KR20190053071A - Organic-inorganic hybrid material coating agent, method for manufacturing the same and coating agent composition comprising the same - Google Patents

Abstract

The present invention relates to an organic-inorganic hybrid coating agent, capable of generally exhibiting excellent physical properties, a preparing method thereof, and a coating agent composition including the same. The organic-inorganic hybrid coating agent of the present invention comprises: a glycidyl group-containing ether-based compound in the presence of an acid catalyst; a carboxyl group-containing compound; a silane compound; and a primary reactant.

Description

TECHNICAL FIELD The present invention relates to a high-flash point / high weather-resistant organic-inorganic hybrid coating agent, a method for producing the same, and a coating composition containing the same. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to an organic-inorganic hybrid coating material having a high flash point / high weather resistance combined with an organic material and an inorganic material, a process for producing the coating material, and a coating composition comprising the coating material.

In general, organic coating agents include epoxy-based coating agents, urethane-based coating agents, and acrylic-based coating agents. However, the organic coating agent has a limitation in obtaining physical properties such as surface hardness, abrasion resistance, chemical resistance, stain resistance, and heat resistance beyond a required level.

As a result, an organic-inorganic hybrid coating agent exhibiting superior physical properties than the organic coating agent has been developed (see Patent Literature). Although the organic-inorganic hybrid coating exhibits excellent physical properties as compared with the organic coating, there is a problem that the weatherability is low and the flammability is high due to limitations of the raw material itself and the manufacturing process. In addition, the workability is lowered due to scattering during spraying, and there is a problem that generation of unusual color due to fast curing speed and deterioration of adhesion between layers are caused.

Due to the above problems, the oil-and-inorganic hybrid coatings have difficulty in expanding the domestic and overseas market even though they have excellent physical properties. Therefore, development of an organic-inorganic hybrid coating material having excellent physical properties is required.

Korean Patent No. 10-0956752

The present invention provides an organic-inorganic hybrid coating material having excellent weather resistance and low flammability in addition to surface hardness, abrasion resistance, chemical resistance, heat resistance, and contamination resistance.

The present invention also provides a process for preparing the above-mentioned organic-inorganic hybrid coating agent.

The present invention also provides a coating composition comprising the oil-inorganic hybrid coating.

In order to solve the above-mentioned problems, the present invention provides a process for producing a glycidyl group-containing ether compound, A carboxyl group-containing compound; Silane compounds; And a primary reaction product obtained by a hydrolysis reaction and a coupling reaction of an inorganic precursor.

The present invention also relates to a method for producing a glycidyl group-containing compound, which comprises the steps of: a) conducting a hydrolysis reaction and a coupling reaction of a glycidyl group-containing ether compound, a silane compound and a carboxyl group-containing compound in the presence of an acid catalyst to obtain a first product; b) subjecting the inorganic precursor and the silane compound to a hydrolysis reaction and a coupling reaction in the presence of an acid catalyst to obtain a second product; And c) reacting the first product with the second product to obtain a first reaction product.

The present invention also relates to a method of manufacturing an organic electroluminescent device, comprising: a main portion including the organic-inorganic hybrid coating; And a curing agent portion comprising an amine curing agent.

The organic-inorganic hybrid coating of the present invention is combined with an inorganic material capable of enhancing the weatherability of a coating film while forming a flexible coating film and capable of enhancing the surface hardness, abrasion resistance, chemical resistance, heat resistance and stain resistance of the coating film . Accordingly, the present invention can provide an organic-inorganic hybrid coating agent which can exhibit overall excellent physical properties over conventional organic-inorganic hybrid coating agents.

In addition, since the organic-inorganic hybrid coating agent of the present invention has a high flash point and is excellent in safety, the cost for handling and transportation can be minimized, and economical efficiency can be secured.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a reference diagram for explaining the organic-inorganic hybrid coating agent of the present invention. Fig.
2 is a reference diagram for explaining a method for producing the organic-inorganic hybrid coating agent of the present invention.

Hereinafter, the present invention will be described.

The present invention relates to an organic-inorganic hybrid coating agent (hereinafter referred to as " inorganic coating composition ") having an inorganic substance capable of enhancing the weatherability of a coating film while forming a flexible coating film and capable of enhancing the surface hardness, abrasion resistance, chemical resistance, , 'Coating agent'), a process for producing the same, and a coating composition containing the same, which will be described in detail as follows.

1. Coating

The coating agent of the present invention includes a primary reaction product obtained by hydrolysis and coupling reaction of a glycidyl group-containing ether compound, a carboxyl group-containing compound, a silane compound, and an inorganic precursor in the presence of an acid catalyst.

In addition, the coating agent of the present invention may include a metal alkoxide in the presence of an acid catalyst and a secondary reaction product obtained by a hydrolysis reaction and a coupling reaction of the primary reaction product.

In addition, the coating agent of the present invention may include a chelating agent and a tertiary reaction product obtained by a coupling reaction of the secondary reaction product.

Specifically, the first reactant is an acid catalyst (first acid catalyst) (a ₁₎ a glycidyl group-containing ether compound (a _2), the carboxyl group-containing compound (a ₄₎ and the silane compound (a second silane compound) in the presence ( a first product (a) as obtained by the hydrolysis reaction and the coupling reaction of a _3),

The acid catalyst (second acid catalyst) (b ₁₎ in the presence inorganic precursor (b ₂₎ and silane compound (second silane compound) (b ₃₎ the second product obtained by the hydrolysis reaction and binding reactions (b) is It may be reacted.

Examples of the glycidyl group-containing ether compound include, but are not limited to, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether (1,6- Hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-cyclohexane dimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, A polypropylene glycol diglycidyl ether and an ethylene glycol diglycidyl ether.

Among the glycidyl group-containing ether compounds, neopentyl glycol diglycidyl ether is a compound represented by the following formula (1)

1,4-cyclohexanedimethanol diglycidyl ether is a compound represented by the following formula (2)

The polypropylene glycol diglycidyl ether is a compound represented by the following formula (3).

The carboxyl group-containing compound is not particularly limited, but may be 1,4-cyclohexane dicarboxylic acid. The 1,4-cyclohexanedicarboxylic acid is a compound represented by the following formula (4).

Here, the glycidyl group-containing ether compound and the carboxyl group-containing compound serve as precursors for imparting an organic substance to the coating agent of the present invention. The coating agent of the present invention does not have a clouding point and can be used at a low temperature (for example, Precipitation can be prevented even if stored in the winter season. Further, the viscosity of the coating agent of the present invention can be increased by these compounds, and when a coating film is formed using the coating composition containing the coating agent, a coating film which is flexible and has excellent weather resistance and alkali resistance can be formed.

The inorganic precursor is not particularly limited, but may be aluminum terminated colloidal silica. The aluminum-terminated colloidal silica has a structure having an OH group on its surface as shown in Fig. The aluminum-terminated colloidal silica is an inorganic precursor having an acidity of pH 1 to 3 and containing 30 parts by weight of silacar. Since the alcohol as a flammable substance is not generated in the hydrolysis reaction, the flammability of the coating material of the present invention Can contribute to lowering. In addition, since the raw material itself contains water, it can serve to provide water required for the hydrolysis reaction.

The silane compound (the first silane compound and the second silane compound) is not particularly limited, but 3-methacryloxypropyltrimethoxy silane, 3-vinyltrimethoxy silane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxy silane, 3-glycidoxypropyltrimethoxy silane, 3-isocyanatopropyltrimethoxysilane, ) And 3-glycidoxypropyltriethoxy silane. [0034] The term " a "

The second reactant is obtained by a hydrolysis reaction and a coupling reaction of the first reactant (c ₂ ) and the metal alkoxide (c ₃ ) in the presence of an acid catalyst (a third acid catalyst) c ₁ , The alkoxide may be tetramethylortho silicate, or tetraethylortho silicate.

Specifically, tetramethyl orthosilicate among the metal alkoxides is a compound represented by the following formula (5)

Tetraethylorthosilicate is a compound represented by the following formula (6).

The inorganic precursor, the silane compound and the metal alkoxide serve as precursors for imparting an inorganic substance to the coating agent of the present invention. When a coating film is formed from the coating composition containing the coating agent of the present invention by these compounds, And a coating film excellent in abrasion resistance, chemical resistance, heat resistance, stain resistance and the like can be formed.

The third reactant is obtained by a reaction between the second reactant (d ₁ ) and a chelating agent (d ₂ ), wherein the chelating agent is selected from oxalic acid, boric acid, iminodiacetic acid, malonic acid, succinic acid and malic acid Lt; / RTI >

Such a tertiary reactant may be represented by the following formula (7), for example.

The acid catalyst (the first acid catalyst, the second acid catalyst, and the third acid catalyst) to be used for obtaining the coating agent of the present invention (used in the hydrolysis reaction) is not particularly limited, but phosphoric acid, hydrochloric acid, And acetic acid.

A solvent may be added to the hydrolysis reaction and the coupling reaction to obtain the coating agent of the present invention. At this time, the solvent is not particularly limited, but a solvent having a high flash point and low toxicity can be used. Specifically, the solvent may be selected from the group consisting of diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether Ether Acetate, Diethylene Glycol Monobutyl Ether, Dipropylene Glycol Monomethyl Ether, Triethylene Glycol Monobutyl Ether and 2,2-Dimethyl-1 , 3-propanediol (2,2-dimethyl-1,3-propanediol).

The coating agent of the present invention may have a hydrolysis rate of 80% or less. When the hydrolysis ratio exceeds 80%, a transparent, turbid coating agent can be obtained. Further, when a coating film is formed with a coating composition containing a coating agent having a hydrolysis ratio exceeding 80%, a coating film having poor surface hardness, abrasion resistance, durability, and the like can be formed. Specifically, the coating of the present invention may have a hydrolysis rate of 40 to 70%, more specifically 55 to 65%.

Here, the hydrolysis rate can be defined as a value obtained by the following equation.

Specifically, a hydrolysis reaction occurs between the silane compound and the metal alkoxide. In this case, the ratio of the amount of water introduced into the hydrolysis reaction to the amount of water required for the complete hydrolysis reaction of the silane compound and the metal alkoxide, It may mean the hydrolysis rate. Wherein the water used in the hydrolysis reaction may be derived from the acid catalyst and the colloidal silica terminated with aluminum.

2. Manufacturing method of coating agent

The present invention provides a method for producing the above-described coating agent, which will be described in detail as follows.

a) Obtaining the first product

The first product is obtained by proceeding the hydrolysis reaction and the coupling reaction of the glycidyl group-containing ether compound, the silane compound (first silane compound) and the carboxyl group-containing compound in the presence of an acid catalyst.

Specifically, the glycidyl group-containing ether-based compound has an OH group at the terminal thereof due to the ring opening of the glycidyl group by the acid catalyst. For example, ring opening of neopentyl glycol diglycidyl ether occurred by acid catalyst as described below.

Further, the hydrolysis reaction is caused by the water contained in the acid catalyst of the silane compound, so that the OH group is present at the terminal. For example, vinyltrimethoxysilane having an OH group at the terminal thereof may be mentioned as follows by a hydrolysis reaction (partial hydrolysis reaction).

Here, the hydrolysis rate of the silane compound (first silane compound) (the ratio of the amount of water introduced into the hydrolysis reaction to the amount of water required for the complete hydrolysis reaction of the silane compound) may be 10 to 30%. As the hydrolysis rate of the silane compound is adjusted to 10 to 30%, the silane compound bonded portion has a low molecular weight, which prevents the coating agent of the present invention from being excessively infiltrated into the substrate.

The ring-opened ether compound having a glycidyl group and the silane compound having undergone the hydrolysis reaction undergo an oxygen bonding reaction as described below,

And the carboxyl group-containing compound is bonded thereto to produce the first product.

b) Obtaining the second product

The hydrolysis reaction and the coupling reaction of the inorganic precursor and the silane compound (second silane compound) proceed in the presence of an acid catalyst to obtain a second product. Specifically, the silane compound (second silane compound) in which the hydrolysis reaction (partial hydrolysis reaction) takes place and the inorganic precursor are oxygen-bonded to produce the second product. Here, the hydrolysis rate of the silane compound (second silane compound) (the ratio of the amount of water introduced into the hydrolysis reaction to the amount of water required for the complete hydrolysis reaction of the silane compound) may be 40 to 60%.

When the inorganic precursor is reacted with the silane compound (the second silane compound), the inorganic precursor is stabilized and the collision with the first product during the reaction with the first product can be prevented.

c) Obtain the first reactant

The first product and the second product are reacted to obtain a first reactant. The reaction temperature for reacting the first product and the second product is not particularly limited, but may be adjusted to 70 ° C or higher (specifically, 70 to 90 ° C) so that the solvent (for example, methanol) .

d) Obtaining the second reactant

Meanwhile, the method for preparing a coating agent of the present invention may further include a step of reacting the metal alkoxide and the first reactant in the presence of an acid catalyst to obtain a second reactant. Specifically, the metal alkoxide is hydrolyzed (partially hydrolyzed) by water contained in the acid catalyst to have an OH group at the end, and the metal alkoxide in which the hydrolysis reaction has occurred is combined with the first reactant to form a second reactant .

Here, the hydrolysis rate of the metal alkoxide (the ratio of the amount of water introduced into the hydrolysis reaction to the amount of water required for the complete hydrolysis reaction of the metal alkoxide) may be 40 to 60%. As the hydrolysis rate of the metal alkoxide is adjusted to 40 to 60%, the metal alkoxide-bonded portion has a high molecular weight, thereby preventing the coating film formed from the coating composition containing the coating agent of the present invention from being brittle or deteriorating in adhesion .

The reaction temperature for reacting the metal alkoxide with the first reactant is not particularly limited, but may be adjusted to 80 ° C or higher (specifically, 80 to 90 ° C) so that the solvent (for example, ethanol) .

e) Obtain tertiary reactant

In addition, the method of the present invention may further include a step of reacting the chelating agent and the second reactant to obtain a third reactant.

The method for producing the coating agent of the present invention described above can be more specifically described as shown in FIG.

As described above, the present invention can produce a coating agent having a structure in which a low molecular weight (low viscosity) part and a high molecular weight (high viscosity) part are bonded to each other by controlling the hydrolysis rates of the silane compound and the metal alkoxide. The invention can provide a coating composition which is excellent in permeability and adhesion to a substrate while forming a hard coating film.

3. Coating composition

The present invention provides a coating composition comprising a main part including a coating agent and a curing agent part, which will be described in detail as follows.

The main part included in the coating composition of the present invention includes the above-mentioned coating material as a main component for forming a coating film.

The curing agent part included in the coating composition of the present invention includes a curing agent as a component that induces the curing reaction of the above-mentioned coating agent. The curing agent is not particularly limited, but may be an amine-based curing agent having an Amine Hydrogen Equivalent Weight (A.H.E.W) of 55 to 90 g / eq.

Specifically, the amine-based curing agent may be at least one selected from the group consisting of polyetherdiamine, polyethertriamine, and cycloaliphatic modified amine. When a curing agent mixed with polyether diamine, polyether triamine and cycloaliphatic modifier amine is used as the amine curing agent, the mixing ratio thereof may be an equivalent ratio of 3: 4: 3. When the curing agent mixed at the above mixing ratio is used, a coating film having excellent physical properties can be formed while appropriately securing the tacky drying time of the coating composition.

Meanwhile, when the ratio of the curing agent to the main part (100 parts by weight) is represented by {(Amine Hydrogen Equivalent Weight) × 100 / Epoxy Equivalent Weight} × K (K: reaction constant), the reaction constant K may be 0.88 have.

The coating composition of the present invention can be used for coating a substrate made of plastic, metal, wood, cement, concrete, glass or the like because it can form a coating film having excellent physical properties.

Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

348 g of a mixed solution obtained by dissolving 1,743 g of neopentyl glycol diglycidyl ether and 100 parts by weight of 2,2-dimethyl-1,3-propanediol in 1,4-cyclohexane dicarboxylic acid (30 parts by weight) in a 5-liter four- , 697 g of vinyltrimethoxysilane and 349 g of diethylene glycol monoethyl ether acetate. The mixture was stirred at room temperature for 30 minutes. 33.3 g of nitric acid (concentration: 9%) was dropwise added and further stirred and reacted at room temperature for 120 minutes to obtain Mixture 1.

 Next, 26.5 g of nitric acid (concentration 9%) was dropwise added to 523 g of vinyltrimethoxysilane and 87 g of diethylene glycol monoethyl ether acetate, and the mixture 2 was obtained by stirring and reacting for 30 minutes.

Then, a mixture of 4.2 g of phosphoric acid and 192 g of water-dispersed aluminum terminated colloidal silica was added to the mixture 2, and the mixture 3 was obtained by stirring and reacting at room temperature for 90 minutes.

Next, the mixture 1 and the mixture 3 were mixed, heated to 70, stirred and reacted for 120 minutes, and discharged and stored at room temperature to prepare a coating agent (hydrolysis ratio: 77%).

180 g of Neopentyl glycol diglycidyl ether and 180 g of 1,2-dimethyl-1,3-propanediol (100 parts by weight) and 1,4-cyclohexane dicarboxylic acid (30 parts by weight) were dissolved in a 5-liter four- , Vinyltrimethoxysilane (602 g) and Diethylene glycol monoethyl ether (241 g). The mixture was stirred for 30 minutes. Then, 23 g of nitric acid (concentration: 9%) was added thereto and stirred at room temperature for 120 minutes.

Subsequently, 120.4 g of diethylene glycol monoethyl ether acetate was added to 602 g of vinyltrimethoxysilane, stirred for 30 minutes, 13.72 g of nitric acid (concentration 9%) was added, and stirred and reacted for 30 minutes to obtain mixture 2.

Then, a mixture of 4.32 g of phosphoric acid and 180.58 g of water-dispersed aluminum terminated colloidal silica was added to the mixture 2, and the mixture 3 was obtained by stirring and reacting at room temperature for 60 minutes.

Next, the mixture 1 and the mixture 3 were mixed, and the mixture was heated to 70, and stirred and reacted for 120 minutes to obtain a mixture 4.

Then, 38.52 g of hydrochloric acid (9%) was dropwise added to a mixture of 301 g of tetraethylorthosilicate and 361 g of diethylene glycol monoethyl ether, and the mixture was stirred and reacted for 60 minutes to obtain a mixture 5.

Then, Mixture 4 and Mixture 5 were mixed, followed by stirring at 70 to 60 minutes. After stirring, 36.11 g of hydrochloric acid (concentration 9%) was dropwise added, the temperature was raised to 80, and the mixture was stirred and reacted for 120 minutes. Then, 8 g of oxalic acid was added, stirred and reacted for 80 to 120 minutes, and discharged and stored at room temperature to prepare a coating agent (hydrolysis rate: 61.5%).

[Comparative Example 1]

159 g of a mixed solution obtained by dissolving 1,590 g of polypropylene glycol diglycidyl ether and 100 parts by weight of 2,2-dimethyl-1,3-propanediol in 1,4-cyclohexane dicarboxylic acid (30 parts by weight) And 1,431 g of Vinyltrimethoxysilane. The mixture was stirred at room temperature for 30 minutes and reacted. Then, 477 g of diethylene glycol monoethyl ether acetate was added and further stirred at room temperature for 30 minutes. After stirring, 31.81 g of nitric acid was dropwise added, followed by stirring and reaction at room temperature for 60 minutes to obtain a mixture 1.

Then, 5 g of phosphoric acid was dropwise added to 270.38 g of water-dispersed aluminum terminated colloidal silica, and the mixture 2 was obtained by stirring and reacting for 60 minutes.

Then, the mixture 1 and the mixture 2 were mixed and stirred at room temperature for 60 minutes. Then, 39.76 g of nitric acid (concentration 9%) was dropwise added to the mixture, and the mixture was heated to 70. After stirring and reacting for 120 minutes, (Hydrolysis ratio: 88.8%) was prepared.

[Comparative Example 2]

1,469 g of Vinyltrimethoxysilane and 378 g of diethylene glycol monoethyl ether acetate were added to a 5 liter round bottom flask and stirred for 30 minutes at room temperature. 18.98 g of nitric acid (concentration 9%) was dropwise added and stirred again at room temperature for 30 minutes. To give Mixture 1.

Next, a mixture of 15.8 g of phosphoric acid dropwise added to 303.8 g of water-dispersed aluminum terminated colloidal silica was added to the mixture 1, and the mixture was heated to 70 and stirred and reacted for 120 minutes to obtain a mixture 2.

Next, 227 g of a mixture of 1,373 g of neopentyl glycol diglycidyl ether and 2,2-dimethyl-1,3-propanediol (100 parts by weight) dissolved in 30 parts by weight of 1,4-cyclohexane dicarboxylic acid, ether 170 g was mixed into the mixture 2, and then stirred and reacted for 70 to 60 minutes. After stirring, 28.47 g of hydrochloric acid (concentration 9%) was dropwise added, followed by stirring and reacting for 120 minutes. after. 7.59 g of oxalic acid was added thereto, stirred and reacted for 120 minutes, and discharged and stored at room temperature to prepare a coating agent (hydrolysis ratio: 87%).

[Experimental Example 1]

The flash points of the coatings prepared in Examples 1 and 2 were measured by a conventional method, and the results are shown in Table 1 below.

Properties Example 1 Example 2 Flash point (℃) 78 73

Referring to Table 1, it can be confirmed that the coating agents of Examples 1 and 2 according to the present invention have high flash point and excellent safety. That is, the flash point temperature of the coating agent of Examples 1 and 2 according to the present invention is higher than 62 ° C., and it is confirmed that the flash point is safe due to the high flash point . [Production Example 1]

The coating composition was prepared by mixing each of the components shown in Table 2 below with 100 parts by weight of the main part containing the coating agent prepared in Example 1, using a polyetherdiamine (polyethertriamine and cycloaliphatic modified amine alone).

Hardener part Topic section 100 parts by weight of the coating agent of Example 1 100 parts by weight of the coating agent of Example 1 100 parts by weight of the coating agent of Example 1 100 parts by weight of the coating agent of Example 1 Polyetherdiamine 23.17 parts by weight 25.03 parts by weight 26.88 parts by weight 28.73 parts by weight Polyethertriamine 33.91 parts by weight 36.62 parts by weight 39.33 parts by weight 42.04 parts by weight Cycloaliphatic modified amine 36.54 parts by weight 39.11 parts by weight 42.01 parts by weight 45.63 parts by weight

[Production Example 2] A coating composition was prepared by mixing the curing agent (polyether diamine, polyethertriamine and cycloaliphatic modified amine alone) according to the composition shown in Table 3 on the basis of 100 parts by weight of the main part containing the coating agent prepared in Example 2, Respectively.

Hardener part Topic section 100 parts by weight of the coating agent of Example 2 100 parts by weight of the coating agent of Example 2 100 parts by weight of the coating agent of Example 2 100 parts by weight of the coating agent of Example 2 Polyetherdiamine 21.49 parts by weight 23.21 parts by weight 24.93 parts by weight 26.65 parts by weight Polyethertriamine 31.45 parts by weight 33.97 parts by weight 36.48 parts by weight 39 parts by weight Cycloaliphatic modified amine 34.23 parts by weight 36.29 parts by weight 38.97 parts by weight 41.46 parts by weight

[Comparative Preparation Example 1] A coating composition composition was prepared by mixing 100 parts by weight of a main component comprising the coating agent prepared in Comparative Example 1, and a curing agent part (polyethertriamine and cycloaliphatic modified amine alone) Respectively.

Hardener part Topic section 100 parts by weight of the coating agent of Comparative Example 1 100 parts by weight of the coating agent of Comparative Example 1 100 parts by weight of the coating agent of Comparative Example 1 100 parts by weight of the coating agent of Comparative Example 1 Polyetherdiamine 15.3 parts by weight 19.07 parts by weight 22.9 parts by weight 26.7 parts by weight Polyethertriamine 20.98 parts by weight 26.23 parts by weight 31.47 parts by weight 36.72 parts by weight Cycloaliphatic modified amine 22.41 parts by weight 28.02 parts by weight 33.62 parts by weight 39.22 parts by weight

[Comparative Preparation Example 2] A curing agent part (polyethertriamine and cycloaliphatic modified amine alone) of 100 parts by weight of the main part containing the coating agent prepared in Comparative Example 2 was mixed with the composition shown in Table 5 below to prepare a coating composition Respectively.

Hardener part Topic section 100 parts by weight of the coating agent of Comparative Example 2 100 parts by weight of the coating agent of Comparative Example 2 100 parts by weight of the coating agent of Comparative Example 2 100 parts by weight of the coating agent of Comparative Example 2 Polyetherdiamine 15.3 parts by weight 19.07 parts by weight 22.9 parts by weight 26.7 parts by weight Polyethertriamine 20.98 parts by weight 26.23 parts by weight 31.47 parts by weight 36.72 parts by weight Cycloaliphatic modified amine 22.41 parts by weight 28.02 parts by weight 33.62 parts by weight 39.22 parts by weight

[Experimental Example 2] Physical properties of the coating film formed after the coating compositions prepared in Production Examples 1 and 2 and Comparative Production Examples 1 and 2 were respectively evaluated, and the results are shown in Tables 6 to 9 below. .

Production Example 1 Pencil hardness Polyetherdiamine 2H 3H 2H H Polyethertriamine 2H 3H 2H H Cycloaliphatic modified amine 3H 4H 3H 2H Wear amount (H-22, 1,000g, 500 Cycle) Polyetherdiamine 0.19 0.17 0.20 0.24 Polyethertriamine 0.18 0.17 0.21 0.23 Cycloaliphatic modified amine 0.17 0.16 0.18 0.21 Touch dry (25 ℃, time) Polyetherdiamine 5.4 5.5 5.8 6.4 Polyethertriamine 5.7 5.9 6.1 6.3 Cycloaliphatic modified amine 1.4 1.5 1.7 2.1

Production Example 2 Pencil hardness Polyetherdiamine 3H 3H 2H H Polyethertriamine 3H 3H 2H H Cycloaliphatic modified amine 4H 4H 3H 2H Wear amount (H-22, 1,000g, 500 Cycle) Polyetherdiamine 0.24 0.19 0.21 0.25 Polyethertriamine 0.23 0.19 0.21 0.27 Cycloaliphatic modified amine 0.21 0.18 0.2 0.25 Touch dry (25 ℃, time) Polyetherdiamine 4.7 4.9 5.1 5.4 Polyethertriamine 5.2 5.3 5.6 5.9 Cycloaliphatic modified amine 1.3 1.4 1.7 1.9

Comparative Preparation Example 1 Pencil hardness Polyetherdiamine B HB B 2B Polyethertriamine B HB B 2B Cycloaliphatic modified amine B 1H HB B Wear amount (H-22, 1,000g, 500 Cycle) Polyetherdiamine 0.41 0.36 0.42 0.48 Polyethertriamine 0.42 0.38 0.43 0.49 Cycloaliphatic modified amine 0.34 0.29 0.36 0.43 Touch dry (25 ℃, time) Polyetherdiamine 6.5 6.8 7.1 7.3 Polyethertriamine 7.4 7.6 7.8 8.1 Cycloaliphatic modified amine 1.5 1.6 1.8 2.1

Comparative Production Example 2 Pencil hardness Polyetherdiamine B B B 2B Polyethertriamine B B B 2B Cycloaliphatic modified amine B HB B 2B Wear amount (H-22, 1,000g, 500 Cycle) Polyetherdiamine 0.36 0.32 0.33 0.39 Polyethertriamine 0.31 0.29 0.32 0.34 Cycloaliphatic modified amine 0.28 0.25 0.29 0.32 Touch dry (25 ℃, time) Polyetherdiamine 6.7 6.9 7.3 7.5 Polyethertriamine 7.4 7.5 7.9 8.1 Cycloaliphatic modified amine 1.6 1.7 1.9 2.1

Referring to Tables 6 to 9, it can be seen that the coating film formed from the coating composition of Examples 1 and 2 having a hydrolysis ratio of 80% or less has a high hardness and a low wear amount. On the other hand, it can be seen that the coating film formed from the coating composition to which the coating agent of Comparative Examples 1 and 2 having a hydrolysis ratio exceeding 80% had a low hardness and a remarkably high wear amount. These results support the fact that application of the coating agent of the present invention to a coating composition results in formation of a coating film having high surface hardness and excellent physical properties such as abrasion resistance and durability.

[Production Example 3]

A coating composition was prepared by mixing a curing agent (polyetherdiamine, a mixture of polyethertriamine and cycloaliphatic modified amine) based on 100 parts by weight of the main part containing the coating agent prepared in Example 2, in the composition shown in Table 10 below.

Hardener part Topic section 100 parts by weight of the coating agent of Example 2 100 parts by weight of the coating agent of Example 2 100 parts by weight of the coating agent of Example 2 100 parts by weight of the coating agent of Example 2 Polyetherdiamine 10.75 parts by weight 9.28 parts by weight 7.48 parts by weight 5.33 parts by weight Polyethertriamine 9.44 parts by weight 13.59 parts by weight 14.59 parts by weight 19.5 parts by weight Cycloaliphatic modified amine 6.85 parts by weight 7.26 parts by weight 11.69 parts by weight 12.44 parts by weight

[Experimental Example 3] After coating films were formed from the coating compositions prepared in Preparation Example 3, physical properties of the coating films formed were evaluated. The results are shown in Table 11 below.

Production Example 3 Pencil hardness Polyetherdiamine + Polyethertriamine + Cycloaliphatic modified amine 3H 4H 4H 4H Wear amount (H-22, 1,000g, 500 Cycle) Polyetherdiamine + Polyethertriamine + Cycloaliphatic modified amine 0.19 0.18 0.16 0.15 Touch dry (25 ℃, time) Polyetherdiamine + Polyethertriamine + Cycloaliphatic modified amine 4.4 4.2 3.8 4.3

Referring to Table 11, it can be seen that a coating film showing excellent physical properties is formed on the whole. In particular, when the polyetherdiamine: polyethertriamine: cycloaliphatic modified amine is mixed at an equivalent ratio of 3: 4: 3, it can be confirmed that the physical properties are the most excellent.

Claims (18)

A glycidyl group-containing ether compound in the presence of an acid catalyst; A carboxyl group-containing compound; Silane compounds; And a primary reaction product obtained by a hydrolysis reaction and a coupling reaction of an inorganic precursor. The method according to claim 1,
Wherein the glycidyl group-containing ether compound is selected from the group consisting of 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, But are not limited to, neopentyl glycol diglycidyl ether, 1,4-cyclohexane dimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, diglycidyl ether and ethylene glycol diglycidyl ether. < RTI ID = 0.0 > 11. < / RTI > The method according to claim 1,
Wherein the carboxyl group-containing compound is 1,4-cyclohexane dicarboxylic acid. 2. The organic-inorganic hybrid coating composition according to claim 1, wherein the carboxyl group-containing compound is 1,4-cyclohexane dicarboxylic acid. The method according to claim 1,
Wherein the inorganic precursor is aluminum terminated colloidal silica having a pH of 13. ≪ RTI ID = 0.0 > 11. < / RTI > The method according to claim 1,
A metal alkoxide in the presence of an acid catalyst; And a secondary reaction product obtained by a hydrolysis reaction and a coupling reaction of the primary reaction product. 6. The method of claim 5,
Wherein the metal alkoxide is tetramethylorthosilicate or tetraethylortho silicate. ≪ RTI ID = 0.0 > 11. < / RTI > 6. The method of claim 5,
A solvent is added to the hydrolysis reaction and the coupling reaction,
Wherein the solvent is selected from the group consisting of diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate ), Diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monobutyl ether, and 2,2-dimethyl-1,3 -propanediol (2,2-dimethyl-1,3-propanediol). 6. The method of claim 5,
Chelating agents; And a tertiary reaction product obtained by the coupling reaction of the secondary reaction product. 9. The method of claim 8,
Wherein the chelating agent is at least one selected from the group consisting of oxalic acid, boric acid, iminodiacetic acid, malonic acid, succinic acid and malic acid. The method according to claim 1,
Wherein the hydrolysis rate is 80% or less. a) conducting a hydrolysis reaction and a coupling reaction of a glycidyl group-containing ether compound, a silane compound and a carboxyl group-containing compound in the presence of an acid catalyst to obtain a first product;
b) subjecting the inorganic precursor and the silane compound to a hydrolysis reaction and a coupling reaction in the presence of an acid catalyst to obtain a second product; And
c) reacting the first product with the second product to obtain a first reaction product. 12. The method of claim 11,
Wherein the hydrolysis rate of the silane compound in step a) is 10 to 30%. 12. The method of claim 11,
d) reacting the metal alkoxide and the first reactant in the presence of an acid catalyst to obtain a second reactant. 14. The method of claim 13,
And the hydrolysis rate of the metal alkoxide in step d) is 40 to 60%. 14. The method of claim 13,
In the step c), the reaction temperature of the first product and the second product is 70 ° C or higher,
Wherein the metal alkoxide and the first reactant are reacted at a temperature of 80 DEG C or higher in step d). 14. The method of claim 13,
e) reacting the chelating agent and the second reactant to obtain a tertiary reactant. < RTI ID = 0.0 > 11. < / RTI > 11. A coating composition comprising: a topical part comprising a oil-in-inorganic hybrid coating according to any one of claims 1 to 10; And
A coating composition comprising a curing agent portion comprising an amine-based curing agent. 18. The method of claim 17,
Wherein the amine curing agent is at least one selected from the group consisting of polyetherdiamine, polyethertriamine, and cycloaliphatic modified amine.

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