KR101139553B1 - Nano-hybride composition and the preparation of thin-film and thick-film using organo-gelation and inorganic sol-gel process - Google Patents

Abstract

The present invention relates to an organic-inorganic nanocomposite thin film coating and film, which is an organic-inorganic composite made by forming a inorganic acid gel by forming a monobasic organic gel and a metal alkoxide by forming a sol-gel. It relates to an organic-inorganic composite composition which can form a. In addition, the brittle surfaces of inorganic oxide and metal oxide films can be processed smoothly, resulting in a simplified process procedure through excellent coating properties and solubility in various solvents.

It is also possible in various solution processes using a simple coating method of spraying, coating, electrophoretic deposition, casting, inkjet printing, offset printing on a variety of substrates.

Organic Gel, Inorganic Gel, Nanocomposite, Thin Film Coating, Film Preparation

Description

Nano-hybride composition and the preparation of thin-film and thick-film using organo-gelation and inorganic sol-gel process}

The present invention relates to a functional thin film coating and a film having increased interest in various fields such as a functional optical film including an AR film, a solar cell, an LED encapsulant, an optical lens coating, a semiconductor, a display, an optical communication cable, an optical waveguide, and the like. The present invention relates to a composition of organic-inorganic nanocomposites of organic gelling and sol-gel methods, as well as thin film coatings and films thereof.

Existing high refractive index thin film has been studied a lot by using polymer-titanium. It is a polymer with good coating property and intrinsic refractive index, but because it has a refractive index of 1.3 ~ 1.7, an organic-inorganic nanocomposite film complexed with metal, which is a high refractive index material, is needed. Polymers used in previous studies are poly (silsesquioxanes), poly (methyl methacrylate), polyimide, etc. (J. Mater. Chem., 2003, 13, 2189, Mater.Chem. Phys., 2004, 83, 71, J. Mater.Chem., 1999, 9, 2999, Chem. Mater., 2001, 13, 1137, J. Mater. Chem., 2003, 13, 1475, Appl. Phys. Lett., 2003, 82, 2691, J. Mater. Chem., 2004, 14, 2978, J. Electroseram., 2006, 16, 431, Chem. , 2006, 18, 5876, J. Polym. Sci.Part A: Polym. Chem., 2001, 39, 3419, Macromol.Mate.Eng., 2006, 291, 1521, Polymer, 2003, 44, 2249)

In the above experiment, the polymer-titanium hybrid film prepared by the sol-gel method had a refractive index of 1.505-1.876 and showed high transmittance in the visible region. However, poly (methyl methacrylate) has a low thermal stability and thus is limited in application to optoelectronic devices. In order to solve this problem, studies using polyimide having high thermal stability instead of poly (methyl methacrylate) have been actively conducted. However, in the case of a high refractive index film using a polymer is not a variety of soluble solvent, there is a hassle of the process of synthesizing the polymer through the design and synthesis of soluble monomer.

delete

Conventional high refractive index thin films are mainly produced by physical vapor deposition (PVD), such as vacuum deposition and sputtering, or chemical vapor deposition (CVD), such as thermal CVD and plasma CVD. .

However, the above-described gas phase method requires a large vacuum equipment, which is expensive and has a problem of low productivity. Recently, a method of manufacturing a high refractive index thin film using a sol (Gel) method, which is a kind of liquid phase method having high productivity at low cost in the air, has attracted attention.

For example, a mixture obtained by dissolving titanium alkoxide in an organic solvent, such as alcohol, is coated on a transparent polymer film, dried to form a thin film, and then irradiated with a specific illuminance and a specific amount of ultraviolet light. A high refractive index transparent laminated film containing titanium oxide (Titaninum) oxide and the like is disclosed. (JP-A 2004-197189)

However, the above-described technique leaves room for improvement as follows. In the case of using the Sol-Gel method and the ultraviolet irradiation method, the hydrolysis condensation reaction does not proceed sufficiently to the inside of the thin film, and thus, the raw material of titanium alkoxide is likely to remain. Therefore, it is desirable to reduce the amount of unreacted components by increasing the amount of ultraviolet light emitted to the thin film as much as possible. However, many ultraviolet rays have a problem due to the coefficient of thermal expansion in which the thin film to shrink in the plane direction is constrained to the transparent polymer film and thus cannot be shrunk, causing cracks in the thin film. In addition, in order to irradiate a large amount of ultraviolet light during the mass production also causes a problem of productivity to reduce the speed of the production line (line).

delete

delete

delete

delete

delete

delete

delete

delete

delete

The problem to be solved by the present invention is to have a solubility in a variety of solvents, and to prepare a composition of the organic-inorganic nanocomposite, a thin film coating and a film thereof in a simpler process.
The problem to be solved by the present invention is to develop a process for a solution that can suppress the occurrence of cracks and can reduce the composition and production cost of the thin film formation and easy film.
Accordingly, an object of the present invention is to develop an organic-inorganic material for a functional thin film coating and film using the method of organic gel and sol-gel, and the thin film coating and film using the conventional sol-gel method are fragile and thus used for flexible substrates. Can not. 1) However, when organic materials and metal alkoxides are combined, excellent coating and flexible films can be formed on the flexible substrate, and the problem of the existing technology is that the adhesion with the flexible substrate is very weak. Adhesion is very strong. Also, 3) various coating methods using organic solvents can be used.

Another object of the present invention is 1) the introduction of organic gel (Organo gel) to smoothly process the brittle surface of the inorganic oxide and metal oxide film, 3) through excellent coating properties and solubility in various solvents, 4) A more simplified process procedure is to provide organic-inorganic nanocomposite transparent thin films on various substrates.

Specifically, by using a simple method of spraying, coating, electrophoretic deposition, casting, inkjet printing, offset printing using the above-mentioned metal nitrate-metal nanocomposite to provide a solution process composition useful in a variety of solution process fields have.

In order to achieve the above object, the transparent organic-inorganic composite thin film composition according to the present invention is characterized in that it comprises a metal alkoxide, a bile acid or a bile acid derivative, water, an organic solvent or a mixed solvent thereof and a catalyst.
In addition, in order to achieve the above object, the method for preparing a transparent organic-inorganic composite thin film according to the present invention comprises the steps of mixing a metal alkoxide with a first organic solvent to form a first mixture, a bile acid or a bile acid derivative to a second organic Mixing with a solvent to form a second mixture, mixing the first mixture and the second mixture, adding a catalyst to form a transparent thin film composition, and applying the transparent thin film composition on a substrate Characterized in that it comprises a step.
And, in order to achieve the above object, the chemical formula of the compound to form the organic gel as a composition of the organic-inorganic complex made by forming the organic gel and the metal alkoxide (metal alkoxide) to form an inorganic gel by the sol-gel Baline acid and its derivatives represented below.

In Formulas 1a to 3a, p1, p2, and p3 are 1 or 2; R3 to R12 are independent of each other, at least one is a substituent having a functional group containing an aliphatic, aromatic or reactive group, Z1, Z2 is a compound having a functional group of two or more tetravalent or less, thus m1 is Is an integer from 2 to 4. In addition, V1 and V2 are couplers.

In the present invention, Formula 1a. It provides a water-soluble derivative of linear, branched or dendrimeric, star type structure around the formula (2a), formula (3a).

In addition, the above-mentioned composition composed of metal alkoxide as a composition via the sol-gel method, and a thin film coating through the organic gelation and the sol-gel method, which is a disadvantage of the thin film, which is a disadvantage of the conventional sol-gel method. Solves the problem of adhesion and solubility with the substrate.

The organic-inorganic composite composition capable of forming a thin film and a film having excellent coating properties according to the present invention can form an excellent coating and a flexible film on a flexible substrate when an organic material and a metal alkoxide are combined, and an organic gel inorganic composite. The coating is very strong in adhesion. In addition, various coating methods using an organic solvent can be used.

delete

delete

Bile acids R1 R2 Cholic acid OH OH Deoxycholic acid H OH Chenodeoxycholic acid OH H Lithocholic acid H H
바일산은 친수성 면(α-face) 즉, 여러 개의 히드록시(-OH)기와 1개의 카르복시산기를 가지고, 또한 완전히 소수성을 가지는 스테로이드와 3개의 메틸(methyl)기 그리고 3개의 키랄중심(chiral center)을 가지는 양쪽성 화합물이다.
이 같은 구조에서 오는 바일산은 특징은 자체결집능력(capacity of self assembling)이 우수하며, 또한 고안정성, 하이드록시기 또는 카르복시기의 반응성 및 단분자임에도 고(高)분자량(콜릭산의 경우 Mw= 408.57)을 가진다.
구조적인 성질에 의해서, 바일산은 미셀(micelle) 또는 다른 초분자구조(supramolecular structure)를 형성할 수 있고, 하이드록시 및 카르복시기는 알려진 방법에 의해서 쉽게 변형할 수 있기 때문에 많은 유도체가 가능하며 많은 응용분야에 사용될 수 있다.(Acc, Chem. Res. 2002, 35, 539-546, Chem Rev. 1997, 97, 283-304, Tetrahedron Lett. 1999, 40, 2849-2852, J. Lipid. Res. 1995, 36, 901-910, J. Pharm. Sci, 1992, 81, 726-730, Tetrahedron Lett. 1992, 33, 195-198.)
종래의 바일산 유도체의 응용분야는 국한 되어 사용되어져 왔다. 그러나 바일산의 고유 성질인 양친성 때문에 계면활성제로서 사용될 수 있고, 또한 자기결합능력(Self-Assembling)을 가지기 때문에 용액공정용 겔 화 소재로서도 사용될 수 있으며, 이 같은 성질을 이용하여, 무기물, 금속물, 무기산화물, 금속산화물 및 유기 화합물과 결합하거나 혼합하여 우수한 분산제로서 사용할 수 도 있으며 이를 이용하여, 분무 방식, 코팅, 전기영동 증착, 캐스팅, 잉크젯 프린팅 및 오프셋 프린팅의 코팅방법에 응용할 수 있는 다양한 용액공정용 소재로서 쓰일 수 있다. 이는 간단한 용액공정을 이용하여 박막을 형성함으로써, 공정 단가의 절감, 대멱적 코팅, 공정의 효율성 등 많은 장점을 가지고 있다.
본 발명에 따르는 유무기 나노복합체는 상기의 금속 알콕사이드(Metal alkoxide)와 바일산을 혼합하거나 바일산 유도체의 반응기와 결합을 통해 유기 겔(Organo gel)을 형성함으로서 고 굴절율 유무기 나노복합체 투명 필름을 제공한다.In addition, the functional organic gel-forming material used in the present invention is a bile acid (Bile acid) has a chemical structure of steroids, and there are various types of bile acid due to differences in the position of the hydroxyl group, steric coordination, number, side chain structure, and the like.

Bile acids R1 R2 Cholic acid OH OH Deoxycholic acid H OH Chenodeoxycholic acid OH H Lithocholic acid H H
Bilic acid has a hydrophilic (α-face), ie, several hydroxy (-OH) groups and one carboxylic acid group, and is also a completely hydrophobic steroid, three methyl groups and three chiral centers. It is an amphoteric compound having.
The bile acid from this structure is characterized by excellent capacity of self assembling, and high molecular weight (Mw = in the case of cholic acid) even though it is high stability, reactive or monomolecular hydroxy or carboxyl group. 408.57).
Due to its structural properties, bilic acid can form micelles or other supramolecular structures, and hydroxy and carboxyl groups can be easily modified by known methods, allowing many derivatives and many applications. (Acc, Chem. Res. 2002, 35, 539-546, Chem Rev. 1997, 97, 283-304, Tetrahedron Lett. 1999, 40, 2849-2852, J. Lipid. Res. 1995, 36, 901-910, J. Pharm.Sci, 1992, 81, 726-730, Tetrahedron Lett. 1992, 33, 195-198.)
The field of application of conventional baline acid derivatives has been limited and used. However, it can be used as a surfactant due to the amphipathy that is intrinsic property of bilic acid, and can also be used as a gelling material for solution process because of its self-assembling ability. It can be used as a good dispersant by combining or mixing with water, inorganic oxides, metal oxides and organic compounds, and can be used for various coating methods for spraying, coating, electrophoretic deposition, casting, inkjet printing and offset printing. It can be used as a material for solution process. This forms a thin film using a simple solution process, has a number of advantages, such as reducing the cost of the process, alternative coating, process efficiency.
The organic-inorganic nanocomposite according to the present invention is a high refractive index organic-inorganic nanocomposite transparent film by forming the organic gel (Organo gel) by mixing the metal alkoxide (metal alkoxide) and the bile acid or by combining with the reactor of the bail derivatives. to provide.

      In the present invention, it can be usefully used in the coating method of the solution process, coating, spray method, electrophoretic deposition, casting, inkjet printing and offset printing described above.

Specifically, the compounds and compositions provided by the present invention are as follows.

1) A composition comprising bamic acid and its derivatives, metal alkoxides, alcohols, organic solvents or mixed solvents thereof, and catalysts (acids and bases).

2) Metal alkoxides include tin (IV) tert-butoxide, titanium butoxide, titanium ethoxide, titanium methoxide, titanium isopropoxide Titanium isopropoxide, Titanium propoxide, Indium hydroxide (In (OH) ₃ ), Aluminum ethoxide, Aluminum isopropoxide, Aluminum phenoxide, Aluminum tert-butoxide, Aluminum tri-butoxide, Aluminum tri-sec-butoxide, Indium (III) tert Indium (III) tert-butoxide, Antimony (III) butoxide, Antimony (III) ethoxide, Antimony (III) methoxide ( Antimony (III) methoxide), antimony III) Propione (Antimony (III) propoxide), Hafnium (IV) n-butoxide, Hafnium (IV) tert-butoxide, Zirconium (IV) ) Zirconium (IV) butoxide, zirconium (IV) ethoxide, zirconium (IV) isopropoxide, zirconium (IV) propoxide (Zirconium (IV) propoxide), zirconium (IV) tert-butoxide, Zirconium (IV) tert-butoxide, Copper (II) methoxide, Calcium isopropoxide, Calcium Calcium methoxide, Magnesium ethoxide, Magnesium methoxide, Tetrabutyl orthosilicate, Tetraethyl orthosilicate, Tetramethyl orthosilicate, Tetrapropyl orthosilicate silicate) and the like. You may use these 1 type or 2 or more types.

Bilic acid and its derivatives include Cholic acid, Chenodeoxycholic acid, Dehydroxycholic acid, Deoxycholic acid, Hiyodeoxycholic acid ), Lithocholic acid, Sodium glycochenodeoxycholate, Sodium taurochenodeoxycholate, Sodium taurocholate hydrate, Sodium dehydrocholate, Sodium deoxycholate, Ursodeoxycholic acid, Sodium cholate hydrate, Hiyodeoxycholic acid methyl ester, 5β-cholanic-3α, 12α -Diol 3-acetate methyl ester (5β-Cholanic acid-3α, 12α-diol 3-acetate methyl ester), 5β-cholanic acid-3-one, 5β-cholanic acid 3 , 7-dione methyl ester (5β 1. A composition in which at least one bail acid compound selected from -Cholanic acid 3,7-dione methyl ester and 5β-cholanic acid-3,7-dione is mixed.

In the composition, it is preferable to use one or a mixture of two or more solvents selected from the group consisting of water, alcohols, ketones, ethers, amides, benzenes, and the like. Specifically, water, methanol, ethanol, propanol, butanol, butanol, pentanol, acetone, methyl ethyl ketone, acetonitrile acetonitrile, diglyme, glyme, cellosolve, DMF, dioxane, ethylene glycol, glycerin, nitromethane nitromethane, pyridine, benzene, toluene, xylene, tetrahydrofuran, pentane, hexane, chloroform, dichloromehtnae , Dichloroethane, trichloroethylene, tetrachloromethane, ether, diethylether, diisopropylether, methyl-t-butyl ether, heptane (heptane), ethylacetate, cyclohexane, butyl acetate (but ylacetate, ionic liquid, and the like, but the present invention is not limited thereto.

       4) A composition comprising a composition and at least one catalyst.

       In the composition, it is preferable to use one or a mixture of two or more selected from the group consisting of acids, bases and the like. Specifically, hydrochloric acid, sulfuric acid, acetic acid, ammonium hydroxide, 1,8-diazabicyclo (5.4.0), undec-7-ene (DBU), triethyl Amines (Triethylamine) and the like, and the present invention is not limited thereto.

Composition comprising a bile acid and its derivatives, metal alkoxides, alcohols, organic solvents or mixed solvents thereof, and catalysts (acids and bases).

delete

The composition of the composition is composed of a bile acid and a bile acid derivative, a metal alkoxide, a solvent and a catalyst, and may be mixed in one or more kinds.

The composition can be coated on a suitable substrate using various coating methods such as spraying, spin coating, electrophoretic deposition, casting, inkjet printing and offset printing. Here, the substrate may be any of paper, semiconductors and metals, ceramics and polymers. Examples include paper, glass, silicon, silicon oxide, gold, polysulfone, polyimide (PI), polytetrafluoroethylene (PTFE), polyethylene terephthalate (PET), polycarbonate, and Polyethylene (Polyethylene), etc., but may be selected in various ways depending on the application, the present invention is not limited thereto.

The general method for preparing the composition is as follows.

Method 1. Preparation of Coating Composition Using Organogelation and Sol-Gel Method

Metal alkoxide and an alcohol solvent were added to a 25 ml round bottom flask and stirred for 10 to 120 minutes. To the mixture was slowly added a solution obtained by dissolving a bile acid and a derivative of bile acid in an organic solvent, and then stirred at room temperature for 10 to 120 minutes. A small amount of acid or base catalyst was diluted in distilled water and an alcohol solvent and slowly added to the mixed solution at room temperature for 1 to 30 minutes, followed by stirring for 10 to 120 minutes. The final mixture solution was filtered through a 0.01 to 1.0 polymer or membrane filter to prepare a coating composition for the preparation of organic-inorganic nanocomposite thin films or films.

Method 2. Preparation of Organic-Inorganic Nanocomposite Thin Film and Film

The composition prepared above was applied onto substrates such as glass, silicon, polymer, etc. by spraying, spin coating, electrophoretic deposition, casting, inkjet printing and offset printing. Spin coating of the above method was performed for 10 ~ 180 seconds at a rotation speed of 1000 ~ 4000rpm. The thin film formed by the above method was dried for 10 to 120 minutes in a hot plate of 60 ~ 100 ℃, dried for 2 to 120 hours in a vacuum oven of 80 ~ 150 ℃ to prepare an organic-inorganic nano-composite transparent thin film and film.

Method 3. Characterization of Organic-Inorganic Nanocomposite Thin Films and Films

The characteristics of the thin film and the film prepared above were measured optical properties, electrical properties and the state of the film surface, the results are shown in Table 2 and Figure of the Examples. The optical properties were measured for the light transmittance and the refractive index, and the measurement results at the wavelength of 633 nm are shown in Table 2. As electrical properties, the sheet resistance and conductivity of the thin film and the film were measured, and the results are shown in Table 2 of the examples.

The present invention will be described in detail using the above embodiments. In addition, this invention is not limited only to these Examples.

Example 1

Titanium butoxide 2.014g and butanol 2.5ml were added to a 25 ml round bottom flask and stirred for 30 minutes. A solution of 0.106 g of cholic acid dissolved in 2.5 ml of dimethylacetamide was slowly added to the mixture using a syringe, followed by stirring at room temperature for 30 minutes. 0.0625 g of hydrochloric acid solution (37%) was diluted in 0.073 g of distilled water and 1.25 ml of butanol and slowly added to the mixed solution at room temperature for 15 minutes, followed by stirring for 30 minutes. The final mixture solution was applied onto a glass substrate using a syringe with a 0.2 polytetrafluoroethylene (PTFE) syringe filter, followed by spin coating at 2000 rpm for 60 seconds using a spin coating method. The formed thin film was dried in a hot plate at 60 ° C. for 30 minutes and then dried in a vacuum oven at 100 ° C. for 12 hours to prepare an organic-inorganic nanocomposite thin film. The properties of the prepared thin film are shown in Tables 1 and 2 below. (Metal alkoxide: bilic acid = 95: 5)

Example 2

In a 25 ml round bottom flask, 1.06 g of titanium butoxide and 2.5 ml of butanol were added and stirred for 30 minutes. A solution of 1.06 g of deoxycholic acid dissolved in 2.5 ml of dimethylacetamide was slowly added to the mixture using a syringe, followed by stirring at room temperature for 30 minutes. 0.0625 g of hydrochloric acid solution (37%) was diluted in 0.073 g of distilled water and 1.25 ml of butanol and slowly added to the mixed solution at room temperature for 15 minutes, followed by stirring for 30 minutes. The final mixture solution was applied onto a glass substrate using a syringe with a 0.2 polytetrafluoroethylene (PTFE) syringe filter, followed by spin coating at 2000 rpm for 60 seconds using a spin coating method. The formed thin film was dried in a hot plate at 60 ° C. for 30 minutes and then dried in a vacuum oven at 100 ° C. for 12 hours to prepare an organic-inorganic nanocomposite thin film. The properties of the prepared thin film are shown in Tables 1 and 2 below. (Metal alkoxide: bilic acid = 50:50)

Example 3

1.06 g of zinc nitrate hexahydrate and 2.5 ml of ethanol were added to a 25 ml round bottom flask and stirred for 45 minutes. A solution of 1.06 g of cholic acid in 2.5 ml of dimethylacetamide was slowly added to the mixture using a syringe, followed by stirring at room temperature for 45 minutes. 0.0625 g of glacial acetic acid was diluted in 0.073 g of distilled water and 1.25 ml of ethanol, and slowly added to the mixed solution at room temperature for 15 minutes, followed by stirring for 45 minutes. The final mixture solution was applied onto a glass substrate using a syringe with a 0.2 polytetrafluoroethylene (PTFE) syringe filter, followed by spin coating at 2500 rpm for 60 seconds using a spin coating method. The formed thin film was dried in a hot plate at 80 ° C. for 60 minutes and then dried in a vacuum oven at 100 ° C. for 24 hours to prepare an organic-inorganic nanocomposite thin film. The properties of the prepared thin film are shown in Tables 1 and 2 below. (Metal alkoxide: bilic acid = 50:50)

Example 4

1.06 g of zinc nitrate hexahydrate and 2.5 ml of ethanol were added to a 25 ml round bottom flask and stirred for 30 minutes. A solution of 1.06 g of deoxycholic acid dissolved in 2.5 ml of dimethylformamide was slowly added to the mixture using a syringe, followed by stirring at room temperature for 45 minutes. 0.0625 g of glacial acetic acid was diluted in 0.073 g of distilled water and 1.25 ml of ethanol, and slowly added to the mixed solution at room temperature for 15 minutes, followed by stirring for 45 minutes. The final mixture solution was applied onto a glass substrate using a syringe with a 0.2 polytetrafluoroethylene (PTFE) syringe filter, followed by spin coating at 2500 rpm for 60 seconds using a spin coating method. The formed thin film was dried in a hot plate at 60 ° C. for 60 minutes and then dried in a vacuum oven at 100 ° C. for 24 hours to prepare an organic-inorganic nanocomposite thin film. The properties of the prepared thin film are shown in Tables 1 and 2 below. (Metal alkoxide: bilic acid = 50:50)

Example 5

Into a 25 ml round bottom flask was added 1.06 g of a mixture of indium hydroxide (In (OH) ₃ ) and hydrochromite (hydroromarchite, Sn ₃ O ₂ (OH) ₂ ) and 2.5 ml of butanol and stirred for 60 minutes. A solution of 1.06 g of cholic acid dissolved in 2.5 ml of dimethylacetamide was slowly added to the mixture using a syringe, followed by stirring at room temperature for 60 minutes. 0.0625 g of ammonia water (27%) was diluted in 0.073 g of distilled water and 1.25 ml of butanol and slowly added to the mixed solution at room temperature for 15 minutes, followed by stirring for 60 minutes. The final mixture solution was applied onto a glass substrate using a syringe with a 0.2 polytetrafluoroethylene (PTFE) syringe filter and then spin coated at 500 rpm for 60 seconds using a spin coating method. The formed thin film was dried in a hot plate at 80 ° C. for 120 minutes and then dried in a vacuum oven at 100 ° C. for 48 hours to prepare an organic-inorganic nanocomposite thin film. The properties of the prepared thin film are shown in Tables 1 and 2 below. (Metal alkoxide: bilic acid = 50:50)

Example 6

Into a 25 ml round bottom flask was added 1.06 g of a mixture of indium hydroxide (In (OH) ₃ ) and hydrochromite (hydroromarchite, Sn ₃ O ₂ (OH) ₂ ) and 2.5 ml of butanol and stirred for 60 minutes. A solution of 1.06 g of deoxycholic acid dissolved in 2.5 ml of dimethylformamide was slowly added to the mixture using a syringe, followed by stirring at room temperature for 60 minutes. 0.0625 g of ammonia water (27%) was diluted in 0.073 g of distilled water and 1.25 ml of butanol and slowly added to the mixed solution at room temperature for 15 minutes, followed by stirring for 60 minutes. The final mixture solution was applied onto a glass substrate using a syringe with a 0.2 polytetrafluoroethylene (PTFE) syringe filter, followed by spin coating at 3000 rpm for 60 seconds using a spin coating method. The formed thin film was dried in a hot plate at 80 ° C. for 120 minutes and then dried in a vacuum oven at 100 ° C. for 48 hours to prepare an organic-inorganic nanocomposite thin film. The properties of the prepared thin film are shown in Tables 1 and 2 below. (Metal alkoxide: bilic acid = 50:50)

Example 7

In a 25 ml round bottom flask, 1.06 g of titanium butoxide and 2.5 ml of butanol were added and stirred for 30 minutes. A solution of 1.06 g of chenodeoxycholic acid dissolved in 2.5 ml of dimethylformamide was slowly added to the mixture using a syringe, followed by stirring at room temperature for 15 minutes. 0.0625 g of hydrochloric acid solution (37%) was diluted in 0.073 g of distilled water and 1.25 ml of butanol and slowly added to the mixed solution at room temperature for 15 minutes, followed by stirring for 15 minutes. The final mixture solution was applied onto a glass substrate using a syringe with a 0.2 polytetrafluoroethylene (PTFE) syringe filter, followed by spin coating at 3000 rpm for 60 seconds using a spin coating method. The formed thin film was dried in a hot plate at 60 ° C. for 30 minutes and then dried in a vacuum oven at 100 ° C. for 24 hours to prepare an organic-inorganic nanocomposite thin film. The properties of the prepared thin film are shown in Tables 1 and 2 below. (Metal alkoxide: bilic acid = 50:50)

Example 8

1.06 g of zinc nitrate hexahydrate and 2.5 ml of ethanol were added to a 25 ml round bottom flask and stirred for 30 minutes. A solution of 1.06 g of chenodeoxycholic acid dissolved in 2.5 ml of dimethylformamide was slowly added to the mixture using a syringe, followed by stirring at room temperature for 30 minutes. 0.0625 g of glacial acetic acid was diluted in 0.073 g of distilled water and 1.25 ml of ethanol, and slowly added to the mixed solution at room temperature for 15 minutes, followed by stirring for 60 minutes. The final mixture solution was applied onto a glass substrate using a syringe with a 0.2 polytetrafluoroethylene (PTFE) syringe filter, followed by spin coating at 2500 rpm for 60 seconds using a spin coating method. The formed thin film was dried in a hot plate at 80 ° C. for 60 minutes and then dried in a vacuum oven at 100 ° C. for 48 hours to prepare an organic-inorganic nanocomposite thin film. The properties of the prepared thin film are shown in Tables 1 and 2 below. (Metal alkoxide: bilic acid = 50:50)

Example 9

In a 25 ml round bottom flask, add 1.06 g of a mixture of indium hydroxide (In (OH) ₃ ) and hydroromarchite (hydroromarchite, Sn ₃ O ₂ (OH) ₂ ) and 2.5 ml butanol in a 25 ml round bottom flask. Stir for 60 minutes. A solution of 1.06 g of chenodeoxycholic acid dissolved in 2.5 ml of dimethylformamide was slowly added to the mixture using a syringe, followed by stirring at room temperature for 60 minutes. 0.0625 g of ammonia water (27%) was diluted in 0.073 g of distilled water and 1.25 ml of butanol and slowly added to the mixed solution at room temperature for 15 minutes, followed by stirring for 60 minutes. The final mixture solution was applied onto a glass substrate using a syringe with a 0.2 polytetrafluoroethylene (PTFE) syringe filter, followed by spin coating at 3500 rpm for 60 seconds using a spin coating method. The formed thin film was dried in a hot plate at 70 ° C. for 60 minutes and then dried in a vacuum oven at 100 ° C. for 48 hours to prepare an organic-inorganic nanocomposite thin film. The properties of the prepared thin film are shown in Tables 1 and 2 below. (Metal alkoxide: bilic acid = 50:50)

Example 10

In a 25 ml round bottom flask, 1.06 g of titanium butoxide and 2.5 ml of butanol were added and stirred for 45 minutes. A solution of 1.06 g of dehydrocholic acid in 2.5 ml of dimethylformamide was slowly added to the mixture using a syringe, followed by stirring at room temperature for 30 minutes. 0.0625 g of hydrochloric acid solution (37%) was diluted in 0.073 g of distilled water and 1.25 ml of butanol and slowly added to the mixed solution at room temperature for 15 minutes and then stirred for 45 minutes. The final mixture solution was applied onto a glass substrate using a syringe with a 0.2 polytetrafluoro ethylene (PTFE) syringe filter, followed by spin coating at 2700 rpm for 40 seconds using a spin coating method. The formed thin film was dried in a hot plate at 70 ° C. for 30 minutes and then dried in a vacuum oven at 90 ° C. for 18 hours to prepare an organic-inorganic nanocomposite thin film. The properties of the prepared thin film are shown in Tables 1 and 2 below. (Metal alkoxide: bilic acid = 50:50)

Example 11

In a 25 ml round bottom flask, 1.06 g of zinc nitrate hexahydrate and 2.5 ml of ethanol were added to a 25 ml round bottom flask and stirred for 30 minutes. A solution of 1.06 g of dihydrocholic acid in 2.5 ml of dimethylformamide was slowly added to the mixture using a syringe, followed by stirring at room temperature for 60 minutes. 0.0625 g of glacial acetic acid was diluted in 0.073 g of distilled water and 1.25 ml of ethanol, and slowly added to the mixed solution at room temperature for 30 minutes, followed by stirring for 60 minutes. The final mixture solution was applied onto a glass substrate using a syringe with a 0.2 polytetrafluoroethylene (PTFE) syringe filter, followed by spin coating at 2000 rpm for 60 seconds using a spin coating method. The formed thin film was dried in a hot plate at 60 ° C. for 80 minutes and then dried in a vacuum oven at 100 ° C. for 36 hours to prepare an organic-inorganic nanocomposite thin film. The properties of the prepared thin film are shown in Tables 1 and 2 below. (Metal alkoxide: bilic acid = 50:50)

Example 12

In a 25 ml round bottom flask, add 1.06 g of a mixture of indium hydroxide (In (OH) ₃ ) and hydroromarchite (hydroromarchite, Sn ₃ O ₂ (OH) ₂ ) and 2.5 ml butanol in a 25 ml round bottom flask. Stir for 45 minutes. A solution of 1.06 g of dihydrocholic acid in 2.5 ml of dimethylformamide was slowly added to the mixture using a syringe, followed by stirring at room temperature for 60 minutes. 0.0625 g of ammonia water (27%) was diluted in 0.073 g of distilled water and 1.25 ml of butanol and slowly added to the mixed solution at room temperature for 15 minutes, followed by stirring for 60 minutes. The final mixture solution was applied onto a glass substrate using a syringe with a 0.2 polytetrafluoroethylene (PTFE) syringe filter, followed by spin coating at 3000 rpm for 60 seconds using a spin coating method. The formed thin film was dried in a hot plate at 60 ° C. for 60 minutes and then dried in a vacuum oven at 100 ° C. for 18 hours to prepare an organic-inorganic nanocomposite thin film. The properties of the prepared thin film are shown in Tables 1 and 2 below. (Metal alkoxide: bilic acid = 50:50)

Example 13

As an example corresponding to Example 2, an organic-inorganic nanocomposite thin film was prepared in the same manner as in the case of using the bilic acid composition in place of deoxycholic acid, except for using a mixture of collic acid and deoxycholic acid in a weight ratio of 5: 5. , The composition and properties of the prepared thin film are shown in Table 1 and Table 2.

Example 14

As an example corresponding to Example 2, the organic acid-inorganic nanocomposite thin film was prepared in the same manner as that of the bilic acid composition except for using a mixture of collic acid and chenodioxycholic acid in a weight ratio of 5: 5 instead of deoxycholic acid. The composition and properties of the prepared thin film are shown in Tables 1 and 2 below.

Example 15

As an example corresponding to Example 2, the organic acid-inorganic nanocomposite thin film was prepared in the same manner except that the acid composition was used in the same manner except that the mixture of collic acid and dihydrocolic acid in a weight ratio of 5: 5 was used instead of deoxycholic acid. , The composition and properties of the prepared thin film are shown in Table 1 and Table 2.

Example 16

As an example corresponding to Example 6, the organic-inorganic nanocomposite thin film was prepared by performing the same method of the bilic acid composition except for using a mixture of collic acid and deoxycholic acid in a weight ratio of 5: 5 instead of deoxycholic acid. , The composition and properties of the prepared thin film are shown in Table 1 and Table 2.

Example 17

As an example corresponding to Example 6, the organic acid-inorganic nanocomposite thin film was prepared in the same manner as in the case of using the bilic acid composition instead of deoxycholic acid, using a mixture of collic acid and chenodioxycholic acid in a weight ratio of 5: 5. The composition and properties of the prepared thin film are shown in Tables 1 and 2 below.

Example 18

As an example corresponding to Example 6, an organic-inorganic nanocomposite thin film was prepared in the same manner except that the acid composition was used instead of the dioxycholic acid and a mixture of collic acid and dihydrocolic acid in a weight ratio of 5: 5. , The composition and properties of the prepared thin film are shown in Table 1 and Table 2.

Example 19

As an example corresponding to Example 1, an organic-inorganic nanocomposite thin film was prepared in the same manner as in the organic solvent composition except that a mixture of DMAc and tetrahydrofuran in a weight ratio of 7: 3 was used instead of DMAc. The composition and properties of are shown in Table 1 and Table 2 below.

Example 20

As an example corresponding to Example 19, the organic acid-inorganic nanocomposite thin film was prepared in the same manner as that of the valine acid composition except for using dioxycholic acid instead of collic acid, and the composition and properties of the prepared thin film are shown in the following table. 1 and Table 2.

Example 21

As an example corresponding to Example 19, the organic acid-inorganic nanocomposite thin film was prepared in the same manner as that of the valine acid composition except for using chenodioxycholic acid instead of collic acid, and the composition and properties of the prepared thin film were as follows. Table 1 and Table 2 are shown.

Example 22

As an example corresponding to Example 19, the organic acid-inorganic nanocomposite thin film was prepared in the same manner as in the case of using the bile acid composition instead of dihydrocholic acid in place of collic acid. 1 and Table 2.

Example 23

As an example corresponding to Example 1, an organic-inorganic nanocomposite thin film was prepared in the same manner as in the organic solvent composition except for using a mixture of DMF and toluene in a weight ratio of 9: 1 in place of DMAc, and the composition of the prepared thin film. And properties are shown in Tables 1 and 2 below.

Example 24

As an example corresponding to Example 19, the organic acid-inorganic nanocomposite thin film was prepared in the same manner as that of the valine acid composition except for using dioxycholic acid instead of collic acid, and the composition and properties of the prepared thin film are shown in the following table. 1 and Table 2.

Example 25

As an example corresponding to Example 19, the organic acid-inorganic nanocomposite thin film was prepared in the same manner as that of the valine acid composition except for using chenodioxycholic acid instead of collic acid, and the composition and properties of the prepared thin film were as follows. Table 1 and Table 2 are shown.

Example 26

As an example corresponding to Example 19, the organic acid-inorganic nanocomposite thin film was prepared in the same manner as in the case of using the bile acid composition instead of dihydrocholic acid in place of collic acid. 1 and Table 2.

Example 27

As an example corresponding to Example 5, the organic-inorganic nanocomposite thin film was manufactured by the same method as the spin speed of the thin film except that the rotational speed was coated at 2500 rpm, and the composition and characteristics of the prepared thin film are shown in Table 1 and Table. 2 is shown.

Example 28

As an example corresponding to Example 5, the organic-inorganic nanocomposite thin film was manufactured by the same method as that of coating the rotational speed at 3000 rpm during spin coating of the thin film, and the composition and properties of the prepared thin film are shown in Table 1 and Table. 2 is shown.

Example 29

As an example corresponding to Example 5, the organic-inorganic nanocomposite thin film was manufactured by the same method as that of coating the rotational speed at 3500 rpm during spin coating of the thin film, and the composition and properties of the prepared thin film are shown in Table 1 and Table. 2 is shown.

Example 30

As an example corresponding to Example 5, the organic-inorganic nanocomposite thin film was manufactured by performing the same process except that the rotational speed was coated at 4000 rpm during spin coating of the thin film, and the composition and characteristics of the prepared thin film are shown in Table 1 and Table. 2 is shown.

Example 31

As an example corresponding to Example 5, the organic-inorganic nanocomposite was carried out in the same manner except that the amount of dimethylacetamide was increased from 2.5ml to 3.0ml when the coating composition was prepared, and the rotational speed was coated at 2500rpm during thin film spin coating. A thin film was prepared, and the composition and properties of the prepared thin film are shown in Tables 1 and 2 below.

Example 32

As an example corresponding to Example 5, the organic-inorganic nanocomposite was carried out in the same manner except that the amount of dimethylacetamide was increased from 2.5ml to 3.5ml when the coating composition was prepared, and the rotational speed was coated at 2500rpm during thin film spin coating. A thin film was prepared, and the composition and properties of the prepared thin film are shown in Tables 1 and 2 below.

Composition of the composition division Composition menstruum catalyst metal
Alkoxide Baishan Alcohol Organic solvent Example 1 titanium Collic acid Butanol DMAc Hydrochloric acid Example 2 titanium Deoxycholic acid Butanol DMF Hydrochloric acid Example 3 zinc Collic acid ethanol DMAc Acetic acid Example 4 zinc Deoxycholic acid ethanol DMF Acetic acid Example 5 indium Collic acid Butanol DMAc ammonia Example 6 indium Deoxycholic acid Butanol DMF ammonia Example 7 titanium Chenodioxycholic acid Butanol DMF Hydrochloric acid Example 8 zinc Chenodioxycholic acid ethanol DMF Acetic acid Example 9 indium Chenodioxycholic acid Butanol DMF ammonia Example 10 titanium Dihydrocholic acid ethanol DMF Hydrochloric acid Example 11 zinc Dihydrocholic acid ethanol DMF Acetic acid Example 12 indium Dihydrocholic acid ethanol DMF ammonia Example 13 titanium Cholic acid: Deoxycholic acid (5: 5) ethanol DMF Hydrochloric acid Example 14 titanium Cholic acid: Cenodioxycholic acid (5: 5) ethanol DMF Hydrochloric acid Example 15 titanium Cholic acid: dihydrocholic acid (5: 5) ethanol DMF Hydrochloric acid Example 16 indium Cholic acid: Deoxycholic acid (5: 5) Butanol DMF ammonia Example 17 indium Cholic acid: Cenodioxycholic acid (5: 5) Butanol DMF ammonia Example 18 indium Cholic acid: dihydrocholic acid (5: 5) Butanol DMF ammonia Example 19 titanium Collic acid Butanol DMAc: THF (7: 3) Hydrochloric acid Example 20 titanium Deoxycholic acid Butanol DMAc: THF (7: 3) Hydrochloric acid Example 21 titanium Chenodioxycholic acid Butanol DMAc: THF (7: 3) Hydrochloric acid Example 22 titanium Dihydrocholic acid Butanol DMAc: THF (7: 3) Hydrochloric acid Example 23 titanium Collic acid Butanol DMF: toluene (9: 1) Hydrochloric acid Example 24 titanium Deoxycholic acid Butanol DMF: toluene (9: 1) Hydrochloric acid Example 25 titanium Chenodioxycholic acid Butanol DMF: toluene (9: 1) Hydrochloric acid Example 26 titanium Dihydrocholic acid Butanol DMF: toluene (9: 1) Hydrochloric acid Example 27 indium Collic acid Butanol DMAc ammonia Example 28 indium Collic acid Butanol DMAc ammonia Example 29 indium Collic acid Butanol DMAc ammonia Example 30 indium Collic acid Butanol DMAc ammonia Example 31 indium Collic acid Butanol DMAc ammonia Example 32 indium Collic acid Butanol DMAc ammonia

Optical and Electrical Properties of Organic-Inorganic Nanocomposites division Refractive index Transmittance (%) Sheet resistance (Ω /) Thin film thickness (nm) 1.891 90.17 ? 207.3 Example 1 1.778 99.85 ? 218.1 Example 2 1.764 91.42 ? 227.8 Example 3 1.737 91.58 ? 221.5 Example 4 ? 98.45 121 564.1 Example 5 ? 98.91 270 213.5 Example 6 1.750 92.14 ? 191.6 Example 7 1.671 92.20 ? 219.1 Example 8 ? 99.05 265 197.3 Example 9 1.706 97.45 ? 192.3 Example 10 1.639 97.55 ? 213.4 Example 11 ? 98.95 267 238.0 Example 12 1.742 96.99 ? 226.4 Example 13 1.611 98.45 ? 214.0 Example 14 1.607 97.98 ? 186.6 Example 15 ? 99.20 266 218.2 Example 16 ? 99.14 259 187.8 Example 17 ? 99.25 254 233.9 Example 18 1.801 98.13 ? 241.3 Example 19 1.732 97.24 ? 230.7 Example 20 1.623 97.58 ? 214.6 Example 21 1.703 96.99 ? 194.4 Example 22 1.594 98.75 ? 207.8 Example 23 1.664 97.49 ? 246.1 Example 24 1.770 98.10 ? 268.6 Example 25 1.721 97.21 ? 179.6 Example 26 ? 99.21 231 245.2 Example 27 ? 99.30 270 238.4 Example 28 ? 99.34 361 221.5 Example 29 ? 99.51 387 200.6 Example 30 ? 99.43 341 215.7 Example 31 ? 99.77 550 89.4

The high refractive index organic-inorganic nanocomposite transparent film according to the present invention not only increases thermal stability by introducing organic-gel, but also has a functional group that can easily react with other molecules, thereby covalently bonding with different molecules. Since it is easy to prepare a composition for a solution process, the organic-inorganic nanocomposite according to the present invention is based on a simple coating method such as spraying, spin coating, electrophoretic deposition, casting, inkjet printing and offset printing It can be useful for manufacturing high refractive index organic-inorganic nanocomposite transparent film in various solution processing fields.

1 illustrates a chemical reaction in which a composition of a bile acid derivative and a metal alkoxide according to an embodiment of the present invention forms a composition for a transparent organic-inorganic composite thin film through a sol-gel reaction.

2 shows the method of Example 2 (solid black line), Example 23 (solid blue line), Example 20 (green solid line), Example 14 (red solid line) and Example 22 (yellow solid line) according to the present invention. It is a figure which shows the refractive index according to the wavelength of the obtained transparent organic-inorganic composite thin film.

Fig. 3 is obtained by the method of Example 31 (solid solid line), Example 29 (solid blue line), Example 23 (green solid line), Example 19 (black solid line), Example 6 (light solid line) of the present invention. The light transmittance of the transparent organic-inorganic composite thin film is shown.

Claims (11)

Metal alkoxides; Bilic acid or bilic acid derivative; Water, an organic solvent or a mixed solvent thereof; And Transparent organic-inorganic composite thin film composition comprising a catalyst. delete The method of claim 1, The metal alkoxide is a composition for a transparent organic-inorganic composite thin film, characterized in that it comprises at least one selected from Sn, Ti, In, Al, Sb, Hf, Zr, Cu, Ca, Si and Mg. The method of claim 1, The valic acid or the valine acid derivative may be cholic acid, chenodioxycholic acid, dihydroxycholic acid, dioxycholic acid, hiyodioxycholic acid, lysocholic acid, sodium chrygonodioxycholate, sodium taurodioxycholate Sodium Taurocholate Hydrate, Sodium Dihydrocholate, Sodium Dioxycholate, Ursodioxycholic Acid, Sodium Cholate Hydrate, Hiyodioxycholic Acid Methyl Ester, 5-cholanic-3,12-diol 3-acetate Methyl Ester Transparent organic-inorganic complex comprising at least one selected from 5-cholanic acid-3-one, 5-cholanic acid 3,7-dione methyl ester and 5-cholanic acid-3,7-dione Thin film composition. The method of claim 1, The solvent is a composition for a transparent organic-inorganic composite thin film comprising at least one selected from water, alcohols, ketones, ethers, amides and benzenes. The method of claim 1, The catalyst is a transparent organic-inorganic composite thin film composition comprising at least one selected from hydrochloric acid, sulfuric acid, ammonia and acetic acid. Mixing the metal alkoxide with the first organic solvent to form a first mixture; Mixing the bile acid or bile acid derivative with a second organic solvent to form a second mixture; Mixing the first mixture and the second mixture, and adding a catalyst to form a transparent thin film composition; And Method for producing a transparent organic-inorganic composite thin film comprising the step of applying the composition for the transparent thin film on a substrate. The method of claim 7, wherein The first organic solvent includes an alcohol solvent, and the second organic solvent comprises an amide solvent. The method of claim 7, wherein The step of applying the composition for a transparent thin film on a substrate is a method of manufacturing a transparent organic-inorganic composite thin film, characterized in that carried out by any one selected from spraying, spin coating, electrophoretic deposition, casting, inkjet printing and offset printing. The method according to any one of claims 7 to 9, Transparent organic-inorganic composite thin film prepared by the above method. The method of claim 10, Transparent organic-inorganic composite thin film, characterized in that the thickness of the thin film is 80nm to 600nm.

Images