KR20020034657A - Methods for preparing organic-inorganic hydrid, hard coating liquid comprising the same, and hard coating thin film using the same - Google Patents

Abstract

PURPOSE: Provided is an organic sulfur-silicon oxide hybrid, a hard coating liquid containing the same, and a method for forming a thin film of hard coating using the same. CONSTITUTION: The organic sulfur-silicon oxide hybrid is prepared by the step of urethane-reacting organic sulfur compound selected from the group consisting of organic sulfur compound having at least difunctional thiol group(-SH) at its ends, organic sulfur compound having at least monofunctional thiol group(-SH) and at least monofunctional hydroxyl group(-OH), and aromatic organic sulfur compound having at least monofunctional thiol group(-OH), aromatic group and at least monofunctional hydroxyl group(-OH) with alkoxysilane compound having isocyanate group(-NCO) in its molecule in the presence of catalyst.

Description

Organic sulfur-silicon oxide hybrid, a hard coating solution comprising the same, and a method for producing a hard coating thin film using the same

The present invention relates to a method for producing a transparent thin film having chemical resistance and high tangerine index. More specifically, the present invention provides a method for preparing an organic sulfur-silicon oxide hybrid, a hard coating solution including the same, and a method for manufacturing the same, and a hard coating thin film having excellent surface hardness, chemical resistance, transparency, and high refractive index. It relates to a manufacturing method.

Optical plastic material has the advantages of being light in weight, easy to process, and easy to impart desired functionality and workability. However, the insufficiency of weather resistance and chemical resistance, which is a limitation of plastic products, acts as a limiting factor in using plastic materials as optical component materials such as glasses. To compensate for this, hard coatings have been introduced to plastic surfaces in earnest since the 1970s, which resulted in overcoming the range and limitations of plastic materials. In particular, as the control of the sol-gel hybrid process and the commercialization of the product using the same have been possible since the 1980s, organic-inorganic hybrid hard coating having a basic skeleton of silicon oxide has been used as an optical plastic material.

Recently, these optical plastic materials have been developed in the direction of higher functionality and characteristics, and the refractive index of the optical plastic material is starting at 1.50 at the beginning and is currently showing a high refractive index of 1.60, 1.64 or more. However, the improvement of weather resistance and chemical resistance of plastic materials does not keep pace with increasing refractive index of the materials.

Recently, optical products made of plastic materials such as lenses, filters, and other transparent parts are replacing conventional glass optical materials due to their excellent impact resistance, light weight of the material, and easy functionality. Moreover, plastic lenses and transparent optical parts are being improved in a direction that can exhibit higher refractive indices having the same optical properties even at a thinner thickness for weight reduction. In general, interference is known to occur more severely as the difference in refractive index between two adjacent materials is increased, and the high refractive index plastic optical material of the old type has been released as a product having a refractive index of 1.60 or more. Since silicon oxide alone is not expected to have a refractive index of 1.50 or more, introduction of a hybrid system of organic-inorganic materials that can increase the refractive index has been studied.

Conventional techniques for increasing the refractive index of hard coatings include nano-sized metal oxides such as iron oxides, titanium oxides, zirconium oxides, antimony oxides, zinc oxides, tin oxides, and mixtures thereof. Increasing the refractive index through the sol-gel process involving hydration and condensation reaction, and -O-, CO-O-, SS, -CO-S- and -CS-S- groups in the center chain of organic compounds It has a -SH group or -OH group which is reactive at the end thereof, and chemically reacts a material having at least one unsaturated group with a silicon compound having an epoxy functional group. There is a method for preparing a coating liquid.

US Pat. Nos. 5,654,090 and 5,858,077 disclose methods for producing high refractive index hard coatings using nanoparticles or organic compounds of metal oxides. However, the conventional high refractive index coating liquid manufacturing method is expensive raw materials, the coating liquid made by the sol-gel method using the same has a short storage period. In addition, in the case of using a metal oxide, the size control is difficult to control because it is controlled from a few hundred nanometers to several microns, and there is a disadvantage in that the light transmittance is lowered due to scattering of light. This may act as a fatal disadvantage when applying an optical product that requires a high degree of transparency. In addition, in the case of using the organic compound, there is a disadvantage in that the degradation in the weather resistance and surface hardness occurs, there is a problem in terms of adjusting the refractive index and transparency, high hardness, weather resistance and work efficiency.

Therefore, there is a demand for a method of manufacturing a hard coating having excellent surface hardness, chemical resistance, and transparency, and having an optically high refractive index.

The present invention is to solve the above problems, the present invention is to provide a method for producing an organic sulfur-silicon oxide hybrid.

In addition, an object of the present invention is to provide a method for producing a hard coating solution from the organic sulfur-silicon oxide hybrid prepared according to the above method and a hard coating solution prepared according to the method.

In addition, an object of the present invention is to provide a method for forming a hard coat thin film using the hard coating solution.

In order to achieve the above object, the present invention,

An organosulfur compound having a bifunctional or higher thiol group (-SH) at its terminals, an organosulfur compound having at least one functional thiol group (-SH) and at least one functional hydroxyl group (-OH), and at least one functional thiol group ( -SH), an organic sulfur compound selected from the group consisting of an aromatic group and an aromatic organic sulfur compound having at least one hydroxyl group (-OH) and an alkoxy silane compound having an isocyanate group (-NCO) in a molecule under a urethane It provides a method for producing an organic sulfur-silicon oxide hybrid comprising the step of reacting.

The present invention also provides a) an organosulfur compound having a bifunctional or higher thiol group (-SH), an organosulfur compound having one or more functional thiol groups (-SH) and at least one hydroxyl group (-OH), And an organic sulfur compound and an isocyanate group (-NCO) selected from the group consisting of at least one functional thiol group (-SH), an aromatic group and an aromatic organosulfur compound having at least one functional hydroxyl group (-OH). Urethane reacting an alkoxy silane compound under a catalyst to produce an organosulfur-silicon oxide hybrid; b) hydrolysis and partial condensation reaction by adding an alkoxysilane and a hydrolysis catalyst to the organosulfur-silicon oxide hybrid prepared in step a); And c) adding a solvent and a curing catalyst to the reaction product obtained in step b) to prepare a hard coating solution.

The present invention also provides an organic-inorganic hybrid hard coating solution prepared according to the above method.

The present invention also provides a) an organosulfur compound having a bifunctional or higher thiol group (-SH), an organosulfur compound having one or more functional thiol groups (-SH) and at least one hydroxyl group (-OH), And an organic sulfur compound and an isocyanate group (-NCO) selected from the group consisting of at least one functional thiol group (-SH), an aromatic group and an aromatic organosulfur compound having at least one functional hydroxyl group (-OH). Urethane reacting an alkoxy silane compound under a catalyst to produce an organosulfur-silicon oxide hybrid; b) hydrolysis and partial condensation reaction by adding an alkoxysilane and a hydrolysis catalyst to the organosulfur-silicon oxide hybrid prepared in step a); c) preparing a hard coating solution by adding a solvent and a curing catalyst to the reaction product obtained in step b); d) coating the organic-inorganic hybrid hard coating solution prepared in step c) on a transparent plastic material; e) drying the coating prepared in step d); And f) provides a method for producing a high refractive index transparent hard coating thin film comprising the step of curing the coating dried in step e).

Hereinafter, the present invention will be described in detail.

A first aspect of the invention relates to a method for producing a hybrid of organosulfur-silicon oxides.

The method consists of urethane reacting an organic sulfur compound and an alkoxy silane compound having an isocyanate group (-NCO) in the molecule under a catalyst.

The organosulfur compound has a high refractive index characteristic, and has an organosulfur compound having at least two functional thiol groups (-SH), at least one functional thiol group (-SH) and at least one functional hydroxyl group (-OH) An organosulfur compound and an aromatic organosulfur compound having at least one functional thiol group (-SH), an aromatic group and at least one functional hydroxyl group (-OH). Examples of the organosulfur compound having two or more functional thiol groups (-SH) at the terminals include 2-mercaptoethylsulfide, and the like. One or more functional thiol groups (-SH) and one or more functional hydroxyl groups Examples of the organosulfur compound having (-OH) include 4-mercapto-2-butanol, 2-mercaptoethanol, and 11-mercapto-1-undecanol C2-C11 mercapto alcohols, such as (11-mercapto-1-undecanol), etc., and have one or more functional thiol group (-SH), an aromatic group, and one or more functional hydroxyl group (-OH) Examples of the aromatic organosulfur compound include 2-mercaptobenzyl alcohol and the like.

The alkoxy silane having the isocyanate group (-NCO) in a molecule has a chemical reactivity with the organic sulfur compound, for example Isocyanatopropyltrimethoxysilane ( -isocyanatopropyltrimethoxysilane). The isocyanate group of the alkoxy silane forms a chemical bond with the organic sulfur compound through a urethane reaction with a thiol or hydroxy group of the organic sulfur compound.

The equivalent ratio of the thiol (-SH) and / or hydroxy (-OH) functional group to the isocyanate (-NCO) functional group is preferably 1.0: 1.2 to 1.0: 2.0. This is to prevent sedimentation and abrasion resistance of the coating liquid that may occur during the preparation of the coating liquid from the hybrid due to the remaining of the reactor of the organic material having a high refractive index characteristic.

The catalyst is selected from dibutyltindiraurate, dibutyltindibromide, dibutyltindichloride, or 1,4-diazabicyclo [2,2,2] octane, preferably Is dibutyl tin dichloride or 1,4-diazabicyclo [2,2,2] octane. The catalyst is preferably used in an amount of 0.001 to 1.000% by weight based on solids relative to the total reactants.

A second aspect of the invention relates to a method of preparing an organic-inorganic hybrid hard coating solution.

The method comprises the steps of a) preparing an organosulfur-silicon oxide hybrid according to the first aspect of the invention; b) hydrolysis and condensation reaction by adding an alkoxysilane and a hydrolysis catalyst to the organosulfur-silicon oxide hybrid prepared in step a); And c) adding a solvent and a curing catalyst to the reaction product obtained in step b) to prepare a hard coating solution.

Step a) is carried out as described in the first aspect of the invention.

The organic sulfur-silicon oxide hybrid is preferably used in an amount of 0.5 to 50% by weight based on the solid component with respect to the total reactant.

In the organic sulfur-silicon oxide hybrid, a component having a high refractive index is an organic substance having a hydroxy or thiol group at the terminal, and among these, a sulfur component is used to increase the refractive index. For example, 2-mercaptoethyl sulfide has a very high self refractive index of 1.5961. The organic material exhibiting high refractive index is mainly bifunctional or tetrafunctional having both ends substituted with thiol groups. To obtain a very high refractive index of 1.64 or more, it is preferable to use a bifunctional or less than bifunctional, and a refractive index of 1.58 or more is about 1.64. In order to obtain high abrasion resistance, which is the main physical property of the hard coating, it is preferable to use a trifunctional or more than one.

Step b) is a step of preparing an alkoxysilane condensate by adding an alkoxy silane to the urethane-reacted organic-inorganic hybrid under a hydrolysis catalyst.

The alkoxy silane is represented by the following general formula:

R _X Si (OR ') _4-X

(Wherein R is an alkyl group of C _1-5 , an aromatic group such as phenyl, a vinyl group, an acryl or methacryl group, an epoxy group, an amino group, a mercapto group or a hydroxyl group, R 'is an alkyl group of C _1-5 , x Determines the number of functional groups in the alkoxy silane.)

Generally the alkoxy silane has a structure of R ₂ Si (OR ′) ₂ or RSi (OR ′) ₃ . The number of R groups is 2 can be used to reduce the crosslinking density of the coating film to give flexibility. In this invention, it is preferable to use the trialkoxysilane whose R is 1 which can maintain abrasion resistance of a coating film.

Examples of the alkoxy silane include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, acryloxypropyltrimethoxysilane, methacryloxytrimethoxysilane, -Glydoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) propyl trimethoxysilane, Mercaptopropyltrimethoxysilane, phenyltrimethoxysilane, Isocyanatopropyltrimethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, -Glycidoxy propyl dimethyl methoxysilane, -Glydoxypropyltrimethoxysilane or β- (3,4-epoxycyclohexyl) propyl trimethoxysilane is preferred.

The alkoxysilane participates in the reaction for preparing the coating solution by forming a colloidal particle of partial condensate or tens of hundreds of nanoscales by a sol-gel process that causes a hydration reaction and a partial condensation reaction. As described above, the alkoxy silane forming the tens-hundreds of nanoscale colloidal particles or the partial condensate is preferably used in an amount of 15 to 95% by weight based on the solid component.

In step b), the hybrid of the organosulfur-silicon oxide participates in the hydration reaction and partial condensation reaction of the alkoxysilane, so that the reaction product has an inorganic bond of silicon oxide. The alkoxysilane is formed from a trialkoxysilane having a structure of RSi (OR ') ₃ through a hydration reaction to form RSi (OH) ₃ under an acid catalyst, and at the same time, the urethane-reacted alkoxy silane is also simultaneously hydrated to form R "Si (OH) _3. And form a condensed material to obtain a partially condensed material.

As the hydrolysis catalyst used in step b), an aqueous hydrochloric acid solution from 0.001 N to 1.20 N may be used.

Step b) is preferably carried out at 20 to 80 ℃ for 2 to 30 hours.

Step c) is a step of preparing a hard coating solution by adding a solvent and a curing catalyst to the reaction product obtained in step b).

As the solvent, an alcohol component is preferable. Since the alkoxy group liberated through the hydration reaction in the step b) is present in the coating solution, the same component is also preferred for forming a coating solution.

As the curing catalyst, ammonium acetate, aluminum acetylacetonate, dimethylamine, tetrabutyl ammonium acetate, tin octylate, and the like may be used, which is 0.001 to 1.000% by weight of solids based on the total reactants. It is preferable to use as.

In step c), auxiliary additives of other curing reactions may be added. Diacids and dicyandiamides such as maleic anhydrie, itaconic acid, phthalic anhydride, adipic acid, etc. may be used as auxiliary additives. It is preferably added in an amount of 1.00 to 10.00 wt% based on the solid component with respect to the total reactants. The auxiliary additive functions to improve physical properties by increasing the hardness and crosslinking density of the cured surface.

It is preferable to add and mix the curing catalyst and other additives and stir for 5 to 48 hours to achieve a uniform composition.

A third aspect of the present invention relates to a hard coating liquid composition prepared according to the second aspect of the present invention.

Hard coating solution is basically excellent storage stability when stored at 5 ~ 20 ℃ low viscosity and sol size should not increase more than a certain level during storage, there is little change in color, precipitation and phase separation of certain components such as high refractive index There should be no.

In the present invention, as described in the second aspect of the present invention, alkoxysilane is added to the urethane-reacted organic-inorganic hybrid, and a hydrolysis catalyst is added to the hydrolysis and partial condensation reaction, followed by a solvent and a curing catalyst. By preparing a coating liquid by adding the, it is possible to obtain the physical properties of the required hard coating liquid.

The coating liquid of the present invention has a pH range of 3.0 to 5.0.

Conventional high refractive index hard coating liquids have problems such as precipitation and turbidity of liquids, abrasion resistance reduction, and shortening of storage time when manufactured using metal oxide fine particles, and are prepared by reaction with a silane having an epoxy reactor. In this case, it is difficult to control the reaction and has a limit of refractive index adjustment. In the present invention, however, the organic-inorganic hybrid is prepared through a urethane reaction, and the content of the coating liquid is adjusted to 0.5 to 50% by weight based on the solid component, thereby controlling the film refractive index freely from 1.58 to 1.70 without changing over time or abrasion resistance. While the coating film can be prepared.

The fourth aspect of the present invention relates to a method for producing a high refractive index transparent hard coat thin film using the hard coating liquid prepared according to the second aspect of the present invention.

The method comprises the steps of a) -c) preparing an organic-inorganic hybrid hard coating solution according to the second aspect of the present invention; d) coating the organic-inorganic hydride hard coating solution prepared in step c) on a transparent plastic material; e) drying the coating prepared in step d); And f) curing the coating dried in step e).

Steps a) to c) may be performed as described in the second aspect of the present invention.

Coating in step d) may be performed by dip coating, flow coating or spin coating.

The drying of step e) is carried out for 5 to 15 minutes at a temperature of 50 to 90 ℃, the curing of the step f) is preferably carried out for 30 to 120 minutes at a temperature of 80 to 125 ℃.

According to the above method, a transparent hard coat thin film having a film refractive index of 1.58 to 1.70 may be manufactured.

In addition, since the high refractive index hard coating thin film prepared according to the above method has a high elastic urethane bond in the molecule, it has excellent impact resistance even without organic primer coating treatment, and since it contains a regulated organic reactor in the molecule, a dye pointed out as a disadvantage after hard coating And it is possible to solve the difficulty of coloring by the pigment.

The high refractive index transparent thin film may be applied to transparent plastic lens protective windows such as digital cameras, camcorders, glasses, telescopes, microscopes, and the like, which require high refractive index and hard coating properties, and other optical materials. In addition, surfactants, UV absorbers, antioxidants, leveling agents, chelating agents and the like may be added to improve the performance of the coating and to ensure applicability to the applied material.

The advantages of the present invention can be summarized in three broad ways. First, it can overcome the limitation of use as an optical material such as interference due to the difference in refractive index with the coating material. Second, by using it as a coating agent for optical lenses and other plastic optical materials requiring high functionality, the weight of the products to which they are applied And cost reduction, and third, can improve the weather resistance and durability of the high-performance transparent plastic material.

Hereinafter, the present invention will be described with reference to the following examples. However, these examples are only for illustrating the present invention, but the present invention is not limited thereto.

Example 1

Step 1: Reaction of Alkoxysilane with Isocyanate Group with Organosulfur Compound with High Refractive Index

136 g of _2- mercaptobenzyl alcohol (HSC ₆ H ₄ CH ₂ OH) were added to the reactor, 0.001 g of dibutyl tin dilaurate was added thereto, followed by stirring. 540 g of isocyanatopropyltrimethoxysilane was added dropwise over 10 minutes to 30 minutes, and then reacted at 40 to 80 ° C. for 30 minutes to 90 minutes, followed by cooling to obtain a reaction product.

Step 2: Hydration and Partial Condensation of Organic Reactant with High Refractive Index and Alkoxysilane

50 g of the reaction product produced in step 1 was taken and added to a reactor maintained at 20 to 30 ° C., 200 g of β- (3,4-epoxycyclopexyl) propyltrimethoxysilane were added to the same reactor, followed by stirring. 25 g of 0.001 N aqueous hydrochloric acid solution was added dropwise over 10 to 30 minutes, and then reacted at 40 to 80 ° C. for 30 minutes to 4 hours, followed by cooling to obtain a reaction product.

Step 3: Synthesis of Optical Hard Coating Solution Having High Refractive Index and Preparation of Hard Coating Film

The reaction product produced in Step 2 was maintained at 20 to 30 ° C., and 10-50% of the hydrated and partially condensed reaction tetraethoxysilane and 50 g of ethanol solution were added to the same reactor, followed by stirring with 100 g of methanol and methyl ethyl. After adding 10 g of ketone and 0.5 g of diacetone alcohol and stirring for 4 hours, 0.5 wt% of aluminum acetylacetonate was added thereto, followed by stirring for 1 hour, thereby obtaining a final composition. Then, it was coated with a poly (diethyleneglyc olbisallyl) carbonate (poly (diethyleneglyc olbisallyl) carbonate) material by immersion method and dried first at 65 ° C. for 20 minutes and then cured at 100 ° C. for 2 hours to form a coating film. Experiments and the results are shown in Table 1 below.

Example 2

5 wt% of itaconic acid and 1 wt% of dicyandiamide were added to the highly refractive transparent thin film composition synthesized in the same manner as in Example 1 to obtain a final composition, and then coated to form a coating film. Experiments and the results are shown in Table 1 below.

Example 3

240 g of pentaerythriytoltetrakis (3-mercaptopropionate) was added instead of 2-mercaptobenzyl alcohol in the reaction step 1 of Example 1. The reaction was carried out in the same manner as in Example 1 except for the addition of the additive of Example 2 to obtain a final composition and coating to form a coating film to test the physical properties and the results are shown in Table 1 below.

Experimental Example

Measurement of the physical properties of the coating film prepared in the embodiment of the present invention was performed by the following method.

1) scratch test

In a scratch experiment using # 0000 steel wool, the steel wool was cut to a size of 2.5 cm in width and contacted the test specimen with a load of 100 g, and rotated five times, and then visually observed.

AAA: No concentric scratches due to steel wool

AA: One to two concentric win scratches with steel wool

A: Less than 5 concentric win scratches with steel wool

B: One or less concentric winks with steel wool are observed in a circular pattern.

C: Two or more concentric win scratches were observed in a circular pattern by steel wool.

2) Adhesion Test [ASTM D3359-87]

2, a cellophane tape having excellent adhesive force thereon created 100 a column of 1mm X 1mm draw knife with a horizontal and vertical 11 line so that it reaches up to the 1mm gap material on the transparent coating film cured difference in the angle of putting a sudden 180 ^o Removed close. This was repeated three times at the same location.

5B: No coating film falling off the cut edges, no coating film peeling in the lattice

4B: Deterioration of the edge is weakly observed and peeling is performed within 5% of the total.

Rising up

3B: Peeling and brittleness of edges is observed and peels within 15%

2B: Peeling and chipping are seen even within the lattice and peels within 35%

1B: Large ribbon peeling is observed and peeled at 35% ~ 65%

0B: Peeled at an area of 65% or more. Poor adhesion.

3) Hot Water Resistance Test

After dipping the specimen in which the coating film was formed in distilled water boiled at 100 °, immersed for 15 minutes, and taken out and dried, the water resistance was evaluated according to the ASTM D3359-87 method. The evaluation method is the same as the adhesion test.

4) Impact resistance test

The impact resistance was evaluated by dropping a steel ball having a diameter of 150 mm and a diameter of 20 g at a height of 150 cm at a temperature of 150 cm at room temperature. The same specimen was repeated three times.

O: No cracks or penetrations

X: Cracks or penetrates

5) Transmittance Test

Based on the uncoated specimens, the transmittance was measured with a spectrophotometer, and based on this, the transmittance of the coated specimen was measured.

6) Refractive Index Measurement Experiment [ASTM F576-95]

The refractive index of the coating film rotated on the silicon wafer was measured by using the Ellipsometry method of ASTM F576-95 method.

7) Chromaticity Experiment

Apply 10% BPI to the coated specimen ^. After dipping for 5 minutes at 96 ℃ in a black solution (distillation shoe) and its light transmittance was measured.

8) Pencil Hardness Experiment [ASTM D3363-74]

When the pencil was placed at a 45 ^° angle on the plane of the coated specimen and pushed with a constant force, the hardness of the pencil was determined as the hardness of the surface when the scratched pattern or the coating film was not broken more than twice.

TABLE 1

division Standard material (no coating) Example 1 Example 2 Example 3 1) scratch C A AA AAA 2) Adhesion - 5B 5B 5B 3) hot water resistance - 5B 5B 5B 4) Impact resistance X O O O 5) Transmittance 85.0 (% T) 92.0 (% T) 91.5 (% T) 92.1 (% T) 6) refractive index - 1.674 1.658 1.612 7) coloring 60.0 (% T) 56.0 (% T) 62.0 (% T) 63.0 (% T) 8) Pencil Hardness HB 3H 4H 5H

As shown in Table 1, the high refractive index hard coated transparent thin film manufactured by the present invention has a refractive index of 1.60 to 1.70, shows a hardness of 3 to 5 H pencil hardness when a plastic material is applied, and a hard coated transparent thin film of optical plastic When applied as a composition, there is no interference due to the difference in refractive index with an excellent light transmission effect of 90% or more, and excellent hardness can be obtained to maintain physical stability of the material surface.

As described above, the present invention has a high refractive index and at the same time has the effect of providing a composition and a transparent thin film to form a transparent thin film excellent in chemical resistance, adhesion, transparency and hardness, and additionally the anti-shock effect in the coating film There is also a coloring effect after coating.

Claims (17)

An organosulfur compound having a bifunctional or higher thiol group (-SH) at its terminals, an organosulfur compound having at least one functional thiol group (-SH) and at least one functional hydroxyl group (-OH), and at least one functional thiol group ( -SH), an organic sulfur compound selected from the group consisting of an aromatic organic sulfur compound having an aromatic group and at least one hydroxyl group (-OH) and an alkoxy silane compound having an isocyanate group (-NCO) in a molecule under a urethane Method for producing an organic sulfur-silicon oxide hybrid comprising the step of reacting. The method of claim 1, wherein the equivalent ratio of thiol (-SH) and / or hydroxy (-OH) functional groups to isocyanate (-NCO) functional groups is 1.0: 1.2 to 1.0: 2.0. The method of claim 1, wherein the catalyst is dibutyltindichloride or 1,4-diazabicyclo [2,2,2] octane. The process according to claim 1, wherein the catalyst is used in an amount of 0.001 to 1.000% by weight based on solids relative to the total reactants. a) an organosulfur compound having at least two functional thiol groups (-SH), an organosulfur compound having at least one functional thiol group (-SH) and at least one hydroxyl group (-OH), and at least one functional thiol Catalyzes an organic sulfur compound selected from the group consisting of an aromatic organic sulfur compound having a group (-SH), an aromatic group and at least one hydroxyl group (-OH) and an alkoxy silane compound having an isocyanate group (-NCO) in a molecule Urethane reaction to prepare an organosulfur-silicon oxide hybrid; b) hydrolysis and partial condensation reaction by adding an alkoxysilane and a hydrolysis catalyst to the organosulfur-silicon oxide hybrid prepared in step a); And c) preparing a hard coating solution by adding a solvent and a curing catalyst to the reaction product obtained in step b). Method of producing an organic-inorganic hybrid hard coating solution comprising a. 6. The method of claim 5, wherein in step b), the organosulfur-silicon oxide hybrid is used in an amount of 0.5 to 50% by weight, based on solid components relative to the total reactants. 6. The process of claim 5, wherein in step c), the alkoxy silane partially condensed in step b) is used in an amount of from 15 to 95% by weight, based on the solid components relative to the total reactant. 6. The process of claim 5, wherein in step b) the alkoxysilane is Glycidoxypropyltrimethoxysilane ( -glycidoxypropyltrimethyoxysilane) or β- (3,4-ethoxycyclohexyl) propyltrimethoxysilane (β- (3,4-epoxycyclohexyl) propyltrimethoxy silane). 6. The process according to claim 5, wherein the hydrolysis catalyst in step b) is hydrochloric acid. 6. The method according to claim 5, wherein the solvent in step c) is an alcohol. 6. The method of claim 5, wherein the curing catalyst in step c) is aluminum acetylacetonate, tetrabutylammonium acetate or ammonium perchlororate. 12. The process according to claim 11, wherein in step c) the curing catalyst is used in an amount of 0.001 to 1.000% by weight, based on solids relative to the total reactants. 6. The method of claim 5, wherein in step c), an auxiliary additive selected from the group consisting of maleic anhydride, itaconic acid, phthalic anhydride, adipic acid, dicyandiamide and mixtures thereof is added. . The method of claim 13, wherein the auxiliary additive is used in an amount of 1.00 to 10.00 weight percent based on solids relative to the total reactants. An organic-inorganic hybrid hard coating solution prepared according to any one of claims 5 to 14. a) an organosulfur compound having at least two functional thiol groups (-SH), an organosulfur compound having at least one functional thiol group (-SH) and at least one hydroxyl group (-OH), and at least one functional thiol Catalyzes an organic sulfur compound selected from the group consisting of an aromatic organic sulfur compound having a group (-SH), an aromatic group and at least one hydroxyl group (-OH) and an alkoxy silane compound having an isocyanate group (-NCO) in a molecule Urethane reaction to prepare an organosulfur-silicon oxide hybrid; b) hydrolysis and partial condensation reaction by adding an alkoxysilane and a hydrolysis catalyst to the organosulfur-silicon oxide hybrid prepared in step a); c) preparing a hard coating solution by adding a solvent and a curing catalyst to the reaction product obtained in step b); d) coating the organic-inorganic hybrid hard coating solution prepared in step c) on a transparent plastic material; e) drying the coating prepared in step d); And f) curing the coating dried in step e) Method for producing a high refractive index transparent hard coating thin film comprising a. The method of claim 15, wherein the film thickness of the hard coating thin film is 1.58 to 1.70.