KR101081431B1 - Preparation method of hard coating material using organic-inorganic hibrid synthesis process - Google Patents

Abstract

PURPOSE: A method for preparing an organic/inorganic hybrid hard coating agent is provided to obtain an organic/inorganic hybrid hard coating agent with excellent scratch resistance and fluidity through surface modification of a material. CONSTITUTION: A method for preparing an organic/inorganic hybrid hard coating agent comprises a polysilicate compound synthesis process and an organic/inorganic hybrid coating agent synthesis process. The polysilicate compound synthesis process comprises the steps of: mixing silicon-based colloidal silica with acid metallic catalyst in a solvent; mixing metal alkoxides with the resultant; mixing a silane coupling agent with the resultant; mixing a stabilizer with the resultant; and mixing the resultant with metal additives.

Description

Preparation method of organic-inorganic hybrid hard coating agent {Preparation method of hard coating material using organic-inorganic hibrid synthesis process}

The present invention relates to a method for preparing an organic-inorganic hybrid coating, and in particular, by synthesizing a polysilicate compound having excellent hardness by a sol-gel process, by synthesizing an organic-inorganic hybrid hard coating agent through a hybrid process with an organic polymer resin, the surface of the material surface The present invention relates to a method for preparing an organic-inorganic hybrid hard coating having flexibility through modification, excellent in various functions such as easy removal of contaminants and scratch resistance.

In general, various surface coating techniques include conventional wet surface coating techniques such as electroplating, and dry surface coatings classified by chemical vapor deposition (CVD) or physical vapor deposition (PVD). By using technology and Sol-Gel process, the advantages of inorganic materials and organic materials can be controlled at the molecular level, and organic-inorganic nano coating solution that can give new functionality by adding functional organic materials is used. There is a coating technology.

Melamine, polyfunctional acryl, urethane, etc. are used for the organic coating agent, and the inorganic coating agent is mainly composed of a silicone-based compound of a metal alkoxide.

Silica monoliths prepared by the sol-gel process show excellent transparency, hardness, heat resistance, etc., but the main disadvantage is that the micropores present in the inorganic chain shrink due to the difference in capillary force due to evaporation of the solvent generated during the drying process. This occurs badly, there is a problem that the cracks occur because the lack of flexibility of the weapon chains can not endure such stress in the end.

A schematic scheme of the organic-inorganic hybrid material through the sol-gel process is as follows.

Hydrolysis

RSi (OR) 3 + 3H2O → RSi (OH) 3 + 3ROH

Condensation

R (OH) 2SiOH + HOSi (OH) 2R → R (OH) 2Si-O-Si (OH) 2R + H2O

Polymerization

O3 = Si-R + R'-Si = O3 → O3 = Si-R "-R" -Si = O3

(R: ethoxy group or methyl group, R ': alkyl group or hydroxyl group, R ": siloxane group or epoxy group)

In the organic-inorganic hybrid material prepared as described above may be divided into three types according to the manner in which the organic material is added to the network structure of the inorganic material.

(1) When the added organic material acts as a modifier of the mesh structure of the inorganic material.

(2) The inorganic and organic materials have a mesh structure, and the inorganic and organic materials are connected by a chemical bond.

(3) Inorganic and organic materials form their respective network structures without chemical bonding to each other.

In the organometallic alkoxide, the organic component directly bonded to the metal, unlike the alkoxy group, cannot be hydrolyzed and condensed, thereby basically acting as a modifier of the mesh structure of the inorganic material.

In the case of (1), it can be easily obtained by hydrolysis and condensation reaction of the organometallic alkoxide to which the organic component is bound (H. Schmidt, J. Non-Cryst. Solids 178 (1994) 302).

In the case of (2), R (methyl group), which does not occur hydrolysis, has a reactor such as an epoxy group or a methacryl group, and hydrolysis and condensation reactions occur, and organic components react with each other by heat or ultraviolet irradiation to polymerize the polymer. The organic component of the organometallic alkoxide and the added organic monomer are polymerized by adding an organic monomer having a reactor. Therefore, such a structure can be connected by chemical bonding between the network structure of the inorganic material and the network structure of the organic material (H. Schmidt, J. Non-Cryst. Solids 178 (1994) 302).

In the case of (3), the formation of the three-dimensional network structure of the inorganic material by the hydrolysis and condensation reaction of the metal alkoxide and the formation of the three-dimensional network structure of the organic material through the polymer polymerization of the organic monomer occur independently of each other. .

In this case, if the difference in reaction rate is severe or if the compatibility between two phases (phase) is small, the possibility of phase separation may be very large.

Looking at the organic-inorganic nano-composite manufacturing technology to solve the above problems as follows.

Silicon dioxide (SiO2) / titanium dioxide (TiO2) with good oxygen permeability and wettability using silicon (Si), titanium (alkoxides), epoxy silanes, and methacrylosisilanes ) -Epoxide complex method, using tetramethoxy silane, zirconium (Zr), aluminum (Al), or titanium (Ti) alkoxides and epoxysilane Hard coating on polycarbonate spectacle lens to greatly improve abrasion resistance, 3-glycidoxypropyl trimethoxy silane (3-GPTMS: 3-glyciddoxypropyltrimethosysilane for use in automotive or aviation applications) ), Aluminum (Al) -alkoxide (alkoxide), propyltrimethoxysilane (PTMS: propyltrimethosysilane) using a coating method for improving the corrosion resistance and wear resistance to the metal surface.

Hybrid materials substituted with groups capable of polymerizing a common silicon alkoxide, such as tetramethylorthosilicate (TMOS) or tetraethylorthosilicate (TEOS), have lower cure temperatures and shorter quenching than conventional sol-gel materials. It has a curing time.

3-Glycidoxyflophyltrimethoxysilane (3-GPTS), which is a precursor of a typical hybrid material, has an epoxy ring (pH) by an appropriate initiator due to the presence of an epoxy group capable of polymerization. Epoxy ring is opened to bond with other reactants.

Hardness and wear resistance may be increased by adding an alkoxide or sol capable of forming a metal oxide such as aluminum (Al), zirconium (Zr), titanium (Ti), or the like to the hybrid material.

At this time, the metal alkoxide or sol to be added may be added to provide refractive index control or other functionality in addition to wear resistance.

In particular, hybrid materials added with aluminum alkoxide or bohemite sol have higher hardness and wear resistance than other metal alkoxide or sol added materials.

In hard coatings requiring strong hardness, aluminum alkoxide has been reported to have a greater effect on the increase in hardness than other metal alkoxides.

Hardness in the hard coating to which alumina is added has a significant effect on the hardness and wear resistance of the particle size of the added alumina precursor.

The larger the size of the alumina particles produced in the coating solution, the higher the hardness of the coating and the higher the wear resistance. However, as the agglomeration of alumina particles increases, the hardness of the coating increases, but the transparency of the coating is lost, and the material becomes unstable, causing cracking of the coating. Binders made from glycidoxyflophyl trimethoxysilane (GPTS) -tetramethyl olisosilicate (TMOS) as precursors can prevent agglomeration between these alumina particles and can impart flexibility to thick coatings.

Optically transparent hard coatings require homogeneous particle size and size distribution of the alumina particles that can produce sufficient abrasion resistance and hardness. For example, a hard boehmite sol with alumina particles may be used in a hard coating containing alumina of the same composition. Hard coatings have higher hardness than aluminum alkoxides (D. Hobbl, M. Nacken, and H. Schmidt, J. Sol-Gel Sci. Technol. 19 (2000) 309).

On the other hand, the silicone-based hard coating agent to compensate for the various physical disadvantages in the plastic, starting with the technology using a hydrolyzate of EIDUPONT tetraalkoxy silane in combination with vinyl acetate in 1943. Technology and markets are dependent on developed countries.

Gilbert et al. Use UV-curable acrylate resins and tetraethoxysilanes and 3-methacryloxypropyltrimethosysilane as a coupling agent. Possible wear resistant organic-inorganic hybrid coatings were prepared.

Urreaga et al. Prepares methyl methacrylate (MMA), propyltrimethoxysilane (PTMS), tetraethylorthosilicate (TEOS) composites, and the wear resistance and microhardness of the process conditions and coating layers. The correlation between microhardness is investigated and applied to wear-resistant coating of plastic spectacle lens.

As a coating agent used for the metal or plastic surface, it can be considered to divide into an organic polymer type and an inorganic type coating agent.

However, the organic polymer system has the advantages of excellent compatibility and flexibility after coating, but has a disadvantage of weak surface hardness and thermally weakness. In the case of inorganic coating solution, temperature control is required in the synthesis step, and the surface hardness after coating is excellent but the coating layer is cracked. This is likely to occur, and there are many industrial applications.

In addition, in the case of inorganic type, as the solid content is increased (more than 30%), storage stability is not good after manufacturing, so refrigeration storage is required, and when stored at room temperature, the gelation of the coating liquid proceeds to the coating liquid when it is left at room temperature for more than one week. It becomes impossible to use.

In order to overcome the disadvantages of the organic polymer and inorganic coating agent, the development of an organic-inorganic hybrid coating agent is urgently required.

The present invention is designed to solve the above problems, the first step of stirring by mixing 10 to 30 parts by weight of silicon-based colloidal silica and 0.01 to 0.5 parts by weight of the acid metal catalyst and 10 to 80 parts by weight of the solvent, and the first step 3 to 10 parts by weight of the metal alkoxide was added to the resultant, and a third step of stirring by adding 10 to 30 parts by weight of the silane coupling agent to the resultant of the second step and the resultant of the third step A polysilicate compound synthesis process comprising a fourth step of adding and stirring 0.1-1 part by weight of a stabilizer and a fifth step of adding 0.1-3 parts by weight of a metal additive to the resultant of the fourth step; A first step of mixing 30-50 parts by weight of the polysilicate compound to 40 to 60 parts by weight of a solvent, and a second step of mixing and mixing 0.01 to 0.1 parts by weight of a pH adjuster to the resultant of the first step, and the second step Organic-inorganic hybrid coating agent comprising a third step of mixing and stirring 10-30 parts by weight of the curing agent to the result of the second step, and a fourth step of mixing and stirring 10-20 parts by weight of the organic polymer resin to the resultant of the third step Synthesis process; characterized in that the method for producing an organic-inorganic hybrid hard coating agent, characterized in that the technical gist.

In addition, the solvent of the first step of the polysilicate compound synthesis process is preferably alcohols or distilled water, and the acid metal catalyst of the first step of the polysilicate compound synthesis process is a metal phosphate catalyst, a metal hydrochloride catalyst and It is preferable to use any one of the phosphoric acid-hydrochloric acid complex catalysts.

In addition, the metal alkoxide of the second step of the polysilicate compound synthesis process, it is preferable to use any one or a mixture of two or more of silicon alkoxide, zirconium alkoxide, titanium alkoxide and aluminum alkoxide.

In addition, the silane coupling agent in the third step of the polysilicate compound synthesis process is preferably one of alkoxy silane, alkyl silane, aminosilane, methoxysilane and methyl silane or a mixture of two or more thereof.

In addition, the stabilizer of the fourth step of the polysilicate compound synthesis process, it is preferable to use any one or a mixture of two or more of acetylacetone, ethyl acetoacetate, iron acetylacetone and alkanoneamine, and the poly The metal additive of the fifth step of the silicate compound synthesis process is preferably an aluminum compound.

In addition, the solvent of the first step of the organic-inorganic hybrid coating agent synthesis process, it is preferable to use a solvent selected from any one of alcohols, cellulsolves, ketones, or distilled water, or a mixture of the solvent and distilled water, The pH adjusting agent in the second step of the organic-inorganic hybrid coating agent synthesis process is preferably any one of organic acids, inorganic acids, ammonium salts, amines or a mixture of two or more thereof.

In addition, the organic polymer resin of the third step of the organic-inorganic hybrid coating agent synthesis process, any one of an aqueous epoxy resin, modified epoxy resin, aqueous acrylic resin, modified acrylic resin, aqueous urethane resin, polyvinyl alcohol resin, polyamide resin or Preference is given to using mixtures of two or more thereof.

In addition, the curing agent of the fourth step of the organic-inorganic hybrid coating agent synthesis process, any one or two or more of aliphatic polyamine-based, acrylonitrile-modified amine, polyamide, amidoamine, dicyandiamide, amide resin, isocyanate, melamine It is preferable to use the mixed mixture.

According to the above-mentioned means for solving the problems, the present invention synthesizes a polysilicate compound having excellent hardness by using a sol coupling process of a silane coupling agent using a silicon-based colloidal silica and a metal alkoxide, which is a metal precursor, and has high material and adhesive strength and low surface energy. In addition, organic-inorganic hybrid functional coating agent is synthesized through hybrid process with organic polymer resin that is easy to clean the surface, and it is flexible through surface modification of material surface, and it is easy to remove contaminants and has excellent scratch resistance. It has the effect of providing a hard coating.

The present invention relates to a method for preparing a functional coating agent for removing contaminants and hard coatings using an organic-inorganic hybrid process, using a silicon-based colloidal silica and a metal alkoxide, which is a metal precursor, and a polysilicate compound having excellent hardness by a sol-gel process of a silane coupling agent. It is largely composed of a process of synthesizing a functional coating agent of organic-inorganic hybrid hard coating through a hybrid process with an organic polymer resin having high adhesion to the material, low surface energy, easy surface cleaning.

Thereby, there is an advantage of providing a hard coating agent having flexibility through surface modification of the material surface, easy to remove contaminants, and excellent scratch resistance.

Hereinafter will be described in more detail with respect to the present invention.

First, the process of synthesizing the polysilicate compound is a first step of mixing 10 to 30 parts by weight of silicon-based colloidal silica and 0.01 to 0.5 parts by weight of the acid metal catalyst to 10 to 80 parts by weight of the solvent and the first step A second step of stirring by adding 3-10 parts by weight of the metal alkoxide to the resultant, a third step of stirring by adding 10-30 parts by weight of the silane coupling agent to the resultant of the second step, and a stabilizer to the resultant of the third step And a fourth step of stirring by adding 0.1 to 1 parts by weight, and a fifth step of adding and stirring 0.1 to 3 parts by weight of a metal additive to the resultant of the fourth step.

The solvent of the first step of the polysilicate compound synthesis process is used alcohols, distilled water (D) or a mixture thereof. Herein, alcohols include ethanol (EtOH), isopropyl alcohol (IPA), methanol (MeOH), t-butyl alcohol (t-BA) and the like.

As the acid metal catalyst of the first step of the polysilicate compound synthesis process, any one of a metal phosphate catalyst, a metal hydrochloride catalyst, and a phosphoric acid-hydrochloric acid complex catalyst is used.

The solvent, the silicon-based colloidal silica and the acid metal catalyst are mixed in an appropriate amount, and stirred at a stirring speed of 100 to 200 rpm at a temperature of 30 to 50 ° C. for 10 to 20 minutes.

Then, a proper amount of the metal alkoxide is mixed with the resultant of the first step and stirred at a stirring speed of 100 to 200 rpm at a temperature of 30 to 50 ℃ for 10 to 20 minutes. Herein, the metal alkoxide may be silicon alkoxide (Si (OR) 4), zirconium alkoxide (Zr (OR) 4), titanium alkoxide (Ti (OR) 4) or aluminum alkoxide (Al (OR) 3). In one embodiment of the present invention, silicon alkoxide (Si (OR) 4, tetraosilicate) is used.

Then, a proper amount of the silane coupling agent is mixed with the resultant of the second step, and stirred at 200 to 500 rpm at a temperature of 30 to 80 ° C. for 20 to 180 minutes, and an appropriate amount of another type of silane coupling agent is mixed to 30 to 120 if necessary. Stir at 1000 rpm for 20 minutes at a temperature of 20-50 ° C.

Here, the silane coupling agent uses any one of alkoxy silane, alkyl silane, aminosilane, methoxysilane and methyl silane or a mixture of two or more thereof. In one embodiment of the present invention, methyltrimethoxysilane and 3-glucidoxitrimethylsilane are used together.

In addition, a proper amount of the stabilizer is mixed with the resultant of the third step and stirred at a temperature of 20-50 ° C. for 10-20 minutes. Here, the stabilizer uses any one of acetylacetone, ethyl acetoacetate, iron acetylacetone and alkanoneamine or a mixture of two or more thereof.

Then, by adding a metal additive for increasing the hardness to the resultant of the fourth step and stirred at a temperature of 20 ~ 50 ℃ 60-120 minutes. Here, the metal additive is an aluminum compound. In one embodiment of the present invention is used by mixing aluminum isopropoxide and aluminum chloride.

Through each of the above steps, an inorganic polysilicate compound having excellent hardness is synthesized by a sol-gel process of a silicon-based colloidal silica, a metal alkoxide, and a silin coupling agent.

Next, the organic-inorganic hybrid coating agent synthesis process, the first step of mixing and stirring 30 to 50 parts by weight of the polysilicate compound to 40 to 60 parts by weight of the solvent, 0.01 to 0.1 weight of the pH adjuster to the resultant of the first step A second step of mixing and stirring the part, and a third step of mixing and stirring 10-30 parts by weight of the curing agent to the resultant of the second step, and stirring by mixing 10-20 parts by weight of the organic polymer resin to the resultant of the third step A fourth step is performed.

The solvent of the first step of the organic-inorganic hybrid coating agent synthesis process is alcohol (ethanol (EtOH), isopropyl alcohol (IPA), methanol (MeOH), t-butyl alcohol (t-BA)), cellulsolves (butyl cellulose Solvent (BC), ethyl cellussolve (EC), ketones (methyl ethyl ketone (MEK), acetone (ACT) using a solvent selected from the group of one, distilled water (D), or using the solvent and distilled water In addition, an appropriate amount of the polysilicate compound is mixed with the solvent and stirred at 200 to 500 rpm at a temperature of 20 to 35 ° C. for 20 to 40 minutes.

Then, a proper amount of the pH adjuster is mixed with the resultant of the first step and stirred at 200-500 rpm at a temperature of 20-35 ° C. for 30-60 minutes. Here, the pH adjuster uses any one of organic acids, inorganic acids, ammonium salts, amines or a mixture of two or more thereof.

Then, an appropriate amount of the curing agent is mixed with the resultant of the second step, and stirred at 200 to 500 rpm at a temperature of 20 to 35 ° C. for 30 to 60 minutes. Herein, the curing agent may be an aliphatic polyamine-based, acrylonitrile-modified amine, polyamide, amidoamine, dicyandiamide, amide resin, isocyanate, melamine, or a mixture of two or more thereof.

Then, an appropriate amount of the organic polymer resin is mixed with the resultant of the third step, stirred at 200 to 500 rpm at a temperature of 20 to 35 ° C. for 60 to 120 minutes, and aged at a temperature of 60 ° C. for 2-3 days. Herein, the organic polymer resin may be any one or a mixture of two or more of an epoxy resin, a modified epoxy resin, an aqueous acrylic resin, a modified acrylic resin, an aqueous urethane resin, a polyvinyl alcohol resin, and a polyamide resin.

As a result, the organic-inorganic hybrid hard coating agent is provided through a hybrid process with an organic polymer resin having high adhesion to the material, low surface energy, and easy surface cleaning, thereby providing flexibility through surface modification of the material surface. It is easy to remove contaminants and provide an organic-inorganic hybrid hard coating agent having excellent functions such as scratch resistance.

Hereinafter, the present invention will be described with reference to the following table, and the physical properties of the coating agent will be evaluated accordingly. Examples 1 to 4 of the present invention are examples for the synthesis of polysilicate compounds, and Examples 5 to 8 are organic-inorganic groups of the polysilicate compounds synthesized in Examples 1 to 4 and the organic polymer resin. This is an example of hybridization.

Table 1-Polysilicate Compound Synthesis

<Table 2-Synthesis of Organic-Inorganic Hybrid Hard Coatings>

* Judging standard

(1) liquid stability

Evaluation of the liquid stability is required to evaluate the change over time at room temperature over time, to evaluate the liquid stability by conducting a harsh test of the coating liquid. Liquid stability was sampled in a 60ml container of the prepared coating liquid and stored in a 60 ℃ oven to confirm the change over time of the liquid. After 1 day at 60 ℃, it is considered to have stability at about room temperature for 1 to 3 months, and after 2 days at 60 ℃, it is considered to be about 3 to 6 months stability at about room temperature. After 3 days at 60 ℃, it was judged that the stability was about 6 to 9 months at about room temperature, the liquid stability criterion was determined that the stability was more than 3 days at 60 ℃ excellent stability. In the examples of the present invention, the liquid stability was found to be very good.

(2) Cross cut

The organic-inorganic hybrid hard coatings according to Examples 1 to 8 were coated on a stainless steel (No. 201) steel plate having a size of 0.5 mm and a size of 7 cm x 7 cm, respectively, using 2000 rpm and a 15 second spin coating method. The heat treatment was performed for about 10 minutes in the furnace, and the heat treatment was performed for 8 minutes in the furnace at 170 ° C. Then, by cooling naturally at room temperature to form an organic-inorganic hybrid functional hard coating film.

A lattice-shaped cut is performed on the coated sample so that it is equilibrium with a sharp blade at 90 degrees. At this time, the interval is 1mm. Gently shake off the specimen using a soft brush in each direction of the grid form, place the tape in the center of the grid in the direction parallel to the cutout, and at least 20 mm long. Ensure strong contact with the coating. The adhesive tape is held at an angle of 60 ° after 5 minutes and quickly pulled off. The criterion of the discrimination is that a good cut surface is intact and no one is dropped. Usually, the middle of the cut surface is determined to fall into a small mass. The damaged part was peeled off within 5% of the area, the middle or edge of the cut edge, and the damaged part was cut off within 5 ~ 35%, the peeled off on the middle or edge of the bad cut edge, and the damaged part was 35% or more. . In the examples of the present invention, the adhesion was found to be very good.

(3) boiling resistance

As a method for evaluating the thermal stability of the coated sample surface, it is evaluated that the properties that do not change well even when immersed in boiling water (98 ℃, boiling water). Dip the specimen into boiling water and examine the coating film for presence and extent of wrinkles, cracks, swelling, peeling, reduction of gloss, cloudiness, whitening, and discoloration. The specimens are immersed in boiling water at 98 ° C for 1 hour. The criteria for evaluation are determined based on how much variation in the above conditions has occurred. In Example 7 of the present invention, the boiling resistance was found to be very good.

(4) corrosion resistance

Corrosion resistance test is the most frequently used reliability evaluation method for the coating sample, the corrosion resistance salt spray test method. This test method is the most basic test for producing products that are well adapted to the global climatic environment. The test method evaluates the resistance to airtightness, discoloration, corrosion, etc. in the cracks and cracks for product defects, and high salt water. It is resistant to the spray atmosphere and is intended to evaluate the storage stability of the coated product. The corrosion resistance (salt spray) test is based on the brine concentration of 5%, temperature 35 ℃, and time of 72 hours to evaluate the durability of the distribution conditions and handling process, and evaluates the pin hole of the coated surface, the swelling and corrosion of the coated surface. In Example 7 of the present invention, corrosion resistance was found to be very good.

(5) chemical resistance test

In order to evaluate the chemical resistance of the coated specimen, put the coated specimen in a solution prepared with 5% Na ₂ CO ₃ (alkali resistance) 5% CH ₃ COOH (acid resistance), and the coated specimen was immersed in at least 50%. Leave on for 24 hours each. After the test, the specimen is taken out and washed with running water to evaluate the swelling and discoloration of the coating film. In Example 7 of the present invention, the chemical resistance was found to be very good.

(6) pencil hardness

To evaluate the pencil hardness in order to evaluate the hardness of the coated specimens, a 1Kg load was performed. The evaluation was made by inserting the pencil into the device at 45 ° angle for each hardness. When three or more were drawn by drawing five lines, the evaluation criteria were satisfied as pencil hardness. All of the examples of the present invention were found to satisfy the pencil hardness.

(7) fingerprint removal of contaminants

In order to evaluate the easy cleaning properties of the coated specimens, the coated specimens were stained with contaminants (fingerprints) and cleaned three times, five times, and ten times using a tissue (Kims Wiper, Kims Wipe). When the fingerprint was erased less than three times, the easy cleaning property was evaluated as being very good, and in Examples 6 and 7 of the present invention, it was possible to remove contaminants in less than three times, which was very good.

As described above, the organic-inorganic hybrid hard coating agent according to the present invention has good liquid stability, pencil hardness, boiling resistance, cross cut, 90 degree bending, chemical resistance, corrosion resistance, and dirt removal (easy cleaning). In particular, in the case of Example 7, all the properties were very good, it was possible to provide a functional organic-inorganic hybrid hard coating.

Claims (11)

10 to 30 parts by weight of the silicon-based colloidal silica and 0.01 to 0.5 parts by weight of the acid metal catalyst are mixed with 10 to 80 parts by weight of the solvent, and 3 to 10 parts by weight of the metal alkoxide is added to the resultant of the first step. A second step of stirring, a third step of stirring by adding 10 to 30 parts by weight of a silane coupling agent to the resultant of the second step, and a fourth step of adding and stirring 0.1 to 1 part by weight of a stabilizer to the resultant of the third step A polysilicate compound synthesis process comprising a step and a fifth step of stirring by adding 0.1 to 3 parts by weight of a metal additive to the resultant of the fourth step;
A first step of mixing 30-50 parts by weight of the polysilicate compound to 40 to 60 parts by weight of a solvent, and a second step of mixing and mixing 0.01 to 0.1 parts by weight of a pH adjuster to the resultant of the first step, and the second step Organic-inorganic hybrid coating agent comprising a third step of mixing and stirring 10-30 parts by weight of the curing agent to the result of the second step, and a fourth step of mixing and stirring 10-20 parts by weight of the organic polymer resin to the resultant of the third step Synthesis process; The organic-inorganic hybrid hard coating method characterized in that consisting of. The method of claim 1, wherein the solvent of the first step of the polysilicate compound synthesis process is alcohol or distilled water. The method of claim 1, wherein the acid metal catalyst of the first step of the polysilicate compound synthesis process is any one of a metal phosphate catalyst, a metal hydrochloride catalyst, and a phosphoric acid-hydrochloric acid combined catalyst. . The organic-inorganic hybrid hard according to claim 1, wherein the metal alkoxide of the second step of the polysilicate compound synthesis process is any one of silicon alkoxide, zirconium alkoxide, titanium alkoxide and aluminum alkoxide or a mixture of two or more thereof. Method of producing a coating agent. The silane coupling agent of the third step of the polysilicate compound synthesis process is any one of alkoxy silane, alkyl silane, aminosilane, methoxysilane and methylsilane or a mixture of two or more thereof. Method for producing an organic-inorganic hybrid hard coating agent. According to claim 1, wherein the stabilizer in the fourth step of the polysilicate compound synthesis process is any one or a mixture of two or more of acetylacetone, ethyl acetoacetate, iron acetylacetone and alkanoneamine, organic-inorganic Method for producing a hybrid hard coating agent. The method of claim 1, wherein the metal additive of the fifth step of the polysilicate compound synthesis process is an aluminum compound. The method of claim 1, wherein the solvent of the first step of the organic-inorganic hybrid coating agent synthesis process using a solvent selected from any one of alcohols, cellulsolves, ketones, or distilled water, or a mixture of the solvent and distilled water Method for producing an organic-inorganic hybrid hard coating agent, characterized in that. The method of claim 1, wherein the pH adjusting agent of the second step of the organic-inorganic hybrid coating agent synthesis process of any one of organic acids, inorganic acids, ammonium salts, amines or a mixture of two or more thereof, the production of organic-inorganic hybrid hard coating agent Way. According to claim 1, wherein the curing agent of the third step of the organic-inorganic hybrid coating agent synthesis process any one of aliphatic polyamine-based, acrylonitrile-modified amine, polyamide, amidoamine, dicyandiamide, amide resin, isocyanate, melamine Or a method for producing an organic-inorganic hybrid hard coating agent, characterized in that a mixture of two or more thereof. The organic polymer resin of the fourth step of the synthesis process of the organic-inorganic hybrid coating agent is an aqueous epoxy resin, a modified epoxy resin, an aqueous acrylic resin, a modified acrylic resin, an aqueous urethane resin, a polyvinyl alcohol resin, a polyamide resin. Method for producing an organic-inorganic hybrid hard coating agent, characterized in that any one or a mixture of two or more thereof.