fourth mixture to form a fifth mixture, and stirring the fifth mixture at a temperature of 30 to 45 ° C. for 30 minutes to 2 hours; f) a sixth step of adding an isopropyl alcohol to the fifth mixture and stirring the mixture for 30 minutes to 2 hours at room temperature to form an inorganic binder; g) a seventh step of leaving the inorganic binder at room temperature for aging for 12 to 36 hours; And h) mixing and dispersing the hollow particle material in the inorganic binder to form an anti-fingerprint coating liquid composition, wherein the inorganic binder contains 12-25 wt% of tetraethoxysilane and methyltrimethoxy. 3 to 13% by weight of silane, 6 to 18% by weight of 3-methacryloxypropyl triethoxysilane, 0.5 to 4% by weight of hexadecyltrimethoxy silane, 0.1 to 3% by weight of polydimethyl siloxane, 8 to 16% by weight of ethanol , 25 to 36% by weight of isopropyl alcohol, 0.05 to 3% by weight of hydrochloric acid and 10 to 20% by weight of water is included.

The method for producing hollow particles for an anti-fingerprint coating liquid according to the present invention enables the hollow particle material to be made of a hollow shell alone, and thus has a lower refractive index and a higher transmittance than a coating liquid made of silica or PMMA resin particles of the prior art. As it rises, the anti-reflection effect is excellent, and the thin film interference fringe phenomenon is suppressed, thereby greatly improving the visibility of the display device.

In addition, the anti-fingerprint coating composition according to the present invention does not emit any volatile organic compounds harmful to humans and the environment because it uses an environmentally friendly inorganic binder, and has the advantage of excellent hardness and scratch resistance of the coating layer.

1 is a view for explaining a conventional anti-fingerprint technology using a coating liquid containing solid particles, when visible light is reflected on the organic water-repellent coating (2) coated on the surface of the liquid crystal display 1, most of the visible light is a solid particle Field (3) causes strong diffuse reflection.
Figure 2 shows in a flow chart form a method for producing a fingerprint coating composition according to the present invention.
Figure 3 is a simplified illustration of the manufacturing process of the hollow particle particles 13 for the anti-fingerprint coating liquid according to the present invention, after the synthesis of hematite core (10) after covering the shell (11) with silica particles The process of making the hollow particle 13 by removing the core 10 is shown.
4 is a scanning electron microscope (SEM) image of the hollow particles 13 manufactured according to the present invention.
Figure 5 shows the content ratio range for each component of the inorganic binder composition used in the anti-fingerprint coating liquid according to the present invention.
FIG. 6 is a SEM photograph of a state in which the inorganic binder 20 prepared according to the present invention is coated on a PET film.
7 is a SEM photograph of the anti-fingerprint coating liquid 30 prepared according to the present invention.
FIG. 8 is a SEM photograph of a cross section of the anti-fingerprint coating liquid 30 shown in FIG. 7.
9 shows that when the anti-fingerprint coating composition according to the present invention is applied on the liquid crystal display 1, most of the visible light passes through the hollow body particles 13 to prevent reflection, thereby preventing the hollow body particles 13 in the coating solution composition. Shows that performing a function of preventing roughness of fingerprints by increasing roughness of the coating layer.
10 and 11 are tables showing the results of measuring various transmittances using a hazemeter after applying the anti-fingerprint coating composition according to the present invention on a film.
Figure 12 is to contrast the anti-fingerprint coating composition and the anti-fingerprint coating composition of the prior art according to each function and effect according to the present invention.

Hereinafter, with reference to the accompanying drawings will be described in detail the configuration and operation effects of the anti-fingerprint coating composition, a method for producing the same and a method for producing hollow particles for producing an anti-fingerprint coating solution.

Figure 2 shows in a flow chart form a method for producing a fingerprint coating composition according to the present invention. Referring to Figure 2, the method for producing a fingerprint coating composition according to the present invention, the process for producing a hollow particle material 100 and the step of synthesizing an inorganic binder (step S7) and the hollow particles produced so Comprising a step (S8) of mixing the substances into the inorganic binder to complete the anti-fingerprint coating solution.

Among these, first, the process of preparing the hollow particle material will be described. A core is synthesized from the hematite component (step S1), and then the hematite core particles are added to distilled water and dispersed evenly by an ultrasonic disperser. Then, sodium hydroxide (NaOH) aqueous solution is added to make a buffer solution (step S2). A buffer solution, also called a buffer solution, refers to a solution that tends to maintain its pH without changing its pH when acid or alkali is added.

After the buffer solution of hematite was prepared, sodium silicate and sodium sulfate aqueous solution were added dropwise to the buffer solution and aged at a temperature of 60-90 ° C. for about 30 minutes to 2 hours to surround the hematite core. The shell (shell) of the silica component is bonded (step S3). Here, "dropping" refers to an operation of adding a drug or a sample by dropping it slowly.

After the core-shell particles are ultrasonically dispersed in distilled water, the hematite core is removed using hydrochloric acid (HCl) to generate hollow particles by leaving only a hollow spherical shell (S4 step). Thus, the hollow particles are still weak in strength and chemically hydrophilic (親水 性), if used in the coating solution as it is easy to leave a mark such as fingerprints on the coating layer, in order to improve the surface properties of these hollow particles, Hydrothermal synthesis reaction of fluoroalkylsilane on the sieve particles to modify the surface properties of the hollow particles to hydrophobic (S5 step), and then complete the hollow particles through cooling, washing and drying process. (Step S6).

Meanwhile, the inorganic binder may include tetra ethoxy silane, methyl trimethoxy silane, 3-methacryloxypropyl triethoxysilane, ethanol, and isopropyl alcohol ( isopropyl alcohol), hexadecyltrimethoxy silane (hexadecyltrimethoxy silane), hydrochloric acid, poly dimethyl siloxane (poly dimethyl siloxane) and water are sequentially mixed to synthesize an inorganic binder (step S7). In the present invention, the inorganic binder used to mix the hollow particles does not use an organic solvent and does not generate health hazards such as volatile organic compounds (VOCs), and has excellent hardness and scratch performance.

When the hollow particles and the inorganic binder are completed in this way, the hollow particles are added to the inorganic binder to disperse well to complete the anti-fingerprint coating solution (step S8).

Figure 3 is a simplified illustration of the manufacturing process of the hollow particle particles 13 for the anti-fingerprint coating liquid according to the present invention, after the synthesis of hematite core (10) after covering the shell (11) with silica particles The process of making the hollow particle 13 by removing the core 10 is shown.

Unlike the conventional anti-fingerprint and anti-reflective coating solution using solid particles, the present invention is characterized by making hollow hollow particles 13 and mixing the hollow particle materials with an inorganic binder to form a coating solution. In the present invention, ferric chloride hexahydrate (FeCl ₃ · 6H ₂ O), sodium hydroxide, and polyvinylpyrrolidone (PVP) are _first subjected to hydrothermal synthesis reaction to prepare a hematite (Fe ₂ O ₃ ) component. After the core 10 is formed, a plurality of grains of silica (SiO ₂ ) components are combined around the core 10 to form a shell 11. The core-shell particles 12 thus formed are treated with hydrochloric acid and When the same acid solution is added, only the hematite core 10 inside the shell 11 can be removed by leaving the shell 11 itself. The present invention is to form an anti-fingerprint coating film by mixing the hollow particles 13 made through this process in an inorganic binder and applying to a target substrate such as a film, glass or the like.

A method of synthesizing the hollow body particles 13 described above with reference to FIGS. 2 and 3 will be described below in more detail with reference to specific examples.

[1] synthesis of hematite core particles

First, in the process of synthesizing the hollow particles 13, a core serving as a skeleton of each hollow particle is composed of hematite (Fe ₂ O ₃ ), which is synthesized through the following process.

[1.1] 4 mmol ferric chloride hexahydrate (FeCl ₃ · 6H ₂ O), 40 mmol sodium hydroxide (NaOH), and 1.0 g polyvinylpyrrolidone (PVP) are prepared and added to a 200 mL reactor.

[1.2] Subsequently, 30 ml of distilled water is added into the reactor to make a mixed liquid, and the mixed liquid is reacted with stirring at 30 to 50 ° C. for 1 to 3 hours.

[1.3] Next, the mixed solution is placed in a Teflon-lined stainless steel hydrothermal reactor, followed by hydrothermal reaction while stirring at a temperature of 150 to 250 ° C. for 10 to 25 hours. Here, hydrothermal synthesis refers to a method of synthesizing a metal salt, oxide, hydrate, or metal powder using a property depending on the solubility, temperature, pressure, and concentration of a solvent in a solution state or suspension state. The reaction is one of the liquid phase synthesis methods to synthesize a substance using water or an aqueous solution under high temperature and high pressure.

[1.4] After the hydrothermal synthesis reaction is completed, the mixture is naturally cooled and cooled to room temperature, followed by washing 2 to 5 times with distilled water and then 2 to 5 times with ethanol to remove impurities. In this washing process, filter media such as filter paper may be used. If the mass production equipment is installed, the washing process may be performed using a filter press device.

[1.5] After washing and filtration, only hematite-containing solids remain, and the solids are dried for 5 to 20 hours at 50-90 ° C under vacuum to hematite core particle material. To complete.

On the other hand, in the synthesis process of [1.1] to [1.5], it is more preferable to proceed with the synthesis operation under the following working conditions. That is, in the above step [1.2], 30 ml of distilled water is added to the reactor to make a mixed solution, and the mixed solution can be reacted with stirring at 40 ° C. for 2 hours. In the above step [1.3], the mixed solution is teflon-lined. The hydrothermal synthesis reaction may be performed while stirring in a stainless hydrothermal synthesis reactor for 18 hours at a temperature of 200 ° C. In the above step [1.4], after the completion of the hydrothermal synthesis reaction, the mixed solution is naturally cooled to room temperature, washed three times with distilled water, and then washed three times with ethanol. The solids remaining after filtration can be dried under vacuum at a temperature of 70 ° C. for 12 hours to complete the hematite core particle material.

[2] core-shell particle synthesis

[2.1] Add 50 g of hematite core particles synthesized by the core synthesis step [1] to 1 liter of distilled water, and disperse for 5 to 30 minutes using an ultrasonic disperser.

[2.2] A buffer solution is prepared by adding 0.1N NaOH aqueous solution to the mixed solution of the hematite core to adjust the pH of the mixed solution to 9.0 to 11.0.

[2.3] The above buffer solution is heated to a temperature of 60 ~ 90 ℃ with stirring.

[2.4] 300 ml of a 2.7% sodium silicate solution and 300 ml of a 1.0% sodium sulfate (Na ₂ SO ₄ ) solution are prepared, and the two aqueous solutions are added dropwise to the above buffer solution, and slowly over 30 minutes to 2 hours. Dropwise, the silica particles are condensed to the hematite core particles to form a silica shell. At this time, sodium silicate (sodium silicate, Na ₂ SiO ₃ ) has a structure in which silica (SiO ₂ ) and sodium oxide (Na ₂ O) are combined, and silica particles are condensed in an aqueous solution to be bonded to the hematite core.

[2.5] After the sodium silicate aqueous solution and the sodium sulfate aqueous solution are added dropwise, the mixture is aged for 30 minutes to 2 hours while maintaining the temperature of the mixture at 60 to 95 ° C.

[2.6] The core-shell particles are obtained by washing and filtering the finished synthetic liquid (containing core-shell particles) with distilled water.

Meanwhile, in the core-shell particle synthesis process of [2.1] to [2.6], the synthesis operation may be performed under the following working conditions. That is, in the above step [2.1], the mixture of hematite core particles can be dispersed for 10 minutes using an ultrasonic disperser, and in step [2.2], the hydrogen ion concentration (pH) of the above mixture can be adjusted to 10.0. In the above step [2.3], the temperature can be maintained at 75 ° C. when the above buffer solution is stirred. In the above step [2.4], when the sodium silicate solution and the sodium sulfate solution are added dropwise to the buffer solution, it is preferably added dropwise over 1 hour. In the above step [2.5], the sodium silicate solution and the sodium sulfate solution are added dropwise to the buffer solution. After aging at 75 ° C. for 1 hour is preferred.

[3] core removal

[3.1] After the core-shell particles filtered by the above [2.6] step are mixed in 1 liter of distilled water, ultrasonic dispersion is performed for 5 to 30 minutes.

[3.2] 35% hydrochloric acid is added dropwise to the mixture of core-shell particles, wherein hydrochloric acid is slowly added dropwise to the core-shell particle mixture until the core in the core-shell particles is removed by hydrochloric acid.

[3.3] Washing and filtering are performed after the cores in the core-shell particles are removed.

On the other hand, in the process of [3.1], it is preferable to ultrasonically disperse the core-shell particles in distilled water for 10 minutes.

[4] surface modification

[4.1] After mixing 100 g of the hollow particles from which the core is removed by the above [3] process to 1000 liters of distilled water, the hydrogen ion concentration (pH) of the mixed solution is adjusted to 2.0 to 4.0 using 0.1 N hydrochloric acid.

[4.2] Add 10 g of fluoroalkylsilane to the mixture and stir at room temperature for 30 minutes to 2 hours.

[4.3] After the mixture is stirred, hydrothermal synthesis is performed for 30 minutes to 2 hours at 120 to 190 ° C using a hydrothermal synthesis reactor.

[4.4] After the hydrothermal synthesis reaction, the mixture is naturally cooled at room temperature, washed 2-5 times with distilled water, washed 2-5 times with ethanol, and then filtered with filter paper.

[4.5] The filtered solid is dried in a vacuum at a temperature of 50 to 90 ° C. for 5 to 20 hours to finally complete synthesis of the hollow particle materials surface-modified with fluoroalkyl silane.

On the other hand, in the hollow surface modification process of the above [4.1] ~ [4.5], the reforming operation can be carried out under the following working conditions. That is, in the above step [4.1], it is preferable to adjust the hydrogen ion concentration of the mixed solution to 3.0. In the above step [4.2], it is preferable to add fluoroalkyl silane to the mixed solution and then stir at room temperature for 1 hour. Preferably, in the above step [4.3], the hydrothermal synthesis reaction is preferably performed at 150 ° C. for 1 hour when the hydrothermal synthesis reaction is performed on the mixed solution. In the above step [4.4], the mixed solution after the hydrothermal synthesis reaction is carried out. When washing with distilled water, it is preferable to wash three times with distilled water and then three times with ethanol. In the above step [4.5], it is preferable to dry the filtered solids at 70 ° C. for 12 hours under vacuum. desirable.

Through the above-described processes [1] to [4], the final composite hollow particles have a structure in which the outer shell (shell part) has a structure in which fluoroalkyl silane is bonded to silica, and the space inside the shell is empty, The size (diameter) of each particle is about 100 to 1000 nm, and the shell thickness of the hollow particles is about 20 to 300 nm. In addition, more preferably, the size (diameter) of the hollow particles finally synthesized by the present invention may be about 300 to 600 nm, and the thickness of the shells of the hollow particles may be about 100 to 200 nm.

If the size of the hollow particles is 300 nm or less, the haze of the anti-fingerprint coating layer is low, but the roughness is low, so that the anti-fingerprint performance is deteriorated, and a thin film interference fringe phenomenon may occur. On the other hand, when the size of the hollow particles is 600nm or more, the anti-fingerprint performance is excellent, but there is a problem that the haze due to the enlargement of the hollow particles may be deepened.

4 is a scanning electron microscope (SEM) photograph of the hollow particles 13 manufactured according to the present invention. As well shown in Fig. 4, the shell portion of the hollow body particles 13 appears black, and the inner space therein appears bright, so it is well shown that the inner space of each hollow particle 13 is empty.

Figure 5 shows the content ratio range for each component of the inorganic binder composition used in the anti-fingerprint coating liquid according to the present invention.

Referring to the composition content ratio table of Figure 5, the inorganic binder constituting the anti-fingerprint coating liquid in the present invention, 12 to 25% by weight of tetra ethoxy silane (tetra ethoxy silane), methyl trimethoxy silane (methyl trimethoxy silane) 3 ~ 13 wt%, 6-18 wt% 3-methacryloxypropyl triethoxysilane, 0.5-4 wt% hexadecyltrimethoxy silane, 8-16 wt% ethanol, 25 to 36% by weight of isopropyl alcohol, 0.05 to 3% by weight of hydrochloric acid, 0.1 to 3% by weight of poly dimethyl siloxane (poly dimethyl siloxane) and 10 to 20% by weight of water.

According to the inventors' experiment, the content ratio of each component constituting the inorganic binder was 17.9 wt% of tetraethoxysilane, 10.4 wt% of methyltrimethoxysilane, and 15.6 wt% of 3-methacryloxypropyl triethoxysilane. Durability of the inorganic binder synthesized when set to 1.7 wt% of hexadecyltrimethoxy silane, 11.4 wt% of ethanol, 29.2 wt% of isopropyl alcohol, 0.1 wt% of hydrochloric acid, 0.4 wt% of polydimethyl siloxane, and 13.3 wt% of water, The strength, scratch resistance, antireflection performance and permeability were all excellent (first optimal embodiment).

On the other hand, according to the experimental results of the present invention, the content ratio of each component constituting the inorganic binder in the present invention, 20.7% by weight of tetraethoxysilane, 5.9% by weight of methyl trimethoxysilane, 3-methacryloxypropyl tri When synthesized with 8.8% by weight of oxysilane, 2% by weight of hexadecyltrimethoxy silane, 13% by weight of ethanol, 33.7% by weight of isopropyl alcohol, 0.1% by weight of hydrochloric acid, 0.5% by weight of polydimethyl siloxane, and 15.3% by weight of water. The performance of the inorganic binder has also been shown to be desirable (second optimal example).

Here, the components of the inorganic binder will be described in more detail.

① Tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) is a basic constituent material of the inorganic binder according to the present invention and has the following molecular structure.

Tetraethoxysilane has the effect of improving the hardness, scratch resistance, abrasion resistance, heat resistance, etc. of the binder coating film, whereas, when a large amount is added, the brittleness of the coating film is increased to form a coating film having a hard and brittle property. As a result, cracks may easily occur in the coating film.

If tetraethoxysilane is added below 20%, hardness, scratch resistance, abrasion resistance, heat resistance, etc. may be lowered.However, when added above 20%, brittle coating film is formed to create a crack risk. There is a problem of getting higher.

② Methyltrimethoxysilane (C ₄ H ₁₂ O ₃ Si) is a basic constituent material of the inorganic binder according to the present invention has the following molecular structure.

The methyltrimethoxysilane is condensed with the tetraethoxysilane to form an inorganic structure, and the methyl (methoxy) group suppresses the occurrence of cracks when using tetraethoxysilane alone, methyl (Methyl) The effect of groups affects the formation of three-dimensional network structure of silica (SiO ₂ ).

In addition, when using tetraethoxysilane alone, silanol formed after hydrolysis has an unstable structure, and thus, methyltrimethoxysilane may be added to suppress instability of silanol.

Methyltrimethoxysilane may be used more than 5.9%, but may cause problems of deterioration in hardness and scratch performance.

③ 3-methacryloxypropyl triethoxysilane (C ₁₀ H ₂₀ O ₅ Si) is a basic constituent material of the inorganic binder according to the present invention and has the following molecular structure.

3-methacryloxypropyl triethoxysilane has a structure substituted with a methacryloxypropyl group with a silane coupling agent (Silane Coupling Agent), which plays an important role in forming a hybrid structure between inorganic and organic.

3-methacryloxypropyl triethoxysilane is used to increase the adhesion between the PET film and the inorganic binder, which is an anti-fingerprint film. When the content of the total composition is added to 8.8% or more, hardness, scratch, wear resistance, Durability may occur and yellowing may occur. And when 3-methacryloxypropyl triethoxysilane is added below 8.8%, adhesiveness with PET film may fall.

④ Hexadecyltrimethoxy silane is an additive that plays an auxiliary role in improving the anti-fingerprint performance in the inorganic binder according to the present invention.

In the hexadecyltrimethoxy silane, the long carbon chain of the hexadecyl group serves to minimize the surface energy of the anti-fingerprint coating layer, thereby preventing the adhesion of contaminants. .

When the addition ratio of hexadecyltrimethoxy silane in the content of the total inorganic binder is 2% or less, the anti-fingerprint performance of the coating solution of the present invention may be deteriorated. Haze may occur, and hardness, wear resistance, durability, and the like may be reduced.

⑤ Ethyl alcohol (Ethyl alcohol, ethanol) is a solvent (solvent) added to the anti-fingerprint coating solution according to the present invention increases the solubility between the additives plays a role of increasing the mixing properties. Ethyl alcohol is water soluble and harmless to humans. In addition, when a small amount of ethyl alcohol is added, the solubility of the coating liquid compositions may be reduced, and thus the uniformity of the synthesized anti-fingerprint coating liquid may be decreased. On the other hand, when a large amount is added, a reaction time may increase and a problem of forming a low molecular weight inorganic coating film may occur. Can be.

⑥ iso propyl alcohol is also a solvent added to the anti-fingerprint coating solution of the present invention, and plays a role of increasing the solubility between the additives to increase the compatibility.

By using isopropyl alcohol in combination with ethyl alcohol, it is responsible for controlling the volatility due to boiling point and solubility difference and forming a uniform coating film during coating film formation.

When a small amount of isopropyl alcohol is added, the solubility of the compositions may be lowered, and thus the uniformity of the synthesized anti-fingerprint coating may be lowered. On the contrary, when a large amount is added, the reaction time may be increased and a low molecular weight inorganic coating may occur. .

⑦ hydrochloric acid (HCl) is a catalyst used in synthesizing the anti-fingerprint coating solution according to the present invention, the anti-fingerprint coating solution of the present invention must be synthesized in an acidic atmosphere. This is because the ionized hydrogen ions attack in the order of high acidity during hydrolysis in acid. Thus, an inorganic binder having a linear structure is formed, so that an inorganic coating coating film can be formed.

When the hydrochloric acid is added at 0.1% or less, the hydrolysis reaction may be slow, and the reaction time may be long. On the contrary, when the hydrochloric acid is added at 0.1% or more, the reaction rate may be increased, and shelf life may be shortened.

⑧ The basic molecular structure of polydimethyl siloxane is as follows.

The poly dimethyl siloxane is an auxiliary additive added to the anti-fingerprint coating liquid according to the present invention, and serves to reduce adhesion of contaminants. In addition, polydimethyl siloxane also plays a role in improving the feel of the anti-fingerprint coating layer, and when added in an amount of 0.5% or less of the total inorganic binder, the function of preventing contaminant adhesion may be deteriorated. On the contrary, when a large amount is added, phase separation, cratering, and whitening may occur.

⑨ Water (H ₂ O) is required for hydrolysis of silane, and the mole ratio of water (H ₂ O) / silane (3) is between 3 and 6 for optimal anti-fingerprint binder properties. do.

When the molar ratio of water / silane is 3 or less, the reaction time of the binder becomes long, there is a possibility that hydrolysis does not occur completely, and the hardness, wear resistance, durability, etc. of the coating layer may be lowered. When the molar ratio of water / silane is 6 or more, durability of the anti-fingerprint coating layer may be reduced.

When preparing the inorganic binder of the anti-fingerprint coating liquid according to the present invention, ultrapure water should be used, and the conductivity should be 18.0 MΩ or more.

<Method of manufacturing inorganic binder>

Next, the manufacturing method of the inorganic binder for the anti-fingerprint coating liquid according to the present invention,

a) a first step of mixing tetraethoxysilane and ethanol in a reaction vessel to form a first mixture and stirring for 5 to 30 minutes;

b) a second step of mixing the first mixture with water and hydrochloric acid in the state of maintaining the first mixture at 20-35 ° C. to form a second mixture and stirring the second mixture for 10 minutes to 1 hour;

c) a third step of preparing a third mixture by mixing methyltrimethoxysilane with respect to the second mixture and stirring the third mixture for 20 minutes to 1 hour;

d) preparing a fourth mixture by mixing 3-methacryloxypropyl triethoxysilane to the third mixture, and stirring the fourth mixture at a temperature of 30 to 45 ° C. for 30 minutes to 2 hours;

e) a fifth step of adding dropwise hexadecyltrimethoxy silane and polydimethyl siloxane to the fourth mixture to form a fifth mixture, and stirring the fifth mixture at a temperature of 30 to 45 ° C. for 30 minutes to 2 hours;

f) a sixth step of adding an isopropyl alcohol to the fifth mixture and stirring the mixture for 30 minutes to 2 hours at room temperature to form an inorganic binder;

g) a seventh step of leaving the inorganic binder at room temperature for aging for 12 to 36 hours; And

h) mixing and dispersing the hollow particle material in the inorganic binder to form an anti-fingerprint coating liquid composition;

At this time, in the inorganic binder, 12 to 25% by weight of tetraethoxysilane, 3 to 13% by weight of methyltrimethoxysilane, 6 to 18% by weight of 3-methacryloxypropyl triethoxysilane, hexadecyltrimethoxy silane 0.5 ~ 4 wt%, 0.1-3 wt% polydimethyl siloxane, 8-16 wt% ethanol, 25-36 wt% isopropyl alcohol, 0.05-3 wt% hydrochloric acid, and 10-20 wt% water The hydrogen ion concentration (pH) of the final mixed solution is in the range of 3-4.

On the other hand, when presenting a more specific embodiment of the manufacturing process of the inorganic binder for an anti-fingerprint coating liquid according to the present invention.

1) Prepare a synthesis equipment equipped with a stirrer, a round flask, a heating mantle, a thermostat, a condenser, and the like. Here, the heating mantle refers to a mechanism used to heat the contents of a flask or beaker.

2) Add 103.5 g of tetraethoxysilane and 65.5 g of ethanol to a 1 liter round flask and stir for 10 minutes ('first mixture'), then fix the first mixture at 30 degrees using a temperature controller. To keep it.

3) A mixture of 76.5 g of water and 0.5 g of hydrochloric acid (HCl) is added dropwise to the first mixture over 10 minutes ('second mixture'), and the second mixture is stirred using a stirrer for 30 minutes.

4) 60 g of methyltrimethoxysilane is added dropwise to the second mixture over 10 minutes ('third mixture'), and the third mixture is stirred for 30 minutes.

5) 90 g of 3-methacryloxypropyl triethoxysilane was added dropwise to the third mixture over 20 minutes ('fourth mixture'), and the fourth mixture was maintained at a temperature of 35 ° C. over 1 hour with stirring. do.

6) To the fourth mixture, 10 g of hexadecyltrimethoxy silane and 2.5 g of polydimethyl siloxane were added dropwise over 5 minutes ('5th mixture'), and the fifth mixture was stirred at a temperature of 35 ° C for 1 hour. do.

7) After adding 168.5 g of isopropyl alcohol to the fifth mixture, the heating was stopped and stirred at room temperature for 1 hour. The inorganic binder for the anti-fingerprint coating liquid thus synthesized is aged by standing at room temperature for 25 hours. In this way, the hydrogen ion concentration (pH) of the finally synthesized inorganic binder should be in the range of 3-4.

6 is a scanning electron microscope (SEM) photograph of a state in which the inorganic binder 20 prepared according to the present invention is coated on a PET film. Referring to FIG. 6, it can be seen that the coating film 20 of the inorganic binder is formed on the PET film with a uniform thickness t.

The inorganic binder coated in FIG. 6 is coated with a uniform thickness by using a tool called a 'bar coater'. In the photo of FIG. 6, the thickness of the coating layer 20 of the inorganic binder is about 0.6 μm and is uniform. It can be seen that one coating film was formed.

Up to now, the method for preparing the hollow particle material and the method for preparing the inorganic binder according to the present invention have been described, respectively. In the following, these two materials (ie, ① hollow particle material and ② inorganic binder) are mixed with each other to prevent fingerprint coating. Explain the process of making.

In the present invention, a method for synthesizing the final anti-fingerprint inorganic coating liquid after mixing the inorganic binder and the hollow body,

(1) First, 500 g of the anti-fingerprint binder is added to a 1 liter beaker, and then 5 g of the hollow material is added to the anti-fingerprint binder.

(2) When the ultrasonic dispersion is performed for 10 minutes using the ultrasonic dispersion machine with respect to the mixed solution of the anti-fingerprint binder and the hollow material, the final anti-fingerprint coating liquid is completed.

Regarding the mixing ratio of the inorganic binder and the hollow body in the present invention, the ratio of binder (containing 10% solids): hollow body = 100: 1 is judged to be ideal. When the hollow body ratio is 1 or less, the anti-fingerprint performance is reduced. The interference fringe phenomenon may occur. And when the ratio of the hollow body is 1 or more, there is a problem that the visibility of the display is reduced by increasing the haze.

7 is a scanning electron microscope (SEM) photograph of the anti-fingerprint coating liquid 30 prepared according to the present invention. The black part in the picture of Fig. 7 is the anti-fingerprint coating liquid 30, and the white spots in several places indicate the presence of the hollow particle material 13. Figure 7 is a photograph of the anti-fingerprint coating liquid according to the present invention after the bar coating using a bar coater (bar coater) to observe the plane of the coated surface by scanning electron microscopy, hollow on the surface throughout the coating material It is observed that the particles 13 are evenly dispersed.

FIG. 8 is a scanning electron microscope (SEM) photograph of the cross section of the anti-fingerprint coating solution 30 shown in FIG. 7.

According to Fig. 8, a coating layer having a thickness of about 500 nm was formed, and a large number of convex spherical protrusions assumed to be hollow bodies 13 were observed.

9 shows that when the anti-fingerprint coating composition according to the present invention is applied on the liquid crystal display 1, most of the visible light passes through the hollow body particles 13 to prevent reflection, thereby preventing the hollow body particles 13 in the coating solution composition. Shows that performing a function of preventing roughness of fingerprints by increasing roughness of the coating layer.

As well shown in Figure 9, the anti-fingerprint coating liquid according to the present invention has a high transmittance and low refractive index through the light particles are contained in the hollow body (中空 体). Accordingly, when visible light is incident on the anti-fingerprint coating layer according to the present invention, most of the light is transmitted as it is and the amount of diffuse reflection is small, thereby greatly improving the visibility of the display. In addition, the coating solution for anti-fingerprint according to the present invention has a large volume of hollow particles, so that the degree of bending of the surface of the coating layer is larger than that of the coating solution using conventional solid particles (see FIG. 1), and thus, contaminants such as fingerprint traces may be formed. It is difficult to stick to the surface of the coating layer. As a result, the anti-fingerprint coating composition according to the present invention has an advantage of preventing fingerprint reflection and greatly improving the visibility of the display and increasing the illuminance to have an excellent anti-fingerprint effect.

In Fig. 9, reference numeral 1 denotes a liquid crystal display coated with a coating layer, and 2a denotes an inorganic water / oil repellent coating film.

10 and 11 are tables showing the results of measuring various transmittances using a hazemeter after applying the anti-fingerprint coating composition according to the present invention on a film. The measurement equipment used to obtain the experimental data of FIGS. 10 and 11 was NDH-5000 haze meter of Nippon Denshoku, Japan, and the light source used in this equipment was a white LED.

First, referring to the measurement results summarized in FIG. 10, the present inventors found haze, total transmittance, and parallelism with respect to five samples having different input contents of the hollow particle material into the binder. The transmittance and diffusion transmittance were measured, and the sample of G-5, which had the lowest amount of hollow material (0.5 wt%), exhibited a thin film interference fringe, resulting in poor display visibility. However, the haze was the lowest and the parallel transmittance was the highest due to the small amount of hollow material. In contrast, the sample of G-1, which had the highest amount of hollow particle material (5 wt%), had the highest haze, the lowest parallel transmittance (P.T), and the highest diffusion transmittance (D.T). Looking at the cases of the five samples shown in Figure 10, it was shown that the sample of G-4 obtains the best results. Therefore, when the hollow particle material was added to the inorganic binder according to the present invention, it was confirmed that the hollow particle material was added at a weight ratio of 100: 1.

On the other hand, Figure 11 is a haze value, haze value, total transmittance (TT), parallel transmittance (PT), diffusion transmittance (DT) for the samples (1, 2, 3) having a different thickness of the anti-fingerprint coating layer according to the present invention ) And the result of measuring the interference pattern, etc., when the thickness of the coating layer is the thinnest at 300 nm (sample 1), the parallel transmittance is too low and the diffusion transmittance is high, indicating that the light refraction and scattering are severe. When the thickness of the coating layer is 700 nm, the thickest (sample 3), the parallel transmittance is good, but there is a problem in that the visibility of the display is poor due to interference fringes. For this reason, the sample 2 of the three samples in FIG. 11 had a thickness of 500 nm of the coating layer, which did not generate interference fringes, exhibited good display visibility, and maintained an appropriate parallel transmittance. As a result, among the three samples of FIG. 11, the case in which the coating thickness of the coating layer was maintained at 500 nm was confirmed that the most preferable results were obtained.

As described above, when the anti-fingerprint coating liquid according to the present invention is applied to a film or glass or the like, maintaining the coating thickness of about 400 to 600 nanometers yielded the most desirable results. If the thickness of the coating layer is less than 400 nanometers, the hollow particle material itself protrudes out of the coating layer so that the haze is deepened due to unevenness of the surface, and the thickness of the coating layer becomes more than 600 nanometers. In this case, the coating layer is too thick, so that the hollow particle materials are buried in the coating layer to lose roughness, and thus anti-fingerprint performance cannot be expected.

According to the above test results, in the anti-fingerprint coating composition according to the present invention, the hollow body contained therein is the most excellent anti-fingerprint when adding 1% by weight of the hollow particle materials of 400 to 600 nanometers to the inorganic binder. It was confirmed that effects and display visibility can be obtained.

Figure 12 is to contrast the anti-fingerprint coating composition and the anti-fingerprint coating composition of the prior art according to each function and effect according to the present invention.

Referring to Figure 12, the conventional anti-fingerprint coating or anti-reflective coating liquid using an organic binder and lacking the hardness and scratch resistance of the coating layer, whereas the anti-fingerprint coating liquid using the inorganic binder according to the present invention has a hardness of the coating film Excellent and good scratch performance was obtained.

In addition, the conventional coating solution for anti-fingerprint has a problem that a large amount of volatile organic compounds (VOCs) are generated due to the organic solvent in the manufacturing process and use process, which adversely affects the human body and the environment, whereas the anti-fingerprint according to the present invention The coating solution has advantages in that physical properties such as durability of the coating solution are improved due to the use of an environmentally friendly inorganic binder and have a favorable effect on the environment and the human body. Volatile organic compounds have a high vapor pressure, which easily evaporates into the atmosphere, resulting in photochemical reactions with nitrogen oxides in the air, creating secondary pollutants such as ozone and peroxyacetal nitrate (PAN), causing photochemical smog. Say

In addition, the conventional anti-fingerprint coating liquid has a problem that low visibility and high refractive index because the particles contained therein are all solid particles such as silica or PMMA, but the anti-fingerprint coating liquid according to the present invention is Since all the granules are composed of hollow particles in which silica is condensed in a hollow shell form, the transmittance is good, the refractive index is low, and the visibility of the display can be greatly improved.

The anti-fingerprint coating composition according to the present invention can be widely used in materials such as films and glass for various display devices. In addition, the inorganic binder developed in the present invention is a non-stick coating, which can be widely applied to the foodware market, and is widely used for metal protection, architectural aluminum panels, subway interior and exterior materials, and screen doors of station platforms. It can be widely applied as a coating of equipment. In addition, the inorganic binder of the present invention can be used to make an insulating coating film of the electronic material, and can be applied to a heating device and a high temperature reactor, etc., which can form an ultra high temperature coating film of up to 1000 ° C. or higher, It can also be used to form hybrid coatings for various applications, and can also be used for water repellent coatings for textiles, clothing, leather, wood, and the like.

In particular, the sol gel process (sol gel procees) adopted in the process of manufacturing the inorganic binder in the present invention is a technique capable of forming an inorganic coating (ceramic) at low temperature is applicable to various fields.

On the other hand, the shell hollow particle material of the silica material developed in the present invention can be used as a light diffusing agent because it can improve the brightness than the existing light diffusing agent, excellent thermal insulation and insulation effect due to the pores of the hollow Therefore, it can be used as a thermal insulation paint. In addition, as the trend toward miniaturization of semiconductor devices and printed circuit boards (PCBs) requires a low dielectric material, the hollow material according to the present invention may be utilized as a low dielectric material for such use. In addition, since the drug release rate can be controlled by efficiently delivering the drug to the target site of the human body, the drug may be used as a drug delivery material. In addition, the hollow particle material proposed by the principles of the present invention can be applied to various fields of various industrial fields according to its size and shape.

1: LCD Screen 2: Organic Water Repellent Film
2a: inorganic water / oil repellent coating solution 3: solid particles
3 ': silica, PMMA 10: core
11: shell 12: core-shell particles
13: hollow body particle 15: shell inner cavity
20: inorganic binder coating layer 30: anti-fingerprint coating liquid

Claims (13)

a) a first step of mixing ferric chloride hexahydrate (FeCl _{3 ·} 6H ₂ O), sodium hydroxide (NaOH) and polyvinylpyrrolidone (PVP) with water and stirring in the reactor;
b) a second step of proceeding the hydrothermal synthesis reaction while stirring the mixed solution stirred in the first step for 15-25 hours at a temperature of 150 ℃ to 250 ℃ in a hydrothermal synthesis reactor;
c) a third step of obtaining the synthesized hematite (Fe ₂ O ₃ ) core particles by performing cooling, washing and drying after completion of the reaction of the second step;
d) a fourth step of mixing the synthesized hematite core particles with water and adding a sodium hydroxide (NaOH) aqueous solution to form a buffer solution (buffer solution);
e) a fifth step of mixing and aging an aqueous solution of sodium silicate (Na ₂ SiO ₃ ) and an aqueous solution of sodium sulfate in the buffer solution;
f) a sixth step of washing the synthesis solution synthesized in the fifth step with distilled water and then filtering to obtain core-shell particles in which a shell is covered around the hematite core particles; And
g) mixing the core-shell particles with water, and then removing the core in the core-shell particles using hydrochloric acid to leave only the shell, thereby forming hollow particles. Method for producing hollow particles for preparing a coating liquid. The method of claim 1,
h) an eighth step of mixing the hollow body particles obtained in the seventh step with water and then adding and stirring fluoroalkylsilane while maintaining hydrochloric acid in an acidic atmosphere; And
i) The hydrothermal synthesis reaction of the mixed solution of the eighth step is carried out for 30 minutes to 2 hours at a temperature of 120 ~ 200 ℃ in the hydrothermal synthesis reactor, cooling, washing and filtering and drying after completion of the hydrothermal synthesis reaction And a ninth step of making the hollow particles surface-modified with fluoroalkyl silane. According to claim 1, wherein the molar ratio of ferric chloride hexahydrate and sodium hydroxide in the first step is 1: 5 to 1: 20, polyvinylpyrrolidone is characterized in that mixing 0.1 to 5g per 30ml of water Method for producing hollow particles for the production of anti-fingerprint coating liquid. The method of claim 1, wherein the cooling in the third step uses a natural cooling method at room temperature, and the washing is performed two to five times with ethanol after washing the cooled hydrothermal reaction product with distilled water two to five times. Using a washing method, the drying is characterized in that for drying for 7 to 20 hours at a temperature of 50 ~ 90 ℃ in a vacuum state, a method for producing hollow particles for anti-fingerprint coating liquid. According to claim 1, wherein the buffer solution in the fourth step is mixed with 20 ~ 100g of hematite core particles in 1 liter of distilled water and then dispersed for 5 to 20 minutes using an ultrasonic disperser, aqueous sodium hydroxide solution of 0.1N concentration It is made by adding, wherein the pH of the buffer solution is characterized in that 9 to 11, a method for producing a hollow body particles for the production of anti-fingerprint coating liquid. According to claim 2, wherein the eighth step, the hollow body particles per 1000 liters (liter) of distilled water is mixed at a ratio of 50 ~ 200g, and the pH of the hollow body particle mixture solution using hydrochloric acid (HCl) of 0.1N concentration It adjusts to 2-4, and adds 2-30g of fluoroalkyl silanes, The manufacturing method of the hollow particle for anti-fingerprint coating liquid manufacture. The method of claim 1 or 2, wherein the hollow particles have a diameter of 100 to 1000 nm and a shell thickness of 20 to 300 nm. Made by mixing the hollow material with an inorganic binder,
At this time, the inorganic binder is 12 to 25% by weight of tetra ethoxy silane (tetra ethoxy silane), 3 to 13% by weight of methyl trimethoxy silane (methyl trimethoxy silane), 3-methacryloxypropyl triethoxysilane (3-methacryloxypropyl 6-18% by weight of triethoxysilane, 8-16% by weight of ethanol, 25-36% by weight of isopropyl alcohol, 0.5-4% by weight of hexadecyltrimethoxy silane, 0.05-3% by weight of hydrochloric acid Anti-fingerprint coating composition, characterized in that it comprises 0.1 to 3% by weight of poly dimethyl siloxane (poly dimethyl siloxane) and 10 to 20% by weight of water. delete a) a first step of mixing tetraethoxysilane and ethanol in a reaction vessel to form a first mixture and stirring for 5 to 30 minutes;
b) a second step of mixing the first mixture with water and hydrochloric acid in the state of maintaining the first mixture at 20-35 ° C. to form a second mixture and stirring the second mixture for 10 minutes to 1 hour;
c) a third step of preparing a third mixture by mixing methyltrimethoxysilane with respect to the second mixture and stirring the third mixture for 20 minutes to 1 hour;
d) preparing a fourth mixture by mixing 3-methacryloxypropyl triethoxysilane to the third mixture, and stirring the fourth mixture at a temperature of 30 to 45 ° C. for 30 minutes to 2 hours;
e) a fifth step of adding dropwise hexadecyltrimethoxy silane and polydimethyl siloxane to the fourth mixture to form a fifth mixture, and stirring the fifth mixture at a temperature of 30 to 45 ° C. for 30 minutes to 2 hours;
f) a sixth step of adding an isopropyl alcohol to the fifth mixture and stirring the mixture for 30 minutes to 2 hours at room temperature to form an inorganic binder;
g) a seventh step of leaving the inorganic binder at room temperature for aging for 12 to 36 hours; And
h) mixing and dispersing the hollow particle material in the inorganic binder to form an anti-fingerprint coating liquid composition;
At this time, in the inorganic binder, 12 to 25% by weight of tetraethoxysilane, 3 to 13% by weight of methyltrimethoxysilane, 6 to 18% by weight of 3-methacryloxypropyl triethoxysilane, hexadecyltrimethoxy silane 0.5 ~ 4 wt%, polydimethyl siloxane 0.1-3 wt%, ethanol 8-16 wt%, isopropyl alcohol 25-36 wt%, hydrochloric acid 0.05-3 wt% and water 10-20 wt% The manufacturing method of the anti-fingerprint coating liquid composition. The method of claim 10, wherein the pH of the anti-fingerprint coating composition obtained in the eighth step is in the range of 3 to 4. The method according to claim 10, wherein the hollow particle material is mixed with the inorganic binder in a weight ratio of 1:50 to 1: 200,
The hollow particle material,
① 8-1 step of mixing ferric chloride hexahydrate (FeCl ₃ · 6H ₂ O), sodium hydroxide (NaOH) and polyvinyl pyrrolidone (PVP) with water and stirring in the reactor;
② 8-2 step of proceeding the hydrothermal synthesis reaction while stirring the mixed solution stirred in the first step for 15 to 25 hours at a temperature of 150 ℃ to 250 ℃ in a hydrothermal synthesis reactor;
③ step 8-3 to obtain the synthesized hematite (Fe ₂ O ₃ ) core particles by performing cooling, washing and drying after the reaction of the second step is completed;
④ 8-4 step of mixing the synthesized hematite core particles with water and adding a sodium hydroxide (NaOH) aqueous solution to create a buffer solution (buffer solution);
⑤ step 8-5 of mixing and aging an aqueous solution of sodium silicate (Na ₂ SiO ₃ ) and an aqueous solution of sodium sulfate in the buffer solution;
(8) steps 8-6 of washing the synthesized liquid synthesized in the fifth step with distilled water and filtering to obtain core-shell particles covered with a shell around the hematite core particles; And
⑦ by mixing the core-shell particles in water and then using the hydrochloric acid to remove the core in the core-shell particles to leave only the shell to make hollow particles; Method for producing hollow particles for preparing an anti-fingerprint coating liquid. The method according to claim 10 or 12, wherein the hollow particles have a diameter of 100 to 1000 nm and a shell thickness of 20 to 300 nm.

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