KR100929547B1 - Gas barrier membrane using oligosiloxane hybrid coating - Google Patents

Abstract

The present invention relates to an oligosiloxane hybrid using a condensation reaction of an organosilane and a gas barrier film using the same. More specifically, oligosiloxane hybrid, characterized in that it comprises at least one organic group or an organic functional group in the center of the inorganic network structure having a high degree of condensation by the non-aqueous condensation reaction of the organosilanediol and the organoalkoxysilane, and It provides a gas barrier film having excellent gas barrier properties consisting of a single layer or multiple layers using the oligosiloxane hybrid.

Oligosiloxane Hybrid, Condensation Reaction, Organoalkoxysilane, Organosilane Diol, Gas Blocking Membrane

Description

Gas barrier layer using oligosiloxanes hybrid coating

The present invention relates to a gas barrier membrane using an oligosiloxane hybrid prepared from the condensation reaction of an organosilane. More specifically, by using the non-aqueous condensation reaction of the organosilanediol and the organoalkoxysilane, the oligosiloxane hybrid, characterized in that it comprises at least one organic group or organic functional group in the center of the inorganic network structure with high degree of condensation The present invention relates to a gas barrier film having excellent gas barrier properties consisting of a single layer or a multilayer.

Many types of products, such as electronics and medicines, are very sensitive to the surrounding environment, that is, gases and liquids, and thus react with gases or liquids and degrade their quality. In order to maintain long-term storage and performance, such electronic products and medicines employ a barrier that can prevent gas or liquid penetration and protect the product.

In particular, organic electronic devices such as organic thin film transistors (OTFTs) and organic light emitting devices (OLEDs) have characteristics that are very vulnerable to the surrounding environment. Moisture and oxygen react with organic substances such as organic semiconductors and organic light-emitting bodies to deteriorate their properties and shorten their lifespan. In particular, the organic electronic device has an advantage of manufacturing a flexible electronic device using a flexible substrate such as a polymer. However, the polymer substrate has a very high transmittance of water or oxygen, thereby degrading the organic material. Therefore, it is necessary to introduce a protective device that can block the inflow of water and oxygen and protect organic matter.

The performance of gas barrier membranes required by OLEDs requires that moisture and oxygen transmittances be less than 10 ^-6 g / m ² / day and 10 ^-5 cc / m ² / day / bar, respectively. In the case of OLED, the gas barrier property is secured by encapsulating a moisture absorbent and a glass or metal can with an ultraviolet curable resin in order to secure a lifetime. However, the use of glass or metal cans increases the thickness of the organic electronic device, and thus requires a sealing technique using a thin film. Carcia et al [Appl. Phys. Lett. 89, 031915 (2006) reported that a single layer using ALD can provide sufficient gas barrier effect. However, ALD uses a vacuum process and is difficult to apply in large areas. In general, a gas barrier film using a single layer inorganic thin film has a high gas permeability due to defects in the material, and thus a gas barrier film using a multilayer film is used. US Patent 4,954,371 and US Patent 6,150,187 disclose a gas barrier film in which a moisture barrier polymer layer and an oxygen barrier polymer layer are alternately stacked. U.S. Patent 5,260,095, U.S. Patent 7,018,713, U.S. Publication 2003/0203210 and the like disclose the formation of a gas barrier film in which a polymer layer and an inorganic layer are alternately stacked. U. S. Patent 6,962, 671 and U. S. Patent 6,623, 861 disclose a flexible substrate having a very low gas permeability in which at least 50 layers of a polymer layer and an inorganic layer are laminated. Kim et al [J. Vac. Sci. Technol. A 23, 971, 2005] report a gas barrier using a concentration gradient layer of SiO x N y Cz layer.

Until now, the technology for manufacturing gas barrier membranes uses vacuum equipment for both organic and inorganic substances, and most organic membranes use organic / inorganic multilayer membranes of four or more layers because they have poor water and oxygen barrier properties. Complicating the process of the organic electronic device that requires is increasing the production cost. Thus, to simplify the process and reduce production costs, new polymer materials and technologies with good gas barrier properties that can replace organic layers are needed.

In the case of the polymer used in the gas barrier membrane having the best gas barrier property, the free volume is very large inside the material, and thus the gas (oxygen, moisture, etc.) to be blocked easily penetrates. In addition, when the inorganic layer is formed on the polymer layer, damage may be caused by plasma or high energy ions, which may cause defects on the surface or the inside of the polymer layer. Improving the gas barrier properties requires new materials with very small free volumes, low gas permeability and low process temperatures. Korean Patent Application No. 1990-0012612 discloses that an inorganic siloxane thin film is formed through a hydrolysis-condensation reaction using a silane monomer or a mixture of silane monomers and water to be applied as a gas barrier layer. However, since the viscosity of the prepared solution is very low, it is difficult to form the required thickness as a gas barrier film, and a high temperature process of more than 500 degrees is required to obtain a thin film having excellent gas barrier properties. U.S. Patent 6,503,634 and U.S. Patent 6,709,757 disclose the application of organic-inorganic hybrids to gas barrier membranes using hydrolysis and condensation reactions. However, since the disclosed organic-inorganic hybrid has insufficient condensation reaction, there are many unreacted functional groups in the material, so that the stability of the material decreases and the barrier property is impeded. do.

The present invention was derived to solve the problems of the prior art described above, forming a dense inorganic network structure to which an organic group or an organic functional group is provided, and thus a gas barrier membrane comprising an oligosiloxane hybrid having a stable and highly condensed structure. The purpose is to provide.

In addition, another object of the present invention is to provide a multi-layered gas barrier membrane having improved gas barrier properties by stacking a highly condensed oligosiloxane hybrid and an inorganic layer having a very high condensation degree.

Another object of the present invention is to provide a substrate for manufacturing an electronic device having excellent light transmittance and gas barrier properties including the gas barrier film, and an organic electronic device including the gas barrier film.

In order to achieve the above object, the present invention provides a gas barrier layer including an oligosiloxane coating layer formed by applying an oligosiloxane hybrid prepared through a condensation reaction of an organoalkoxysilane and an organosilanediol on a device or a substrate requiring gas barrier properties. to provide.

The oligosiloxane hybrid is a compound in which inorganic components and organic components or organic functional groups are bonded to the result in a molecular unit, and is prepared through a condensation reaction of an organic silane.

The oligosiloxane hybrid according to the present invention is prepared through the condensation reaction of an organoalkoxysilane and organosilanediol, and the degree of condensation is high, and the coating layer is very dense when the coating layer is formed by applying it on a device or a substrate requiring gas barrier properties. There is no pinhole and the adhesion to the substrate is very good, and thus has excellent gas barrier properties compared to the gas barrier layer using a conventional polymer layer.

In another aspect, the present invention provides a gas barrier film having a multi-layered gas barrier film having a two-layered gas barrier film or an oligosiloxane coating layer and an inorganic layer alternately stacked with an inorganic layer formed on the oligosiloxane coating layer.

In another aspect, the present invention provides a substrate for manufacturing an electronic device excellent in transparency and gas barrier properties, and more preferably a flexible substrate for manufacturing an electronic device by including the gas barrier film, an organic light emitting device, an organic solar cell, etc. comprising the gas barrier film Provided are organic electronic devices.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a gas barrier film having excellent gas barrier properties using an oligosiloxane hybrid, and more particularly, to a coating layer formed by coating an oligosiloxane hybrid having a high degree of condensation prepared through a condensation reaction of an organoalkoxysilane and an organosilanediol. It relates to a gas barrier film, a substrate for manufacturing an electronic device including the same, and an organic electronic device including the same. The gas barrier film according to the present invention has excellent mechanical properties, thermal stability, coating properties, and excellent gas barrier properties.

The gas barrier film according to the present invention includes an oligosiloxane hybrid coating layer prepared from the following steps.

a) preparing an oligosiloxane hybrid by a condensation reaction of an organoalkoxysilane and an organosilanediol; And

b) forming a coating layer by applying a coating liquid containing the oligosiloxane hybrid on an element or a substrate requiring gas barrier properties.

The oligosiloxane hybrid of step a) is prepared through the sol-gel reaction, and in particular, the condensation reaction of the organoalkoxysilane and the organosilanediol according to the present invention is added to the non-aqueous sol-gel reaction as shown in the following scheme. Without condensation reaction of organoalkoxysilane and organosilanediol. The non-aqueous sol-gel method differs from the traditional hydrophilic sol-gel reaction in that water is used. The hydrous sol-gel method is difficult to form a complex oxide due to the difference in reaction rate between the two materials, and thus the selection of precursors is restricted. In addition, there is a limit inevitably generated by using water, for example, a high temperature heat treatment process is required, and the stability of the material is deteriorated by unreacted hydroxyl groups present in the material. However, the non-aqueous sol-gel reaction can be used to form organic oligosiloxane nano hybrids using various precursors as well as composite oxides, and can overcome the disadvantages of the hydrosol-gel method.

As can be seen from the above reaction scheme, a condensation reaction of a hydroxyl group of an organosilane diol as a starting material with an alkoxy group of an organoalkoxysilane as another monomer forms an inorganic network structure, and organic groups such as R 'and R "are formed around the inorganic network structure. To form a modified oligosiloxane hybrid.

When the oligosiloxane hybrid is prepared by using the non-aqueous sol-gel reaction, the oligosiloxane hybrid is formed through the condensation reaction of the hydroxyl group-modified organic silane and the organic silane, so that the reaction temperature is lowered and the sol-gel reaction is performed. A catalyst may be preferably added to facilitate this. As a usable catalyst, metal hydroxides such as barium hydroxide, strontium hydroxide and the like can be used. The amount of catalyst to be added is not particularly limited and it is sufficient to add 0.0001-10 mol% of the monomer. The reaction is sufficient to stir at about 6 to 72 hours at room temperature, and in order to promote the reaction rate and to proceed with a complete condensation reaction, inducing condensation reaction at 0 to 100 ℃, preferably 40 to 80 ℃ for 1 to 10 hours. Inorganic mesh structure can be formed.

In addition, by-product alcohol is present in the oligosiloxane hybrid prepared through the condensation reaction, which is carried out under atmospheric pressure and reduced pressure at 0 ° C. to 120 ° C., preferably at −0.1 MPa and 40 to 80 ° C. for 10 minutes to 1 hour. Can be removed.

The organoalkoxysilane may be selected from a compound represented by the following Formula 1 or a mixture thereof as a silane compound having a substituted or unsubstituted organic chain and an alkoxy group bonded to a functional group.

[Formula 1]

[In Formula 1, R ¹ is (C ¹ -C 20) alkyl, (C 3 -C 8) cycloalkyl, (C 3 -C 8) alkyl substituted with (C 3 -C 8) cycloalkyl, (C 2 -C 20) alkenyl, (C 2 ~ C20) alkynyl, (C6 ~ C20) aryl is selected from, wherein R ¹ is an acryl group, methacryl group, allyl group, halogen group, amino group, mercapto group, ether group, ester group, (C1-C20) alkoxy May have one or more functional groups selected from groups, sulfone groups, nitro groups, hydroxyl groups, cyclobutene groups, carbonyl groups, carboxyl groups, alkyd groups, urethane groups, vinyl groups, nitrile groups, and epoxy groups; R ² is straight or branched chain (C 1 -C 7) alkyl.]

More specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, propylethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrie Methoxysilane, vinyltripropoxysilane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- (3-acryloxy-2-hydroxy Roxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltripropoxysilane, 3-acryloxypropylmethylbis (trimethoxy) silane , 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyl Propoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltripropoxysilane, N- (aminoethyl-3 -Aminopropyl) trimethoxysilane, N- (2-aminoethyl-3-aminopropyl) triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, chloropropyltrimethoxy It may be selected from silane, chloropropyltriethoxysilane, heptadecafluorodecyltrimethoxysilane or a mixture thereof, but is not necessarily limited thereto.

The organosilanediol may be selected from a compound of Formula 2 or a mixture thereof as a silane compound in which a functional group is substituted or unsubstituted, an organic chain and two hydroxyl groups are bonded thereto.

[Formula 2]

[R ³ in Formula 2 And R ⁴ is independently (C 1 -C 20) alkyl, (C 3 -C 8) cycloalkyl, (C 3 -C 8) alkyl substituted with (C 3 -C 8) cycloalkyl, (C 2 -C 20) alkenyl, (C 2 -C 20 ) Alkynyl, (C6 ~ C20) aryl and R ³ And R ⁴ is an acryl group, methacryl group, allyl group, halogen group, amino group, mercapto group, ether group, ester group, (C1-C20) alkoxy group, sulfone group, nitro group, hydroxy group, cyclobutene group, It may have one or more functional groups selected from carbonyl group, carboxyl group, alkyd group, urethane group, vinyl group, nitrile group, and epoxy group.]

Specific compounds include, but are not limited to, diphenylsilanediol, diisobutylsilanediol or mixtures thereof.

The oligosiloxane hybrid prepared in step a) has a degree of condensation of at least 60%, specifically, 60 to 99% and more preferably 90 to 99%. The degree of condensation of the oligosiloxane hybrid is evaluated using ²⁹ Si NMR. As shown in FIG. 1, the species marked D in the ²⁹ Si NMR spectra are those having two reactors of alkoxysilanes, and the species marked T are those having three reactors of alkoxysilanes. Using the area of each peak of the ²⁹ Si NMR spectra, the degree of condensation (DC) is quantitatively calculated through the following equation.

The high degree of condensation of the oligosiloxane hybrid means that the inorganic mesh structure inside the oligosiloxane hybrid is densely formed, which means that the free volume of the oligosiloxane hybrid is small so that gas penetration can be effectively blocked.

Step b) is a step of forming a coating layer by coating a coating liquid comprising a oligosiloxane hybrid prepared in step a) on a substrate.

The coating solution including the oligosiloxane hybrid may be added to the solvent to control the viscosity of the oligosiloxane hybrid and to stabilize the resin. The solvent that can be used is not particularly limited but is preferably an aliphatic hydrocarbon solvent such as hexane or heptane or a ketone solvent such as methyl isobutyl ketone, 1-methyl-2-pyrrolidinone, cyclohexanone, acetone or tetrahydro. Ether solvents such as furan, isopropyl ether and propylene glycol propyl ether or acetate solvents such as ethyl acetate, butyl acetate and propylene glycol methyl ether acetate or alcohol solvents such as isopropyl alcohol and butyl alcohol or dimethylacetamide and dimethyl Amide solvents such as formamide or silicone solvents or mixtures thereof may be used.

The oligosiloxane hybrid preferably has a molecular weight of 10000 or less and more preferably has a value between 100 and 5000, and improves secondary performance, for example, mechanical, thermal and coating properties, and improves gas barrier properties. In order to add an appropriate amount of curing agent, dyes, pigments and surfactants, antioxidants to the coating liquid containing the oligosiloxane hybrid, and may further add nano-sized oxide or nitride particles to further improve the gas barrier properties. This is not restrictive.

Application methods of the oligosiloxane hybrid coating solution usable in the present invention include, but are not limited to, spin coating, dip coating, spray coating, flow coating, and screen printing.

After the application is completed, a step of evaporating the solvent may be included if necessary, and may include the step of thermosetting or photocuring when the organic functional group capable of thermal polymerization or photopolymerization is modified. When the oligosiloxane hybrid has a photocurable or thermosetting functional group, a monomer having a photocurable or thermosetting functional group or other kinds of functional groups may be added to adjust the density, free volume, adhesion to the substrate, refractive index, and the like of the oligosiloxane hybrid. In the preparation of the oligosiloxane hybrid, the oligosiloxane hybrid prepared when the organic alkoxysilane or the organic silane diol has a thermosetting or photocurable functional group such as an epoxy group, a (meth) acryl group, a vinyl group, an amino group, or a hydroxy group Since a more dense coating layer is formed by performing a thermal curing or photocuring step between organic groups, there is an advantage in that a coating layer having better mechanical properties, thermal characteristics, and gas barrier properties can be manufactured.

The thermosetting or photocuring step may be performed under a commonly used catalyst. In addition, after thermal curing or photocuring may include a step of heat treatment at 150 ℃ or less, specifically 50 to 150 ℃, preferably 120 ℃ or less, specifically 50 to 120 ℃. If the curing temperature is too high, more than 150 degrees, there is a problem that can destroy the bond chain of the organic functional period, if too low may not remove the incidentally added solvent.

The oligosiloxane hybrid coating resin prepared by the present invention undergoes a condensation reaction and has various kinds of organic functional groups, and the degree of condensation of the inorganic mesh structure is 60% or more, more preferably 90% or more, thereby providing excellent coating properties on various substrates. Since the inorganic and organic components are uniformly mixed at the molecular level, the stability of the resin is very high, the mechanical and thermal properties are excellent, and the light transmittance is excellent. In addition, since various organic groups or organic functional groups can be provided, various physical properties can be controlled and gas barrier properties are excellent.

Gas barrier properties are evaluated using a calcium test. Calcium, when exposed to humidity, causes calcium to denature into oxides or hydrates, resulting in a change in electrical resistance. This change in resistance is used to evaluate the gas barrier properties. The calcium test is performed by vacuum depositing a calcium layer over a patterned aluminum or silver electrode and then forming a gas barrier directly over the calcium layer or placing a gas barrier formed on the polymer substrate. Subsequently, the characteristics of the gas barrier membrane are evaluated by exposing calcium bound to the gas barrier membrane to a humid atmosphere having a relative humidity of 100% and measuring a change in electrical resistance.

The oligosiloxane hybrid coating layer according to the invention is very dense, without pinholes and very good adhesion to the substrate. In addition, since the oligosiloxane hybrid coating layer has a very smooth surface, the area of contact with the infiltrating gas is small, so the gas barrier property is excellent and the pinholes or defects of the inorganic layer that can be formed on the oligosiloxane hybrid coating layer are excellent. ) Can be used to offset. In addition, since the damage due to plasma, high energy ions, heat, etc., which may occur when forming the inorganic layer is less than that of the polymer layer, the gas barrier property is excellent.

The gas barrier layer using the oligosiloxane high lead may be formed on a calcium substrate, an upper structure of an OLED, or a flexible substrate such as a polymer substrate, and the gas barrier layer according to the present invention may be formed of an oligosiloxane hybrid coating layer alone, or It may have a multilayer structure having one or more gas barrier layers formed over the siloxane hybrid coating layer. The gas barrier layer formed on the oligosiloxane hybrid coating layer may be a composite layer including oxide or nitride nanoparticles together with the oligosiloxane hybrid, may be composed of an inorganic layer, or as shown in FIG. 2. ) May be composed of a multilayer film in which a plurality of layers selected from the inorganic layers 41 and 42 and the aforementioned oligosiloxane hybrids 31 and 32 are alternately formed on the substrate 10. Compared to the gas barrier film of the oligosiloxane hybrid coating layer alone, the gas barrier is significantly improved when the composite layer or the multilayer film is laminated on the oligosiloxane hybrid coating layer. The thickness of the oligosiloxane hybrid coating layer according to the invention is advantageously in the range of 0.1 μm to 10 μm and preferably in the range of 0.1 μm to 2 μm. When the thickness of the oligosiloxane hybrid coating layer is less than 0.1 μm, there is a problem in that the gas blocking effect is insufficient and the pinhole removing effect of the upper inorganic layer is inferior. . Each inorganic layer can be selected from transparent oxides, nitride oxynitrides and combinations thereof. For example, the inorganic layer includes oxides such as silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, indium oxide, indium tin oxide, tin oxide, and oxy nitrides such as silicon oxynitride (SiON) and aluminum oxynitride material (AlON). This is available. The inorganic layer may be formed by various kinds of thin film formation processes such as heat evaporation, electron beam evaporation, sputtering, chemical vapor deposition, and plasma chemical vapor deposition. The thickness of the inorganic layer used for the multilayer gas barrier film is in the range of 5 nm to 500 nm and preferably in the range of 30 nm to 150 nm. If the thickness of the inorganic layer is less than 5nm, there is a problem that the gas barrier effect is not sufficient and the pinhole removal effect of the upper inorganic layer is inferior, and if it is too thick exceeding 500nm, it may be disadvantageous from an economical point of view.

The oligosiloxane hybrid coating layer according to the present invention has a light transmittance of 80% or more, specifically, 80 to 95% in the visible region, and 80 even when a multilayer gas barrier layer is formed by stacking a transparent oxide layer such as aluminum oxide. It may have a light transmittance of% or more, specifically 80 to 95%.

The present invention provides a substrate for manufacturing an electronic device comprising the gas barrier film according to the present invention. The substrate for manufacturing the electronic device may be a flexible substrate such as a calcium substrate or a polymer substrate, and the material of the polymer substrate may be polyamide, polyimide, polyether sulfone, polycarbonate, polyethylene naphthalate, polyester, Polyethylene terephthalate or mixtures thereof, and the like.

In another aspect, the present invention provides a substrate having excellent gas barrier properties by forming a thicker by adjusting the viscosity of the oligosiloxane hybrid to be used as a substrate and alternately laminated a plurality of oligosiloxane hybrid coating or inorganic layer thereon. Since the oligosiloxane hybrid can easily form a thickness of 100 μm or more with a single coating through viscosity control, it can be used as a substrate, and a plurality of alternating oligosiloxane hybrid coating layers or oligosiloxane hybrid coating layers and inorganic layers thereon can be used. The multilayered gas barrier layer is formed by laminating to provide a flexible substrate having excellent gas barrier properties.

In another aspect, the present invention provides an organic electronic device comprising a gas barrier film according to the present invention. The organic electronic device may be an organic thin film transistor, an organic light emitting device, or an organic solar cell.

As described above, the gas barrier layer using the oligosiloxane hybrid according to the present invention is very dense, has no pinholes, and has excellent adhesion to the substrate, and thus has excellent gas barrier properties compared to the gas barrier layer using the conventional polymer layer. Since the oligosiloxane hybrid can be formed by using a solution process without using a vacuum equipment, etc., compared to a gas barrier film using a conventional polymer layer, it is possible to form a cheap and excellent gas barrier film. Since the oligosiloxane hybrid is optically transparent, the gas barrier film using the oligosiloxane hybrid is also transparent, so that the oligosiloxane hybrid can be used as a gas barrier film of a display such as an OLED.

In addition, since the oligosiloxane hybrid coating layer has a very dense and smooth surface, it has an excellent gas barrier property and can offset the pinholes or defects of the inorganic layer that can be formed on the oligosiloxane hybrid coating layer. There is this. In addition, since damage due to plasma, high energy ions, heat, etc., which may occur when forming the inorganic layer is less than that of the conventional polymer layer, the gas barrier film having a multilayered structure has excellent gas barrier properties.

The invention is illustrated by the following examples. However, these do not limit the technical scope of the present invention.

[Organic Oligosiloxane Preparation]

Example 1 Preparation of Oligosiloxane Hybrid Modified with Epoxy and Phenyl Groups

2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS, Aldrich) and diphenylsilanediol (DPSD) were added in a 200 ml flask with a 2: 3 molar ratio. % Was added and the mixture was stirred at 80 ° C. for 72 hours, and then propylene glycol methyl ether acetate (PGMEA, Aldrich) was added. An organic oligosiloxane resin obtained by modifying an epoxy group and a phenyl group was obtained. The degree of condensation of the obtained organic oligosiloxane was 97% when evaluated using ²⁹ Si NMR (FIG. 1). In addition, as a result of analyzing the molecular weight using MALDI-TOF, the molecular weight of the oligosiloxane hybrid prepared according to the present example has a distribution of 300 to 3000 and a number average molecular weight of 1200.

Example 2 Preparation of Oligosiloxane Hybrid Modified with Methacrylic Group, Floro Group and Phenyl Group

3-methacrylopropyltrimethoxysilane (MPTMS, Aldrich) and perfluoroalkoxysilane (PFAS, Gelist) are mixed at a molar ratio of 3: 1, and then diphenysilanediol is 3-methacrylopropyltrimethoxy Add so that the molar ratio is 2: 3 relative to the sum of silane (MPTMS, Aldrich) and perfluoroalkoxysilane (PFAS). To promote the reaction, barium hydroxide was added as a catalyst to 0.1 mol% of silane and stirred at 80 ° C. for 72 hours, followed by addition of propylene glycol methyl ether acetate (PGMEA, Aldrich) and using a reduced pressure evaporator -0.1 MPa, 60 After the reaction at 30 ° C. for 30 minutes, methanol remaining in the resin was removed to obtain an organic oligosiloxane resin modified with an epoxy group, a fluoro group and a phenyl group. The degree of condensation of the obtained organic oligosiloxane was 72% when evaluated using ²⁹ Si NMR. In addition, as a result of analyzing the molecular weight using MALDI-TOF, the molecular weight of the oligosiloxane hybrid prepared according to the present example has a distribution of 300 to 3000 and a number average molecular weight of 1400.

[Gas barrier film manufacturing]

The Ca layer for evaluating the gas barrier properties was prepared by thermal evaporation on an aluminum pattern using a metal mask engraved with a pattern on a soda lime glass substrate. The Ca deposited glass substrates were transferred and stored in a glove box.

Example 3 Fabrication of Single Layer Gas Blocking Membrane Using Oligosiloxane Hybrid Coating Layer

The oligosiloxane hybrid coating layers prepared in Examples 1 and 2 used as gas barrier films were formed on the thermally deposited Ca layer by spin coating to a thickness of 2 μm. In order to remove impurities in the organic oligosiloxane solution diluted with PGMEA, spin coating was performed through a PTFE (polytetrafluoroethylene) membrane syringe filter having 0.45 μm pores. The coating film prepared by the above method was first irradiated with ultraviolet light for 3 minutes using a UV lamp to cause a photopolymerization reaction, and then an organic oligosiloxane hybrid coating layer was obtained through heat treatment at 120 ° C. for 2 hours. The surface roughness (RMS roughness) of the oligosiloxane hybrid coating layer formed at this time has a very low value of 1 nm or less. The Ca layer coated with the oligosiloxane hybrid coating layer was exposed to a humid atmosphere having a relative humidity of 100% to measure the change in electrical resistance, thereby evaluating the characteristics of the gas barrier membrane, and the transmittance of moisture is shown in Table 1 below.

<Example 4> Preparation of a two-layer gas barrier film using an oligosiloxane hybrid coating layer and an aluminum oxide layer

The oligosiloxane hybrid coating layer prepared in Example 1 used as a gas barrier layer was formed on the thermally deposited Ca layer by spin coating to a thickness of 2 μm. In order to remove impurities in the organic oligosiloxane solution diluted with PGMEA, spin coating was performed through a PTFE (polytetrafluoroethylene) membrane syringe filter having 0.45 μm pores. The coating film prepared by the above method was first irradiated with ultraviolet light for 3 minutes using a UV lamp to cause a photopolymerization reaction, and then an organic oligosiloxane hybrid coating layer was obtained through heat treatment at 120 ° C. for 2 hours. A 100 nm thick aluminum oxide thin film was formed on the oligosiloxane hybrid coating layer using electron beam deposition. The Ca layer on which the two-layer gas barrier film was formed was exposed to a humid atmosphere having a relative humidity of 100% to measure the change in electrical resistance, and the characteristics of the gas barrier film were evaluated.

<Example 5> Preparation of a four-layer gas barrier film using an oligosiloxane hybrid coating layer and an aluminum oxide layer

After forming a 2 μm thick oligosiloxane hybrid coating layer and a 100 nm thick aluminum oxide thin film on the Ca layer by the method of Example 4, a 2 μm thick oligosiloxane hybrid coating layer and a 100 nm thick aluminum oxide thin film were laminated in the same manner. As shown in FIG. 2, a gas barrier film having a four-layer structure was formed. The Ca layer on which the four-layer gas barrier film was formed was evaluated by measuring the change in electrical resistance by exposing it to a humid atmosphere having a relative humidity of 100%. Table 1 shows the transmittance of moisture. As a result of evaluating the light transmittance in the visible light region of the gas barrier membrane, a transmittance of 85% or more was obtained.

Table 1 Moisture Permeability of Gas Barrier Membrane Using Oligosiloxane Hybrid

From the results of Table 1, it can be seen that the performance of the gas barrier membrane using the oligosiloxane hybrid according to the present invention is very excellent. Polyethylene terephthalate (PET), which is generally used in gas barrier membranes, has a high water permeability of 272 g / m ² per 1 μm per day, indicating that oligosiloxane hybrids have excellent gas barrier properties. Can be. In addition, the oligosiloxane hybrid can be expected to have very good gas barrier properties and a very good gas barrier property of a multilayer gas barrier layer in which an inorganic layer and an inorganic layer are alternately stacked. In addition, since the oligosiloxane hybrid uses a solution process, expensive equipment such as vacuum equipment is not required, and thus it can be expected to form a gas barrier film very cheaply.

1 is an Si-NMR spectrum of an oligosiloxane hybrid prepared by Example 1 of the present invention.

2 shows a laminated structure of a gas barrier film according to Embodiment 5 of the present invention.

<Explanation of symbols for the main parts of the drawings>

10: substrate

20: gas barrier membrane

31, 32: oligosiloxane hybrid coating layer

41, 42: inorganic layer

Claims (16)

a) preparing an oligosiloxane hybrid by a nonaqueous condensation reaction of an organoalkoxysilane represented by the following formula (1) with an organosilanediol represented by the following formula (2); And b) forming a coating layer by coating the coating liquid containing the oligosiloxane hybrid on an element or a substrate requiring gas barrier properties; Gas barrier film comprising an oligosiloxane hybrid coating layer prepared from. [Formula 1]

[In Formula 1, R ¹ is (C ¹ -C 20) alkyl, (C 3 -C 8) cycloalkyl, (C 3 -C 8) alkyl substituted with (C 3 -C 8) cycloalkyl, (C 2 -C 20) alkenyl, (C 2 ~ C20) alkynyl, (C6 ~ C20) aryl is selected from, wherein R ¹ is an acryl group, methacryl group, allyl group, halogen group, amino group, mercapto group, ether group, ester group, (C1-C20) alkoxy May have one or more functional groups selected from groups, sulfone groups, nitro groups, hydroxyl groups, cyclobutene groups, carbonyl groups, carboxyl groups, alkyd groups, urethane groups, vinyl groups, nitrile groups, and epoxy groups; R ² is straight or branched chain (C 1 -C 7) alkyl.] [Formula 2]

[In Formula 2, R ³ and R ⁴ are independently (C 1 -C 20) alkyl, (C 3 -C 8) cycloalkyl, (C 3 -C 8) cycloalkyl substituted with (C 1 -C 20) alkyl, (C 2 -C 20) Alkenyl, (C2-C20) alkynyl, (C6-C20) aryl, wherein R ³ and R ⁴ are an acryl group, methacryl group, allyl group, halogen group, amino group, mercapto group, ether group, ester At least one functional group selected from a group, a (C1-C20) alkoxy group, a sulfone group, a nitro group, a hydroxyl group, a cyclobutene group, a carbonyl group, a carboxyl group, an alkyd group, a urethane group, a vinyl group, a nitrile group, and an epoxy group Can have] delete delete The method of claim 1, The organic alkoxysilane is 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4 Epoxycyclohexyl) ethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, propylethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltri Ethoxysilane, Vinyltripropoxysilane, Phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- (3-acryloxy-2- Hydroxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltripropoxysilane, 3-acryloxypropylmethylbis (trimethoxy) Silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxyprop Tripropoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltripropoxysilane, N- (aminoethyl- 3-aminopropyl) trimethoxysilane, N- (2-aminoethyl-3-aminopropyl) triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, chloropropyltrimeth A gas barrier membrane selected from oxysilane, chloropropyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, or mixtures thereof. The method of claim 1, Wherein said organic silanediol is selected from diphenylsilanediol, diisobutylsilanediol or mixtures thereof. The method of claim 1, Condensation degree of the oligosiloxane hybrid is 60 to 99% gas barrier membrane. The method of claim 1, The condensation reaction is a gas barrier membrane formed under a metal hydroxide catalyst. The method of claim 1, The oligosiloxane hybrid is a gas barrier membrane comprising a functional group capable of thermosetting or ultraviolet curing. The method of claim 8, The gas barrier membrane undergoes thermal curing or photocuring after the coating in step b). The method of claim 1, B) The gas barrier membrane further comprises at least one selected from a solvent, a curing agent, a dye, a pigment, a surfactant, an antioxidant, an oxide or a nitride nanoparticle. The method of claim 1, And forming an inorganic layer selected from an oxide, nitride or oxynitride on the oligosiloxane hybrid coating layer after step b). The method of claim 11, After forming the inorganic layer further comprises the step of laminating at least one layer selected from an oligosiloxane hybrid coating layer and an inorganic layer. The method of claim 1, The gas barrier membrane has a light transmittance of 80 to 95% in the visible light region. The method of claim 1, The substrate is an organic polymer substrate made of polyamide, polyimide, polyethersulfone, polycarbonate, polyetherene naphthalate, polyester, polyethylene terephthalate or mixtures thereof. A substrate for manufacturing an electronic device comprising the gas barrier film of any one of claims 1 and 4 to 14. An organic electronic device comprising the gas barrier film of any one of claims 1 and 4 to 14.

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