KR101489959B1 - Gas barrier film, method for preparing thereof and display display member comprising the same - Google Patents

Abstract

The gas barrier film of the present invention comprises a dry barrier layer; And a wetting barrier layer formed on the dry barrier layer, wherein the wetting barrier layer comprises a hydrogenated polysiloxazane. The gas barrier film has excellent oxygen and water vapor barrier properties by increasing the density of the film through the self-healing effect of penetrating the wet barrier layer between pinholes and cracks to induce covalent bonding. In addition, the gas barrier film provides improved thermal stability, processability, gas permeability, surface hardness, and affinity with the dry barrier layer which is a gas permeable barrier without cracking and deformation.

Description

TECHNICAL FIELD [0001] The present invention relates to a gas barrier film, a method of manufacturing the same, and a display member including the gas barrier film.

The present invention relates to a gas barrier film, a method of manufacturing the same, and a display member comprising the same. More particularly, the present invention relates to a process for forming a wet-type barrier layer comprising a hydrogenated polysiloxazane on a dry-type barrier layer, which penetrates the wet-type barrier layer between pinholes and cracks to increase the density of the film through self- And a display member comprising the gas barrier film.

BACKGROUND ART Conventionally, plate glass has been widely used as a display substrate for an electrode substrate for a liquid crystal display panel, a plasma display, an electroluminescence (EL), a fluorescent display tube, and a light emitting diode. However, the plate glass is prone to breakage, has no bending property, has a large specific gravity, is thin, and has a limited lightness. In order to solve such a problem, a plastic film has attracted attention as a material replacing a plate glass. The plastic film is a lightweight material that is difficult to break and is easily thinned, which is an effective material capable of coping with the increase in the size of a display device.

However, since a plastic film has a high gas permeability as compared with glass, a display device using a plastic film as a substrate has a problem that light emission performance of the display element tends to deteriorate due to permeation of oxygen or water vapor.

Accordingly, attempts have been made to form an organic or inorganic gas barrier film on a plastic film to minimize the influence of oxygen or water vapor. As such a gas barrier film, inorganic materials such as silicon oxide (SiOx), aluminum oxide (AlxOy), tantalum oxide (TAXOy), and titanium oxide (TiOx) are mainly used. These gas barrier thin films are coated on the surface of a plastic film by vacuum deposition or sol-gel method such as plasma enhanced chemical vapor deposition (PECVD), sputtering or the like in a high vacuum state.

The gas barrier thin film may be in the form of a single layer composed of an inorganic material, a two-layer structure of an organic layer and an inorganic layer, a three-layer structure of an organic layer / a clay layer / an organic layer or an inorganic layer / an organic layer / The structure is repeated several times, and the like. In general, more than one inorganic layer exists in the gas barrier thin film. Here, the organic layer serves to prevent the defects of the thin film, which may occur in the inorganic layer, from propagating to the next inorganic layer, rather than the gas barrier property.

Korean Patent No. 2009-0007590 discloses a method for manufacturing a gas barrier film, which comprises providing a dry barrier layer deposited by an inorganic compound on one side of a substrate film, providing a gas barrier layer formed of a polyurethane resin on the dry barrier layer, An overcoat layer formed of a polyester resin and / or a polyacrylic resin is provided. However, in the case of an overcoat layer using such a resin, deformation of the organic substrate and cracking and peeling of the inorganic thin film may occur due to a large difference in linear expansion coefficient between the dry barrier layer and the overcoat layer. Therefore, it is very important to design an appropriate multi-layer structure and adhesion between the coating layers so as to minimize the stress at the interface of each layer. In addition, when the thickness is about 1 탆, the water vapor transmission rate is 0.3 g / m ² / day, which is not suitable for use as a gas barrier film.

In U.S. Patent No. 7,638,925, a multilayered plastic substrate was produced by repeating the process of manufacturing a dry barrier layer by sputtering on an organic layer to show excellent water vapor transmission rate. However, such a multi-layer structure may complicate the process, increase the thickness, and cause cracks due to the difference in thermal expansion coefficient.

Korean Patent No. 2005-0010375 discloses a laminated plastic film and a first organic-inorganic hybrid buffer layer, a gas barrier layer and a second organic-inorganic hybrid buffer layer sequentially laminated on both sides of the bonded plastic film, Layered plastic substrate having a symmetrical structure. However, such a multi-layer structure has disadvantages such as coating and lapping processes.

Japanese Patent Application Laid-Open No. 2011-161891 proposes a polysilazane film having two or more layer structures in order to recover pinholes and cracks in a gas barrier sheet to minimize occurrence of pinholes or cracks passing through all the silica films and deteriorate abrupt gas barrier properties "He said. However, this method can cause cracks due to an increase in thickness as compared with the silazane single layer. It also increases the coating process and is not suitable for use as a gas barrier film with a water vapor transmission rate of 0.5 g / m ² / day.

Thus, in order to overcome the disadvantages of pinholes and cracks, the present invention has been applied to multilayer coating of silazane or vapor deposition and application of an organic layer and an inorganic layer. However, in the above method, deformation of the organic substrate and cracking and peeling of the inorganic thin film may occur due to a large difference in linear expansion coefficient of the dry barrier layer. Therefore, it is very important to design an appropriate multi-layer structure and adhesion between the coating layers so as to minimize the stress at the interface of each layer.

An object of the present invention is to provide a gas barrier film excellent in gas barrier property even with only a single wet-type barrier layer.

Another object of the present invention is to provide a gas barrier film capable of reducing defects such as pinholes and cracks.

Another object of the present invention is to provide a gas barrier film having a wet barrier layer penetrating between pinholes and cracks of the dry barrier layer to increase the density of the film through the self-healing effect and to have excellent oxygen and water vapor barrier properties.

Another object of the present invention is to provide a gas barrier film having a short production time, excellent flexibility and transparency.

Another object of the present invention is to provide a gas barrier film which can prevent cracking and deformation and can provide an affinity with a dry barrier layer which is an improved thermal stability, processability, gas permeability, surface hardness and gas barrier layer will be.

It is still another object of the present invention to provide a process for producing a gas barrier film which is simple in manufacture and can prevent damage to the substrate.

It is still another object of the present invention to provide a display member to which the gas barrier film is applied.

One aspect of the invention relates to a gas barrier film. Wherein the gas barrier film comprises a dry barrier layer; And a wetting barrier layer formed on the dry barrier layer, wherein the wetting barrier layer comprises a hydrogenated polysiloxazane.

The hydrogenated polysiloxazane has a structure represented by the following general formula (3), having a unit represented by the formula (1) and a unit represented by the following formula (2) in the structure:

[Chemical Formula 1]

(2)

(3)

In the general formulas (1) and (2), R1 to R7 each independently represent hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 aryl , A substituted or unsubstituted C3 to C30 arylalkyl group, a substituted or unsubstituted C3 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 heterocycle alkyl group, a substituted or unsubstituted C3 to C30 alkenyl group, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxy group, or combinations thereof.

The hydrogenated polysiloxazane may have an oxygen content of 0.2% to 3% by weight.

The terminal group represented by the formula (3) may be contained in an amount of 15 to 35% by weight based on the total amount of Si-H bonds in the structure.

The hydrogenated polysiloxazane may have a weight average molecular weight (Mw) of 1000 to 5000 g / mol.

The gas barrier film may have a water permeability of 0.0001 to 0.1 g / m ² / day as measured by JIS K7129.

The wet-type barrier layer may have a thickness of 5 nm to 3 탆.

Wherein the dry barrier layer comprises at least one selected from the group consisting of silicon oxide (SiOx), silicon nitride (SiNx), silicon oxynitride (SiOxNy), aluminum oxide (AlxOy), tantalum oxide (TAXOy), titanium oxide .

Another aspect of the present invention relates to a method for producing a gas barrier film. The method comprises coating a coating liquid comprising a hydrogenated polysiloxazane and a solvent on a dry barrier layer to form a coating layer; And curing the coating layer, wherein the coating solution is a hydrogenated polysiloxazane having a unit represented by the formula (1), a unit represented by the following formula (2) and a terminal represented by the following formula (3); And a solvent. ≪ RTI ID = 0.0 >

[Chemical Formula 1]

(2)

(3)

In the general formulas (1) and (2), R1 to R7 each independently represent hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 aryl , A substituted or unsubstituted C3 to C30 arylalkyl group, a substituted or unsubstituted C3 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 heterocycle alkyl group, a substituted or unsubstituted C3 to C30 alkenyl group, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxy group, or combinations thereof.

The thickness of the coating layer may be 5 nm to 3 탆.

The dry barrier layer on which the wet barrier layer is not formed may further include an organic-inorganic hybrid layer.

Another aspect of the present invention relates to a display member comprising the gas barrier film. The display member comprising: a substrate film; And the gas barrier film formed on the base film.

It is an object of the present invention to provide a wet-type barrier layer which is excellent in gas barrier property and can reduce defects such as pinholes and cracks by only a single wet-type barrier layer and permeates the wet-type barrier layer between pinholes and cracks of the dry- A dry barrier layer which is superior in oxygen and water vapor barrier properties, has a short production time, has excellent flexibility and transparency, does not cause cracking and deformation, and has improved thermal stability, processability, gas permeability, surface hardness, And a display member to which the gas barrier film is applied. The present invention also provides a gas barrier film which can be easily manufactured and can prevent damage to a substrate, a method of manufacturing the same, and a display member using the gas barrier film.

1 is a schematic cross-sectional view of a display member to which a gas barrier film according to one embodiment of the present invention is applied.
2 is a schematic cross-sectional view of a display member to which a gas barrier film according to another embodiment of the present invention is applied.

Embodiments of the present application will now be described in more detail with reference to the accompanying drawings. However, the techniques disclosed in this application are not limited to the embodiments described herein but may be embodied in other forms. It should be understood, however, that the embodiments disclosed herein are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, the width, thickness, and the like of the components are enlarged in order to clearly illustrate the components of each device. In addition, although only a part of the components is shown for convenience of explanation, those skilled in the art will be able to easily grasp the rest of the components. It is to be understood that when an element is described as being located on another element, it is meant that the element is directly on top of the other element or that additional elements can be interposed between the elements . It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention. In the drawings, the same reference numerals denote substantially the same elements.

The term " layer formed on a layer "in the present invention is intended to indicate the position of a layer and a layer, and not only that the layer and the layer are directly contacted with each other, .

gas Barrier  film

The gas barrier film of the present invention comprises a dry barrier layer; And a wetting barrier layer formed on the dry barrier layer, wherein the wetting barrier layer comprises a hydrogenated polysiloxazane.

The dry barrier layer may be formed of silicon oxide (SiOx), silicon nitride (SiNx), silicon oxynitride (SiOxNy), aluminum oxide (AlxOy), tantalum oxide (TAXOy), titanium oxide (TiOx) These may be used alone or in combination of two or more.

The dry barrier layer may be formed by a sputtering method, a chemical vapor deposition method, a plasma chemical vapor deposition method, or the like. The dry barrier layer may have a thickness of 5 nm to 1,000 nm, preferably 10 nm to 500 nm, more preferably 20 nm to 300 nm. The light transmittance is excellent in the above range.

Wherein the wetting barrier layer is formed by coating a coating liquid comprising a hydrogenated polysiloxazane and a solvent on the dry barrier layer to form a coating layer; And may be formed by curing the coating layer.

In an embodiment, the coating liquid comprises 0.1 to 50% by weight hydrogenated polysiloxazane; And 50 to 99.9% by weight of a solvent.

The hydrogenated polysiloxazane incorporates silicon-oxygen-silicon (Si-O-Si) bonding units in addition to silicon-nitrogen (Si-N) bonding units in the structure. Such silicon-oxygen-silicon (Si-O-Si) bonding units can reduce shrinkage by relaxing stress during curing.

In an embodiment, the hydrogenated polysiloxazane has a unit represented by the following formula (1), a unit represented by the following formula (2), and a terminal represented by the following formula (3)

[Chemical Formula 1]

(2)

(3)

In the general formulas (1) and (2), R1 to R7 each independently represent hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 aryl , A substituted or unsubstituted C3 to C30 arylalkyl group, a substituted or unsubstituted C3 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 heterocycle alkyl group, a substituted or unsubstituted C3 to C30 alkenyl group, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxy group, or combinations thereof.

The term "substituted" in the present invention means hydrogen, halogen atom, hydroxyl group, nitro group, cyano group, amino group, azido group, amidino group, hydrazino group, carbonyl group, carbamyl group, A carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, an alkyl group having 1-20 carbon atoms, an alkenyl group having 2-20 carbon atoms, an alkynyl group having 2-20 carbon atoms, an alkoxy group having 1-20 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkenyl group having 3 to 30 carbon atoms, a cycloalkynyl group having 3 to 30 carbon atoms, or a combination thereof.

The hydrogenated polysiloxazane may have an oxygen content of 0.2% to 3% by weight. In the case where it is contained in the above range, stress relaxation by the silicon-oxygen-silicon (Si-O-Si) bond in the structure is sufficient to prevent shrinkage during the heat treatment and cracks are formed in the formed gas barrier layer . Preferably, the hydrogenated polysiloxazane has an oxygen content of 0.4 to 2.5% by weight, more preferably 0.5 to 2% by weight.

In addition, the hydrogenated polysiloxazane has a structure in which the terminal portion is capped with hydrogen, and the terminal group represented by Formula 3 may be contained in an amount of 15 to 35% by weight based on the total amount of Si-H bonds in the hydrogenated polysiloxazane structure. When it is included in the above range, the oxidation reaction occurs sufficiently during curing, but SiH 4 portion is prevented from being scattered due to SiH 4 during curing, thereby preventing shrinkage and preventing cracks from being formed in the formed gas barrier layer. Preferably, the terminal group of Formula 3 may be included in an amount of 20 to 30% by weight based on the total amount of Si-H bonds in the hydrogenated polysiloxazane structure.

The hydrogenated polysiloxazane of the present invention may have a weight average molecular weight (Mw) of 1000 to 5000 g / mol. In the case of the above range, a dense gas barrier layer can be formed by thin film coating while reducing the components to be vaporized during the heat treatment. Preferably, the weight average molecular weight (Mw) may be 1500 to 3500 g / mol.

The hydrogenated polysiloxazane may be included in an amount of about 0.1 to 50% by weight based on the total amount of the coating liquid. When it is included in the above-mentioned range, it can maintain an appropriate viscosity and can be formed flat and even without bubbles and voids.

The solvent may be any solvent that is not reactive with the hydrogenated polysiloxazane and is capable of dissolving the hydrogenated polysiloxazane. However, when OH is contained, a solvent containing no -OH group is preferable because it is reactive with the hydrogenated polysiloxazane. Examples of the solvent include hydrocarbon solvents such as aliphatic hydrocarbons, reductive hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers, and alicyclic ethers. Specific examples thereof include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and tallow, halogen hydrocarbons such as methylene chloride and tricholoroethane, ethers such as dibutyl ether, dioxane and tetra- And so on. The solubility of the hydrogenated polysiloxane and the evaporation rate of the solvent may be appropriately selected and a plurality of solvents may be mixed.

The coating liquid is coated and cured on the dry-type barrier layer to form a wet-type barrier layer.

Examples of the method of applying the coating solution to the base film include roll coating, spin coating, dip coating, flow coating, spray coating, and the like, but are not limited thereto .

The thickness of the coating layer may be 5 nm to 3 탆. Preferably 20 to 250 nm. Cracks do not occur in the above range, and the effect of gas barrier property is excellent.

The coating layer thus coated may be cured by ultraviolet irradiation, plasma treatment, heat treatment, or the like. The "curing" process here is the process of changing the hydrogenated polysiloxazane to silica and ceramicizing it.

In one embodiment, the coating layer can be cured by heat treatment. Further, in order to increase the rate of silica change, a method of drying by ultraviolet irradiation, plasma treatment or high humidity may be applied.

In the case of curing by ultraviolet irradiation, the ultraviolet ray irradiation is preferably conducted by a vacuum ultraviolet lamp, and the irradiation intensity is 10 to 200 mW / cm 2, and the irradiation amount is 100 to 6000 mJ / cm 2.

The plasma treatment may be performed at normal pressure or in vacuum, but it is convenient to treat atmospheric pressure in order to continuously treat the plasma treatment and reduce the process cost. In the case of the atmospheric plasma, a method of irradiating the substrate with a nitrogen gas, an oxygen gas, or a mixed gas thereof, preferably oxygen gas, between the two electrodes through a gas, And a method in which plasma is made through gas. As the plasma condition, the gas amount is 0.01 to 100 L / min. The moving speed of the substrate is 0.1 to 1000 m / min. In the case of vacuum plasma, nitrogen gas, oxygen gas or such mixed gas is preferably disposed in an enclosed space maintained at a degree of vacuum of about 20 Pa to 50 Pa by oxygen gas, and electric power such as direct current, alternating current, radio wave, Alternatively, any plasma can be generated by using and applying a waveguide. The output of the plasma treatment is 100W to 5000. The time for the plasma treatment is 1 minute to 30 minutes

In addition, the hydrogenated polysiloxazane can be cured by heat treatment under high humidity and low temperature conditions. In this case, the heat treatment can be performed at a temperature of 40 to 350 DEG C and a relative humidity of 40 to 100%. A sufficient amount of ceramic can be obtained without generating cracks in the above range.

As described above, the wet barrier layer including the hydrogenated polysiloxazane having a reduced thickness on the dry barrier layer may be coated on the dry barrier layer to convert the wet barrier layer into a silica film to enhance the water vapor barrier property. In particular, when the hydrogenated polysiloxazane is applied thinly on the dry barrier layer, the adhesion is improved and the unconverted hydrogenated polysiloxazane inside the cell is self-healing function while controlling the silica conversion rate, thereby improving the crack prevention effect and increasing the density.

In another embodiment of the present invention, the dry barrier layer on which the wet barrier layer is not formed may further include an organic-inorganic hybrid layer on the other surface. In this case, the gas barrier film has a laminated structure in the order of the organic-inorganic hybrid layer / dry barrier layer / wet barrier layer. When the organic-inorganic hybrid layer is sandwiched between the base film and the dry-type barrier layer, cracking and deformation of the film are prevented, and excellent thermal stability, processability, gas permeability, surface hardness and affinity with the gas barrier film are provided do. When the organic-inorganic hybrid layer is interposed between the base film and the dry barrier layer in the buffer layer as described above, cracks, peeling, and discoloration may occur in the substrate process due to the difference in thermal expansion coefficient between the base film and the dry barrier layer. To compensate for or buffer different physical properties between the organic substrate film and the dry barrier.

The organic-inorganic hybrid layer may be formed by blending silica nanoparticles, silica sol, siloxane, silazane, or siloxane with an acrylic compound, or by curing the siloxane, silazane, or siloxane-modified acrylic copolymer . In an embodiment, the organic-inorganic hybrid layer may include a hybrid of an acrylic organic material and silica nanoparticles, silica sol, siloxane, silazane, or siloxane. In addition, urethane hybrid polysilazane, urethane hybrid polysiloxazane, urethane hybrid polysiloxane, and the like can be applied as the organic-inorganic hybrid layer. The double urethane hybrid polysilazane is preferable in terms of preventing cracking and deformation of the barrier film and improving the affinity with the dry barrier layer which is an improved thermal stability, processability, gas permeability, surface hardness and gas permeation barrier.

The above-mentioned curing method can be preferably applied with the uv curing method in consideration of the influence on the substrate located below.

The thickness of the organic-inorganic hybrid layer may be 5 占 퐉 or less, for example, in the range of 1 to 3 占 퐉. Cracks and deformation in the above range are prevented, and the processability, gas permeability, surface hardness and affinity with the gas permeable barrier film are excellent.

The gas barrier film has a water permeability of 0.0001 to 0.1 g / m ² / day, preferably 0.0001 to 0.08 g / m ² / day, more preferably 0.0001 to 0.03 g / m ² / day as measured by JIS K7129 Lt; / RTI >

Further, the gas barrier film formed with the wet-type barrier layer can be improved in pinholes or cracks in the grain boundary of the dry-type barrier layer due to the self-healing effect of the wet-type barrier layer.

Absence of display

The display member of the present invention comprises the gas barrier film.

1 is a schematic cross-sectional view of a display member to which a gas barrier film according to one embodiment of the present invention is applied. As shown, the display member 100 of the present invention comprises a base film 10; And a gas barrier film (20) of the present invention laminated on at least one side of the base film. Although the gas barrier film 20 is laminated on one side of the base film 10 in the figure, it may be laminated on both sides of the base film 10. A dry barrier layer 21 of the gas barrier film 20 is laminated on a base film and a wet barrier layer 22 is formed on the dry barrier layer 21. Although not shown, the base film may be coated with a planarization layer or a buffer layer.

2 is a schematic cross-sectional view of a display member to which a gas barrier film according to another embodiment of the present invention is applied. As shown, the display member 300 includes a base film 10; And a gas barrier film (20) of the present invention laminated on at least one side of the substrate film, wherein an organic-inorganic hybrid layer (23), a dry barrier layer (21) and a wet barrier layer (22) may be sequentially stacked. Although the gas barrier film 20 is laminated on one side of the base film 10 in the figure, it may be laminated on both sides of the base film 10.

In this case, the organic-inorganic hybrid layer 23 serves as a buffer layer between the organic base film 10 and the inorganic dry barrier layer 21. As described above, when the organic-inorganic hybrid layer 23 is formed between the base film 10 and the dry barrier layer 21, cracking and deformation of the film are prevented, and thermal stability, processability, gas permeability, surface hardness, Thereby providing affinity for the blocking film. The thickness of the organic-inorganic hybrid layer 23 may be 5 占 퐉 or less, for example, in the range of 1 to 3 占 퐉. In the above range, cracks and deformation are prevented, the thermal stability is excellent, and the processability, gas permeability, surface hardness and affinity with the gas permeable barrier film are excellent.

The base film 10 is not particularly limited, but preferably a high heat-resistant plastic film having excellent heat resistance and a low coefficient of thermal expansion can be used. For example, it may be at least one selected from the group consisting of polyethersulfone, polycarbonate, polyimide, polyetherimide, polyacrylate, polyethylene naphthalate and polyester film, but is not limited thereto.

The thickness of the base film 10 may be 20-150 占 퐉, preferably 70-100 占 퐉. Within the above range, the base film of the gas barrier film may have excellent mechanical strength, flexibility, transparency, heat resistance and the like.

The base film 10 may further include an inorganic filler. As the inorganic filler, for example, at least one particle or glass cloth selected from the group consisting of silica, plate-shaped or spherical glass flake and nano-clay may be used. The coefficient of thermal expansion (CTE) of the base film may be 1-100 ppm / 占 폚.

The gas barrier film of the present invention is excellent in gas barrier property, so that the conventional multilayer gas barrier layer can be realized by only a single wet barrier layer.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. However, the following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited to the following examples. The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Example

Specific specifications of the components used in the following examples and comparative examples are as follows.

Preparation Example 1: Preparation of wet barrier coating liquid

The inside of the 2 L reactor equipped with the stirring device and the temperature control device was replaced with dry nitrogen. Then, 2.0 g of pure water was poured into 1,500 g of dry pyridine, and the mixture was thoroughly mixed. The mixture was placed in a reactor and kept at 5 ° C. Subsequently, 100 g of dichlorosilane was slowly added thereto over a period of 1 hour. Then, 70 g of ammonia was slowly added thereto over 3 hours while stirring. Then, dry nitrogen was injected for 30 minutes to remove ammonia remaining in the reactor. The obtained white slurry-like product was filtered using a 1 m-thick Teflon filter in a dry nitrogen atmosphere to obtain 1,000 g of a filtrate. 1,000 g of dry xylene was added thereto, and the operation of replacing the solvent with xylene in pyridine using a rotary evaporator was repeated three times in total to adjust the solid content concentration to 20%. Finally, the pore size of 0.03 mu m Filtered through a Teflon filter. The hydrogenated polysiloxazane thus obtained was measured for oxygen content by using FlashEA 1112 (manufactured by Thermo Fisher Scientific Inc.) at 0.5%, SiH 3 / SiH (total ) Was 0.20, and the weight average molecular weight measured by GPC (HPLC Pump 1515, RI Detector 2414 (manufactured by Waters Corporation) and Colum: KF801, KF802, and KF803 (manufactured by Shodex) was 2,000 g / mol.

Example  One

The coating solution of Preparation Example 1 was spin-coated to a thickness of 170 nm on a PET film (manufactured by Cheil Industries) on which SiOx and SiNx were deposited to a thickness of 100 nm. Thereafter, the resultant was dried at 80 ° C for 3 minutes, irradiated at 1500 mJ / cm ² using a Low Pressure UV Lamp, and dried at room temperature for 1 day.

Example  2

The procedure of Example 1 was repeated except that the coating layer thickness was changed to 510 nm.

Example  3

A mixed solution of 60% by weight of hybrid polysilazane (manufactured by Clariant, product name: HSU 200S) and 40% by weight of butyl acetate (manufactured by Seonjeon Pharm) as a coating solution for buffer layer was spin-coated on a 125 탆 PEN film (TEONEX PQDA5, manufactured by Teijin Dupont) Respectively. Spin Coating was coated at 1000 rpm for 20 seconds and dried at 80 ° C for 3 minutes in a convection oven. Spin coating was again applied at 1000 rpm for 20 seconds and dried at 80 ° C for 3 minutes in a convection oven. In the same manner, a total of 5 times of spin coating was performed, and the film was dried at 80 ° C. for 3 minutes in a convection oven to form a film having a thickness of 1 μm to 3 μm. Then, it was irradiated with 2000 mJ / cm ² in a UV irradiator and dried in convection oven at 120 ° C for 1 hour. Next, in order to form a vapor-deposited film, a silicon oxynitride was placed in a chamber as a target by placing it in a chamber of a batch-type sputtering apparatus. The distance between the silicon oxynitride and the acrylic resin layer was set at 50 mm. Oxygen and argon were used as additive gases at the time of film formation. The chamber was evacuated to a vacuum of 2.5 x 10 < ^-4 > Pa, oxygen gas was introduced into the chamber at a flow rate of 10 sccm (standard cubic centimeter per minute), argon gas was introduced at a flow rate of 30 sccm, and RF magnetron sputtering ) A dry barrier layer, which is a silicon oxynitride film with a thickness of 100 nm, was formed on the acrylic resin layer.

The coating solution of Preparation Example 1 was spin-coated on the dry barrier layer to a thickness of 510 nm. Thereafter, the resultant was dried at 80 ° C for 3 minutes, irradiated at 1500 mJ / cm ² using a Low Pressure UV Lamp, and dried at room temperature for 1 day.

Example  4

Except that a mixed solution of 60% by weight of a hybrid polysilazane (manufactured by Clariant, product name: HSU 300B) and 40% by weight of butyl acetate (manufactured by Seonjeon) was used as a coating solution for a buffer layer.

Comparative Example  One

To a 10 L four-necked flask equipped with a polysiloxane (a mechanical stirrer, a cooling tube, a dropping funnel, and a nitrogen gas inlet tube) was charged 2100 g of methyltrimethoxysilane to a PET film (manufactured by Cheil Industries) deposited with SiOx and SiNx to a thickness of 100 nm And phenyltrimethoxysilane (340 g) were dissolved in 5600 g of PGMEA. Then, 925 g of a 1000 ppm nitric acid aqueous solution was added to the solution. After reacting at 60 ° C for 1 hour, methanol and methanol The reaction was allowed to proceed for one week while maintaining the reaction temperature at 50 ° C. After the reaction, an appropriate amount of hexanes was added to the resulting solid to separate a polymer having Mw = 15K and polydispersity = 1.50 10 g of this solid was dissolved in 100 g of PGMEA and 100 g of ethyl lactate to prepare a solution) was spin-coated to a thickness of 170 nm. The subsequent steps were carried out in the same manner as in Example 1 above.

Comparative Example  2

A mixed solution of 60% by weight of hybrid polysilazane (manufactured by Clariant, product name: HSU 200S) and 40% by weight of butyl acetate (manufactured by Seonjeon Pharm) as a coating solution for buffer layer was spin-coated on a 125 탆 PEN film (TEONEX PQDA5, manufactured by Teijin Dupont) Respectively. Spin Coating was coated at 1000 rpm for 20 seconds and dried at 80 ° C for 3 minutes in a convection oven. Spin coating was again applied at 1000 rpm for 20 seconds and dried at 80 ° C for 3 minutes in a convection oven. In the same manner, a total of 5 times of spin coating was performed, and the film was dried at 80 ° C. for 3 minutes in a convection oven to form a film having a thickness of 1 μm to 3 μm. Then, it was irradiated with 2000 mJ / cm ² in a UV irradiator and dried in convection oven at 120 ° C for 1 hour. Next, in order to form a vapor-deposited film, a silicon oxynitride was placed in a chamber as a target by placing it in a chamber of a batch-type sputtering apparatus. The distance between the silicon oxynitride and the acrylic resin layer was set at 50 mm. Oxygen and argon were used as additive gases at the time of film formation. The chamber was evacuated to a vacuum of 2.5 x 10 < ^-4 > Pa, oxygen gas was introduced into the chamber at a flow rate of 10 sccm (standard cubic centimeter per minute), argon gas was introduced at a flow rate of 30 sccm, and RF magnetron sputtering ) On the acrylic resin layer, a dry barrier layer as a silicon oxynitride film having a thickness of 100 nm was formed.

Comparative Example  3

10.0 parts of a polyepoxy resin coating agent (MEXUSB M-100 (main product) manufactured by Mitsubishi Gas Co., Ltd., M-93 (hardening agent)), , 99.2 parts of methanol and 12.2 parts of ethyl acetate were stirred for 30 minutes to prepare a coating liquid 1 having a solid content concentration of 20% by weight using a wire bar, followed by drying at 140 ° C for 30 seconds to form a coating having a thickness of 0.8 μm . Thereafter, the substrate was dried at 80 ° C for 3 minutes, thermally cured at 150 ° C for 10 minutes to form a first wet-type barrier layer, and then a polyester-based resin coating agent (polyester-based coating agent manufactured by Tanaka Chemical Co., 10 parts of Resin Coating Agent No. 8800 and 18 parts of methyl ethyl ketone were stirred for 30 minutes to apply a coating solution 2) having a solid concentration of 10% by weight to the wire immediately and dried at 140 占 폚 for 30 seconds to form a coating layer To form a second wet-barrier layer.

Comparative Example  4

(Polyester tetraacrylate resin) was weighed into a three-necked glass flask, and a solution of methyl methacrylate (methyl (meth) acrylate) was added to a PET film (manufactured by Cheil Industries) having SiOx and SiNx deposited to a thickness of 100 nm Methacrylate was added to the resin in an amount of 20 to 50% by weight and stirred, and ethanol was added in an amount of 5 to 10% by weight of the polymer, and the mixture was stirred while the resin was completely dissolved. The starting solution of the polymer was prepared by adding ethyl methacrylate or isobutyl acrylate to the resin in an amount of 10 to 20% by weight and stirring the solution. To the prepared polymer starting solution, tetraethyl silicate ( tetraethyl-silicate) alkoxide is added in an amount of 5 to 20% by weight based on the polymer content, tetraethyl silicate The hydrolysis was carried out by slowly adding distilled water corresponding to 10 times molar amount to tetraethyl silicate for hydrolysis. The organic polymer and inorganic The solution mixed with tetraethyl silicate is not mixed with each other, and polyoxyethylene nonylphenyl ether as a surfactant is added in an amount of 1 to 5% by weight based on the total weight of the solution for hybridization. , 5 to 10% by weight based on the total weight of tetramethylethylsilane as a binder for the binder, and stirring was continued until the solution became transparent. When the solution became transparent, AIBN (α, α'-azobisisobutyronitrile) 0.8% by weight based on the total weight of the polyether-modified polydimethylsiloxane, and the mixture was stirred until completely dissolved. The hybrid inorganic / organic hybrid coating was completed by adding 3% by weight of the total ceramic alumina nanoparticles having a size of 20 nm) to a thickness of 3 μm to form a wire bar And dried at 80 DEG C for 1 hour to form a hybrid layer.

Comparative Example  5

10.0 parts of a polyepoxy resin coating agent Makushib M-100 (main product), 32.1 parts of M-93 (curing agent), and 99.2 parts of a methanol-based resin coating agent (manufactured by Mitsubishi Gas Corporation) were added to a PEN film (TEONEX PQDA5, Teijin Dupont) And 12.2 parts of ethyl acetate were stirred for 30 minutes to obtain a wet barrier coating solution 1) having a solid content concentration of 20% by weight. The wet barrier coating solution 1 was applied using a wire bar and dried at 140 ° C for 30 seconds to form a 0.8 μm thick layer. Thereafter, the resultant was dried at 80 DEG C for 3 minutes, and thermally cured at 150 DEG C for 10 minutes to form a wet-type barrier layer. Next, in order to form a vapor-deposited film, a silicon oxynitride was placed in a chamber as a target by placing it in a chamber of a batch-type sputtering apparatus. The distance between the silicon oxynitride and the acrylic resin layer was set at 50 mm. Oxygen and argon were used as additive gases at the time of film formation. The chamber was evacuated to a vacuum of 2.5 x 10 < ^-4 > Pa, oxygen gas was introduced into the chamber at a flow rate of 10 sccm (standard cubic centimeter per minute), argon gas was introduced at a flow rate of 30 sccm, and RF magnetron sputtering ) On the acrylic resin layer, a dry barrier layer as a silicon oxynitride film having a thickness of 100 nm was formed. This was repeatedly performed to form a structure in which a wet barrier layer-dry barrier layer-wet barrier layer-dry barrier layer-wet barrier layer were sequentially laminated.

Comparative Example  6

The coating solution of Preparation Example 1 was spin-coated on the PET film (A4300, manufactured by Toyobo) to a thickness of 240 nm. Thereafter, the substrate was dried at 80 DEG C for 3 minutes, and then again coated to a thickness of 240 nm. Irradiated at 1500 mJ / cm ² using a low-pressure UV lamp, and dried at room temperature for 1 day.

The properties of the display members prepared in the above Examples and Comparative Examples were measured according to the following criteria, and the results are shown in Table 1 below.

How to measure property

1. Water Transmittance (WVTR): A water vapor permeability transmittance measurement apparatus (model name, Pharmatran (registered trademark) W3 / 31) manufactured by MOCON CORPORATION was used under the conditions of a temperature of 40 DEG C and a humidity of 90% Was measured based on the B method (infrared sensor method) described in JIS K7129 (2000 edition). However, the number of test pieces was two for each of the examples and comparative examples. The average value of the measured values obtained by each test piece was regarded as the water vapor permeability in each of the Examples and Comparative Examples.

2. Crack: Confirm the fracture of the coating layer of the specimen with an optical microscope.

The evaluation was carried out in three stages as described below, and the evaluation results are shown in the table.

(1) Excellent (indicated by "○" in the table): The cracked portion of the coating layer is not seen.

(2) Usually (marked with "?" In the table): a crack is seen in a part of the coating layer.

(3) Poor (Marked with "x" in the table): The cracks are seen in the entire coating layer.

3. Appearance: The naked eye was inspected to see if any change in appearance or delamination was observed.

The evaluation was carried out in three stages as described below, and the evaluation results are shown in the table.

(1) Excellent (Marked with "○" in the table): Appearance defects such as whiteness and delamination were not observed on the coated surface.

(2) Normally (marked with "?" In the table): Appearance defects such as whitening on the coated surface and delamination were observed in a part (area).

(3) Inferiority (indicated by "x" in the table): Appearance defects such as whitening and delamination on the coated surface were observed over the entire area.

4. Initial warpage: The prepared film was placed on a flat surface of 100 mm x 100 mm, and the height of the lowest point and the highest point were measured to measure the warped peak height. "Good" when the maximum height is less than 5 mm, and "Bad"

division The buffer layer or the wet- deflation
Barrier layer Wet
Barrier layer deflation
Barrier layer Wet
Barrier layer vapor
Transmittance
(g / m ² / day) crack Exterior Initial bending Example 1 - SiOxNy
100 nm Hydrogenated polysiloxazane
170 nm - - ≤0.005 ○ ○ Good Example 2 - SiOxNy
100 nm Hydrogenated polysiloxazane
510 nm - - 0.01 ○ ○ Good Example 3 HSU 200S
1.2 탆 SiOxNy
100 nm Hydrogenated polysiloxazane
510 nm - - ≤0.005 ○ ○ Good Example 4 HSU 300B
1.2 탆 SiOxNy
100 nm Hydrogenated polysiloxazane
510 nm - - ≤0.005 ○ △ Good Comparative Example 1 - SiOxNy
100 nm Polysiloxane
170 nm - - 1.2 × ○ Good Comparative Example 2 HSU 200S
3 탆 SiOxNy
100 nm - - - 0.3 × ○ Good Comparative Example 3 - SiOxNy
100 nm Polyepoxy system
0.8 탆 - Polyester-based
0.6 탆 0.3 △ ○ Bad Comparative Example 4 - SiOxNy
100 nm Sol-gel organic hybrid layer
3 탆 - - 0.8 △ △ Bad Comparative Example 5 Polyepoxy system
0.8 탆 SiOxNy
100 nm Polyepoxy system
0.8 탆 SiOxNy
100 nm Polyepoxy system
0.8 탆 ≤0.005 × ○ Bad Comparative Example 6 - - Hydrogenated polysiloxazane
240 nm - Hydrogenated polysiloxazane
240 nm 3.8 △ ○ Good

As shown in Table 1, it can be seen that the gas barrier films of Examples 1 to 4 have excellent gas barrier properties, no cracks, and excellent appearance. On the other hand, in Comparative Examples 1 to 4 and 6, the water vapor permeability was not good as compared with the examples, and cracks and appearance were deteriorated in some cases. Comparative Example 5 exhibited excellent gas barrier property but had an initial warpage and had a complicated coating process. Comparative Example 6 shows that when the wet-type barrier layer is coated with two layers without the dry-type barrier layer, the dry-type barrier layer and the gas-barrier property are degraded without the self-healing effect. It can be seen that Example 1 has an excellent barrier film characteristic without causing cracks due to an increase in thickness by coating an ultra-thin wet-type barrier layer. In Example 2, the thickness of the wet-type barrier layer increases, and the crack is slightly reduced. Examples 3 to 4 are examples in which a buffer layer capable of complementing and buffering different physical properties is formed in order to reduce the stress between the interface of the base film and the dry barrier layer due to the difference in elastic modulus and thermal expansion coefficient, And the gas barrier property is also excellent. It is also seen that cracks do not occur even when the thickness increases.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

10: substrate film 20: gas barrier film
21: dry barrier layer 22: wet barrier layer
23: Organic-inorganic hybrid layer
100, 300: display member

Claims (12)

A dry barrier layer; And
A wet barrier layer formed on the dry barrier layer;
Wherein the wet barrier layer comprises a hydrogenated polysiloxazane,
Wherein the hydrogenated polysiloxazane has, in its structure, a unit represented by the formula (1) and a unit represented by the following formula (2) and having a terminal group represented by the following formula (3)
[Chemical Formula 1]

(2)

(3)

In the general formulas (1) and (2), R1 to R7 each independently represent hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 aryl , A substituted or unsubstituted C3 to C30 arylalkyl group, a substituted or unsubstituted C3 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 heterocycle alkyl group, a substituted or unsubstituted C3 to C30 alkenyl group, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxy group, or combinations thereof.

delete The gas barrier film of claim 1, wherein the hydrogenated polysiloxazane has an oxygen content of 0.2% to 3% by weight.
The gas barrier film according to claim 1, wherein the terminal group represented by the formula (3) is contained in an amount of 15 to 35% by weight based on the total amount of Si-H bonds in the structure.
The gas barrier film of claim 1, wherein the hydrogenated polysiloxazane has a weight average molecular weight (Mw) of 1000 to 5000 g / mol.
The gas barrier film according to claim 1, wherein the gas barrier film has a water permeability measured by JIS K7129 of 0.0001 to 0.1 g / m ² / day.
The gas barrier film of claim 1, wherein the wet-type barrier layer has a thickness of 5 nm to 3 μm.
The dry barrier layer of claim 1, wherein the dry barrier layer comprises a material selected from the group consisting of silicon oxide (SiOx), silicon nitride (SiNx), silicon oxynitride (SiOxNy), aluminum oxide (AlxOy), tantalum oxide (TAxOy), and titanium oxide ≪ / RTI >
The gas barrier film of claim 1, wherein the dry barrier layer on which the wet-type barrier layer is not formed comprises an organic-inorganic hybrid layer on the other surface.
Coating a coating liquid containing a hydrogenated polysiloxazane and a solvent on the dry-type barrier layer to form a coating layer; And
Curing the coating layer;
Wherein the coating solution comprises a hydrogenated polysiloxazane having a unit represented by the formula (1), a unit represented by the following formula (2) and a terminal represented by the following formula (3); And a solvent. The method for producing a gas barrier film according to claim 1,
[Chemical Formula 1]

(2)

(3)

In the general formulas (1) and (2), R1 to R7 each independently represent hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 aryl , A substituted or unsubstituted C3 to C30 arylalkyl group, a substituted or unsubstituted C3 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 heterocycle alkyl group, a substituted or unsubstituted C3 to C30 alkenyl group, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxy group, or combinations thereof.
11. The method of claim 10, wherein the thickness of the coating layer is from 5 nm to 3 占 퐉.
A base film; And
9. A display member comprising the gas barrier film according to any one of claims 1 to 9 formed on the base film.

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